CN115417972A - Aromatic waterborne polyurethane resin and preparation method thereof - Google Patents
Aromatic waterborne polyurethane resin and preparation method thereof Download PDFInfo
- Publication number
- CN115417972A CN115417972A CN202211228101.5A CN202211228101A CN115417972A CN 115417972 A CN115417972 A CN 115417972A CN 202211228101 A CN202211228101 A CN 202211228101A CN 115417972 A CN115417972 A CN 115417972A
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- Prior art keywords
- stirring
- parts
- polyurethane resin
- aromatic
- reaction
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 44
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000003756 stirring Methods 0.000 claims abstract description 53
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 40
- 229920000570 polyether Polymers 0.000 claims abstract description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000004383 yellowing Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 24
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 150000003077 polyols Chemical class 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims abstract description 15
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 15
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 aromatic isocyanate Chemical class 0.000 claims abstract description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 230000003449 preventive effect Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 42
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000013067 intermediate product Substances 0.000 claims description 12
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 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 7
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 7
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002649 leather substitute Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- YNBCPPPGORNBRW-UHFFFAOYSA-N 1-benzyl-2,4-diisocyanatobenzene Chemical compound O=C=NC1=CC(N=C=O)=CC=C1CC1=CC=CC=C1 YNBCPPPGORNBRW-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 2
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- 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
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to an aromatic waterborne polyurethane resin and a preparation method thereof, belonging to the technical field of waterborne polyurethane resin preparation, and the preparation steps are as follows: the preparation method comprises the steps of dehydrating fluorine-containing polyether polyol, adding aromatic isocyanate, introducing nitrogen, heating to 88-90 ℃, keeping the temperature, stirring, reacting for 2 hours, cooling to 50 ℃, adding acetone, a yellowing-resistant auxiliary agent, a catalyst, dimethylolpropionic acid, trimethylolpropane and methyl propylene glycol, heating to 55 ℃, stirring, reacting for 4-5 hours, adding epoxy resin, stirring, adding triethylamine, distilling under reduced pressure to remove acetone, cooling to 45 ℃, adding water and a mildew preventive, and stirring to obtain the aromatic waterborne polyurethane resin.
Description
Technical Field
The invention belongs to the technical field of preparation of waterborne polyurethane resin, and particularly relates to aromatic waterborne polyurethane resin and a preparation method thereof.
Background
Along with the enhancement of environmental awareness of people, the waterborne polyurethane resin is more and more popular, the waterborne polyurethane resin is mostly prepared from aliphatic isocyanate and polyalcohol, the method has the advantages that the process is simple, the reaction is easy to control, the quality is stable, the yellowing resistance of products is good, but the cost of the products is high due to the high price of the aliphatic isocyanate, the polyurethane resin used for the synthetic leather is aromatic waterborne polyurethane resin and is prepared from aromatic isocyanate, the wear resistance and the solvent resistance of the products are high, but the aromatic isocyanate contains benzene rings, the benzene rings are easy to isomerize under the irradiation of ultraviolet light to form a quinoid structure to yellow, meanwhile, the synthetic leather also can absorb moisture in the air, the degradation and isomerization of the polyurethane resin are accelerated under the action of ultraviolet light, so that the polyurethane resin is easier to yellow, in order to overcome the factor, an ultraviolet absorbent is often added into the aromatic waterborne polyurethane resin, but the ultraviolet absorbent is easy to migrate, separate out and has limited yellowing effect, and the problem that the aromatic polyurethane resin is accelerated by water cannot be improved is provided, and therefore, the technical problem of yellowing resistance and good yellowing of the waterborne polyurethane resin is needed to be solved at present.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention provides an aromatic waterborne polyurethane resin and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
an aromatic waterborne polyurethane resin comprises the following raw materials in parts by weight: 400-450 parts of fluorine-containing polyether polyol, 200-250 parts of aromatic isocyanate, 0.4-0.5 part of catalyst, 24-28 parts of dimethylolpropionic acid, 1 part of trimethylolpropane, 30.2-35.2 parts of methyl propylene glycol, 200-250 parts of acetone, 4-5 parts of epoxy resin, 18-19.5 parts of triethylamine, 8-10 parts of KH-550 silane coupling agent, 800-840 parts of water, 12-15 parts of yellowing-resistant auxiliary agent and 4-5 parts of mildew preventive;
the aromatic waterborne polyurethane resin is prepared by the following steps:
dehydrating fluorine-containing polyether polyol in a reaction kettle in vacuum at 110 ℃ for 0.5h, then cooling to 60 ℃, adding aromatic isocyanate, charging nitrogen, heating to 88-90 ℃, keeping the temperature, stirring for reaction for 2h, cooling to 50 ℃, adding acetone, a yellowing-resistant auxiliary agent, a KH-550 silane coupling agent, a catalyst, dimethylolpropionic acid, trimethylolpropane and methyl propylene glycol, heating to 55 ℃, stirring for reaction for 4-5h, adding epoxy resin, stirring for 1-2min, adding triethylamine, stirring for 1min, carrying out reduced pressure distillation to remove acetone, cooling to 45 ℃, adding water and a mildew preventive, and stirring for 10-15min to obtain the aromatic waterborne polyurethane resin.
Further, the fluorine-containing polyether polyol is prepared by the following steps:
adding hexafluorobisphenol A and a double metal cyanide complex catalyst (DMC catalyst) into a reaction kettle, replacing the air in the kettle with nitrogen, vacuumizing, heating to 130 ℃, keeping the temperature for 1h, dropwise adding propylene oxide under a negative pressure state, then raising the pressure in the kettle to 0.1-0.15MPa, carrying out an induction reaction at the temperature of 130-150 ℃ for 10-15min, after the induction reaction is finished, dropwise adding propylene oxide again, controlling the dropwise adding speed to be 1-2 drops/second, after the dropwise adding is finished, keeping the temperature for reaction for 1h at 135 ℃, vacuumizing, cooling to 90 ℃, adding a polyether antioxidant, and uniformly stirring to obtain the fluorine-containing polyether polyol;
wherein the mass ratio of the hexafluorobisphenol A to the propylene oxide is 0.5:10-11.5, wherein the mass ratio of the first propylene oxide to the second propylene oxide is 15-18: 82-85%, the dosage of the double metal cyanide complex catalyst is 0.035-0.05% of the mass sum of the hexafluorobisphenol A and the propylene oxide, the polyether antioxidant is 0.15-0.5% of the mass sum of the hexafluorobisphenol A and the propylene oxide, the polyether antioxidant is purchased from Shanghai Qike fluorosilicon materials Co., ltd, and is selected from one or more of Chic PU 3325 polyether antioxidant, chic PU 5057 polyether antioxidant and Chic PU 3318 polyether antioxidant to be mixed according to any proportion, the hexafluorobisphenol A is used as an initiator, the double metal cyanide complex catalyst catalyzes the ring-opening polymerization of the propylene oxide to obtain the fluorine-containing polyether polyol, the covalent bond energy of C-F in the fluorine-containing polyether polyol is higher and is close to the light wave with the maximum ultraviolet light energy, therefore, the damage possibility of the C-F bond in the visible ultraviolet light wave range is extremely low, the C-F bond with high bond energy is introduced, and the C-C bond with low bond energy is protected, and the ultraviolet resistance of the product is improved.
Further, the yellowing resistant auxiliary agent is prepared by the following steps:
step S1, adding cyanuric chloride and acetone into a three-neck flask, stirring for 20min at 0 ℃, then dropwise adding a DMF (dimethyl formamide) solution of 4-nitrophenol, controlling the dropwise adding speed to be 1-2 drops/second, after the dropwise adding is finished, adjusting the pH to be 5-6, stirring and reacting at 0-5 ℃ until the pH value of the system does not change, heating to 10 ℃, dropwise adding a DMF solution of 2, 4-dihydroxybenzophenone, after the dropwise adding is finished, heating to 35-40 ℃, adjusting the pH to be 6-7, stirring and reacting until the pH value does not change, continuously heating to 60-70 ℃, adding 2, 6-tetramethylpiperidine amine, slowly evaporating acetone, adjusting the pH value of the system to be neutral, heating to 85-90 ℃, stirring and reacting until the pH value of the system does not change, cooling to room temperature, pouring a reaction product into acetone, carrying out vacuum constant pressure filtration, repeatedly washing a filter cake with acetone, and drying at 60 ℃ to be dry to obtain an intermediate product;
wherein, the pH value is adjusted by using 10 percent by mass of sodium hydroxide aqueous solution, and the molar ratio of cyanuric chloride, 4-nitrophenol, 2, 4-dihydroxy benzophenone and 2, 6-tetramethyl piperidine amine is 1:1:1:1, cyanuric chloride, 4-nitrophenol, 2, 4-dihydroxy benzophenone and 2, 6-tetramethyl piperidine amine are subjected to HCl elimination reaction to obtain an intermediate product;
step S2, adding the intermediate product, absolute ethyl alcohol and ethyl acetate into a reaction kettle, starting stirring, adding a palladium-carbon hydrogenation catalyst, heating until reflux, dropwise adding a hydrazine hydrate solution with the mass concentration of 85%, after dropwise adding, carrying out reflux reaction for 5-6 hours, filtering while hot, collecting filtrate, cooling to room temperature, carrying out suction filtration, washing a filter cake with deionized water, and drying at 100 ℃ to constant weight to obtain a yellowing-resistant auxiliary agent;
wherein the mass ratio of the intermediate product, the absolute ethyl alcohol, the ethyl acetate, the palladium-carbon hydrogenation catalyst and the 85% hydrazine hydrate solution is 10.5-11.6:26-30:4-6:0.4:4.3-4.8, reducing the nitro group in the intermediate product into amino group under the action of palladium-carbon hydrogenation catalyst and hydrazine hydrate, and obtaining the yellowing-resistant auxiliary agent.
Further, the aromatic isocyanate is one or more of tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate mixed in an arbitrary ratio.
Further, the catalyst is stannous octoate or dibutyltin dilaurate.
Further, the epoxy resin is epoxy resin E-51.
Further, the mildew inhibitor is one or the combination of two of cason and tributyltin chloride.
The invention has the beneficial effects that:
1. the aromatic waterborne polyurethane resin provided by the invention has excellent mechanical properties and high yellowing resistance, and the polyurethane resin is modified by the epoxy resin, so that the cohesive force of polyurethane molecules is effectively improved, the adhesive force of a product is increased, and the heat resistance of the product is improved by networking the polyurethane molecules through crosslinking.
2. The fluorine-containing polyether polyol is introduced into the waterborne polyurethane resin, the fluorine-containing polyether polyol not only contains a plurality of C-F bonds, but also contains a rigid benzene ring structure, the existence of the rigid benzene ring and the epoxy resin play a synergistic effect, and the heat resistance of the product is improved.
3. In order to further enhance the yellowing resistance of the product, the yellowing resistance auxiliary agent is introduced, contains a benzophenone structure, a hindered amine structure and active amino, can improve the yellowing resistance of the product in the aspects of absorbing ultraviolet rays and capturing photo-aging free radicals, can participate in polyurethane curing reaction, introduces the benzophenone structure and the hindered amine structure into the product through chemical bonds, and overcomes the problems of easy migration and precipitation of the traditional yellowing resistance agent.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The double metal cyanide complex catalyst in the examples was purchased from Huaian Bade polyurethane technology, inc.
Example 1
A fluorine-containing polyether polyol is prepared by the following steps:
adding 0.5g of hexafluorobisphenol A and double metal cyanide complex catalyst into a reaction kettle, replacing the air in the kettle with nitrogen, vacuumizing, heating to 130 ℃, keeping the temperature for 1h, dropwise adding 1.5g of alkylene oxide under the negative pressure state, then raising the pressure in the kettle to 0.1MPa, carrying out an induction reaction at the temperature of 130 ℃ for 10min, after the induction reaction is finished, dropwise adding 8.5g of propylene oxide again, controlling the dropwise adding speed to be 1 drop/second, after the dropwise adding is finished, keeping the temperature for reaction for 1h at 135 ℃, vacuumizing, cooling to 90 ℃, adding a polyether antioxidant, and uniformly stirring to obtain the fluorine-containing polyether polyol, wherein the dosage of the double metal cyanide complex catalyst is 0.035% of the sum of the mass of the hexafluorobisphenol A and the mass of the propylene oxide, the polyether antioxidant is 0.15% of the sum of the mass of the hexafluorobisphenol A and the propylene oxide, and the polyether antioxidant is Chic PU 3325 polyether antioxidant.
Example 2
A fluorine-containing polyether polyol is prepared by the following steps:
adding 0.5g of hexafluorobisphenol A and double metal cyanide complex catalyst into a reaction kettle, replacing the air in the kettle with nitrogen, vacuumizing, heating to 130 ℃, keeping the temperature for 1h, dropwise adding 2.07g of epoxypropane under a negative pressure state, then raising the pressure in the kettle to 0.15MPa, carrying out an induction reaction at the temperature of 150 ℃ for 15min, after the induction reaction is finished, dropwise adding 9.43g of epoxypropane again, controlling the dropwise adding speed to be 2 drops/second, after the dropwise adding is finished, keeping the temperature for reaction for 1h at 135 ℃, vacuumizing, cooling to 90 ℃, adding a polyether antioxidant, and uniformly stirring to obtain the fluorine-containing polyether polyol, wherein the dosage of the double metal cyanide complex catalyst is 0.05 percent of the sum of the mass of hexafluorobisphenol A and the mass of the epoxypropane, the polyether antioxidant is 0.5 percent of the sum of the mass of the hexafluorobisphenol A and the epoxypropane, and the polyether antioxidant is Chic PU 3325 polyether antioxidant.
Example 3
An anti-yellowing additive is prepared by the following steps:
step S1, adding 0.025mol of cyanuric chloride and 60mL of acetone into a three-neck flask, stirring for 20min at 0 ℃, then dropwise adding 20mL of DMF solution containing 0.025mol of 4-nitrophenol, controlling the dropwise adding speed to be 1 drop/S, after the dropwise adding is finished, adjusting the pH to be 5, stirring and reacting at 0 ℃ until the pH value of the system does not change, heating to 10 ℃, dropwise adding 20mL of DMF solution containing 0.025mol of 2, 4-dihydroxy benzophenone, after the dropwise adding is finished, heating to 35 ℃, adjusting the pH to be 6, stirring and reacting until the pH value does not change, continuously heating to 60 ℃, adding 0.025mol of 2, 6-tetramethyl piperidine amine, slowly evaporating the acetone, adjusting the pH value of the system to be neutral, heating to 85 ℃, stirring and reacting until the pH value of the system does not change, finishing the reaction, cooling to room temperature, pouring a reaction product into the acetone, carrying out vacuum filtration, washing a filter cake with the acetone, drying at 60 ℃ to constant weight, and obtaining an intermediate product;
and S2, adding 10.5g of intermediate product, 26g of absolute ethyl alcohol and 4mL of ethyl acetate into a reaction kettle, starting stirring, adding 0.4g of palladium-carbon hydrogenation catalyst, heating until reflux, dropwise adding 4.3g of hydrazine hydrate solution with the mass concentration of 85%, after dropwise adding, carrying out reflux reaction for 5h, filtering while hot, collecting filtrate, cooling to room temperature, carrying out suction filtration, washing filter cakes with deionized water, and drying at 100 ℃ to constant weight to obtain the yellowing-resistant auxiliary agent.
Example 4
An anti-yellowing auxiliary agent is prepared by the following steps:
step S1, adding 0.025mol of cyanuric chloride and 60mL of acetone into a three-neck flask, stirring for 20min at 0 ℃, then dropwise adding 20mL of DMF solution containing 0.025mol of 4-nitrophenol, controlling the dropwise adding speed to be 2 drops/second, after the dropwise adding is finished, adjusting the pH to be 6, stirring and reacting at 5 ℃ until the pH value of the system is not changed, heating to 10 ℃, dropwise adding 20mL of DMF solution containing 0.025mol of 2, 4-dihydroxy benzophenone, after the dropwise adding is finished, heating to 40 ℃, adjusting the pH to be 7, stirring and reacting until the pH value is not changed, continuously heating to 70 ℃, adding 0.025mol of 2, 6-tetramethyl piperidine amine, slowly evaporating out the acetone, adjusting the pH value of the system to be neutral, heating to 90 ℃, stirring and reacting until the pH value of the system is not changed, finishing the reaction, cooling to room temperature, pouring a reaction product into the acetone, carrying out vacuum filtration, washing a filter cake with the acetone, drying at 60 ℃ to constant weight, and obtaining an intermediate product;
and S2, adding 11.6g of intermediate product, 30g of absolute ethyl alcohol and 6mL of ethyl acetate into a reaction kettle, starting stirring, adding 0.4g of palladium-carbon hydrogenation catalyst, heating until reflux, dropwise adding 4.8g of hydrazine hydrate solution with the mass concentration of 85%, after dropwise adding, carrying out reflux reaction for 6h, filtering while hot, collecting filtrate, cooling to room temperature, carrying out suction filtration, washing filter cakes with deionized water, and drying at 100 ℃ to constant weight to obtain the yellowing-resistant auxiliary agent.
Example 5
An aromatic waterborne polyurethane resin comprises the following raw materials in parts by weight: 400 parts of fluorine-containing polyether polyol in example 1, 200 parts of phenyl toluene diisocyanate, 0.4 part of stannous octoate, 24 parts of dimethylolpropionic acid, 1 part of trimethylolpropane, 30.2 parts of methyl propylene glycol, 200 parts of acetone, 4 parts of epoxy resin E-51, 18 parts of triethylamine, 8 parts of KH-550 silane coupling agent, 800 parts of water, 12 parts of yellowing-resistant assistant in example 3 and 4 parts of Kathon;
the aromatic waterborne polyurethane resin is prepared by the following steps:
the preparation method comprises the steps of dehydrating fluorine-containing polyether polyol in a reaction kettle in vacuum at 110 ℃ for 0.5h, cooling to 60 ℃, adding phenyl toluene diisocyanate, charging nitrogen, heating to 88 ℃, carrying out heat preservation and stirring reaction for 2h, cooling to 50 ℃, adding acetone, a yellowing-resistant auxiliary agent, a KH-550 silane coupling agent, stannous octoate, dimethylolpropionic acid, trimethylolpropane and methyl propylene glycol, heating to 55 ℃, carrying out stirring reaction for 4h, adding epoxy resin E-51, stirring for 1min, adding triethylamine, stirring for 1min, carrying out reduced pressure distillation to remove acetone, cooling to 45 ℃, adding water and kathon, and stirring for 10min to obtain the aromatic waterborne polyurethane resin.
Example 6
An aromatic waterborne polyurethane resin comprises the following raw materials in parts by weight: 430 parts of fluorine-containing polyether polyol in example 1, 240 parts of diphenylmethane diisocyanate, 0.4 part of dibutyltin dilaurate, 26 parts of dimethylolpropionic acid, 1 part of trimethylolpropane, 33 parts of methyl propylene glycol, 220 parts of acetone, 4.5 parts of epoxy resin E-51, 19 parts of triethylamine, 9 parts of KH-550 silane coupling agent, 830 parts of water, 14 parts of yellowing-resistant assistant in example 4 and 4.5 parts of tributyltin chloride;
the aromatic waterborne polyurethane resin is prepared by the following steps:
dehydrating fluorine-containing polyether polyol in a reaction kettle in vacuum at 110 ℃ for 0.5h, then cooling to 60 ℃, adding diphenylmethane diisocyanate, charging nitrogen, heating to 88 ℃, carrying out heat preservation and stirring reaction for 2h, cooling to 50 ℃, adding acetone, dibutyltin dilaurate, an anti-yellowing auxiliary agent, a KH-550 silane coupling agent, dimethylolpropionic acid, trimethylolpropane and methyl propylene glycol, heating to 55 ℃, carrying out stirring reaction for 4.5h, adding epoxy resin E-51, stirring for 1min, then adding triethylamine, stirring for 1min, carrying out reduced pressure distillation to remove acetone, cooling to 45 ℃, adding water and tributyltin chloride, and stirring for 13min to obtain the aromatic waterborne polyurethane resin.
Example 7
An aromatic waterborne polyurethane resin comprises the following raw materials in parts by weight: 450 parts of fluorine-containing polyether polyol of example 2, 250 parts of naphthalene diisocyanate, 0.5 part of dibutyltin dilaurate, 28 parts of dimethylolpropionic acid, 1 part of trimethylolpropane, 35.2 parts of methyl propylene glycol, 250 parts of acetone, 5 parts of epoxy resin E-51, 19.5 parts of triethylamine, 10 parts of KH-550 silane coupling agent, 840 parts of water, 15 parts of yellowing-resistant assistant of example 4 and 5 parts of tributyltin chloride;
the aromatic waterborne polyurethane resin is prepared by the following steps:
dehydrating fluorine-containing polyether polyol in a reaction kettle in vacuum at 110 ℃ for 0.5h, then cooling to 60 ℃, adding naphthalene diisocyanate, charging nitrogen, heating to 90 ℃, carrying out heat preservation and stirring reaction for 2h, cooling to 50 ℃, adding acetone, dibutyltin dilaurate, KH-550 silane coupling agent, yellowing-resistant auxiliary agent, dimethylolpropionic acid, trimethylolpropane and methyl propylene glycol, heating to 55 ℃, carrying out stirring reaction for 5h, adding epoxy resin E-51, stirring for 1-2min, adding triethylamine, stirring for 1min, carrying out reduced pressure distillation to remove acetone, cooling to 45 ℃, adding water and tributyltin chloride, and stirring for 15min to obtain the aromatic waterborne polyurethane resin.
Comparative example 1
The fluorine-containing polyether polyol of example 5 was replaced with polytetramethylene ether glycol sold by Nanjing Kunna chemical Co., ltd. The other raw materials and the preparation method were the same as those of example 5.
Comparative example 2
The yellowing resistant assistant in example 6 was replaced with 2, 4-dihydroxybenzophenone, and the other raw materials and preparation methods were the same as in example 6.
Comparative example 3
The yellowing-resistant assistant in example 7 was replaced with 2, 6-tetramethylpiperidinamine, and the remaining raw materials and preparation method were the same as in example 7.
The polyurethane resins prepared in examples 5 to 7 and comparative examples 1 to 3 were applied to a glass plate having a smooth surface with a squeegee, dried at 40 ℃ for 24h and dried at 120 ℃ for 1h to obtain resin films having a film thickness of 0.1mm, each group of resin films was allowed to stand in deionized water at 50 ℃ for 24h, and the surface moisture was quickly wiped off to calculate the water absorption (%), water absorption (%) = (mass after immersion-mass before immersion)/mass before immersion x 100%, and the examples and comparative examples were a polyurethane resin, a PU white cement (beautiful printing material limited, guan city, and DMF in a mass ratio of 60:12:40, mixing the mixture into synthetic leather slurry, transferring the film onto wet leather by using the same bonding layer resin on release paper to prepare synthetic leather, placing a synthetic leather sample in an ultraviolet weathering box according to the stipulation of QB/T4672-2014 'detection of yellowing resistance of the artificial leather synthetic leather test method', irradiating for 300h, taking out a color difference instrument to test the color difference delta E of the sample before and after ultraviolet irradiation, wherein the test result is shown in table 1:
TABLE 1
| Item | Water absorption (%) | Color difference Δ E |
| Example 5 | 0.49 | 1.9 |
| Example 6 | 0.47 | 1.8 |
| Example 7 | 0.45 | 1.6 |
| Comparative example 1 | 3.4 | 2.5 |
| Comparative example 2 | 0.52 | 2.8 |
| Comparative example 3 | 0.58 | 2.7 |
As can be seen from Table 1, compared with comparative examples 1 to 3, the polyurethane resins prepared in examples 5 to 7 have lower water absorption, smaller color difference Delta E and better yellowing resistance, and are more suitable for the field of synthetic leather preparation.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only, and it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made to the embodiments described without departing from the scope of the invention as defined in the appended claims.
Claims (8)
1. The aromatic waterborne polyurethane resin is characterized by comprising the following raw materials in parts by weight: 400-450 parts of fluorine-containing polyether polyol, 200-250 parts of aromatic isocyanate, 0.4-0.5 part of catalyst, 24-28 parts of dimethylolpropionic acid, 1 part of trimethylolpropane, 30.2-35.2 parts of methyl propylene glycol, 200-250 parts of acetone, 4-5 parts of epoxy resin, 18-19.5 parts of triethylamine, 8-10 parts of KH-550 silane coupling agent, 800-840 parts of water, 12-15 parts of yellowing-resistant auxiliary agent and 4-5 parts of mildew preventive;
the fluorine-containing polyether polyol is prepared by the following steps:
adding hexafluorobisphenol A and a double metal cyanide complex catalyst into a reaction kettle, replacing air in the kettle with nitrogen, vacuumizing, heating to 130 ℃, preserving heat for 1h, dripping propylene oxide in a negative pressure state to increase the pressure in the kettle to 0.1-0.15MPa, carrying out induction reaction at the temperature of 130-150 ℃ for 10-15min, after the induction reaction is finished, dripping propylene oxide again, preserving heat for reaction at the temperature of 135 ℃ for 1h after the dripping is finished, vacuumizing, cooling to 90 ℃, adding a polyether antioxidant, and uniformly stirring to obtain the fluorine-containing polyether polyol.
2. The aromatic aqueous polyurethane resin according to claim 1, wherein the mass ratio of hexafluorobisphenol a to propylene oxide is 0.5:10-11.5, wherein the mass ratio of the first propylene oxide to the second propylene oxide is 15-18:82-85.
3. The aromatic aqueous polyurethane resin according to claim 1, wherein the amount of the double metal cyanide complex catalyst is 0.035 to 0.05% by mass based on the sum of the amounts of hexafluorobisphenol A and propylene oxide.
4. The aromatic aqueous polyurethane resin according to claim 1, wherein the polyether antioxidant is a sum of 0.15 to 0.5 mass% of hexafluorobisphenol A and propylene oxide.
5. The aromatic aqueous polyurethane resin according to claim 1, wherein the yellowing resistance auxiliary is prepared by the following steps:
step S1, cyanuric chloride and acetone are mixed, a DMF solution of 4-nitrophenol is dropwise added after stirring at 0 ℃, after the dropwise addition is finished, the pH is adjusted to be 5-6, the stirring reaction is carried out at 0-5 ℃ until the pH of the system is not changed, the temperature is raised to 10 ℃, a DMF solution of 2, 4-dihydroxybenzophenone is dropwise added, the temperature is raised to 35-40 ℃, the pH is adjusted to be 6-7, the stirring reaction is carried out until the pH is not changed, the temperature is continuously raised to 60-70 ℃,2, 6-tetramethylpiperidine amine is added, acetone is slowly evaporated, the pH of the system is adjusted to be neutral, the temperature is raised to 85-90 ℃, the stirring reaction is carried out until the pH of the system is not changed, and an intermediate product is obtained;
and S2, mixing the intermediate product, absolute ethyl alcohol and ethyl acetate, adding a palladium-carbon hydrogenation catalyst under stirring, heating until reflux, dropwise adding a hydrazine hydrate solution with the mass concentration of 85%, and after dropwise adding, carrying out reflux reaction for 5-6 hours to obtain the yellowing-resistant auxiliary agent.
6. The aromatic aqueous polyurethane resin according to claim 5, wherein the molar ratio of cyanuric chloride, 4-nitrophenol, 2, 4-dihydroxybenzophenone, 2, 6-tetramethylpiperidinamine is 1:1:1:1.
7. the aromatic aqueous polyurethane resin according to claim 5, wherein the mass ratio of the intermediate product, absolute ethyl alcohol, ethyl acetate, palladium-carbon hydrogenation catalyst, and 85% hydrazine hydrate solution is 10.5-11.6:26-30:4-6:0.4:4.3-4.8.
8. The method for preparing the aromatic aqueous polyurethane resin according to claim 1, comprising the steps of:
dehydrating fluorine-containing polyether polyol, adding aromatic isocyanate, introducing nitrogen, heating to 88-90 ℃, keeping the temperature, stirring, reacting for 2h, cooling to 50 ℃, adding acetone, a yellowing-resistant auxiliary agent, a KH-550 silane coupling agent, a catalyst, dimethylolpropionic acid, trimethylolpropane and methyl propylene glycol, heating to 55 ℃, stirring, reacting for 4-5h, adding epoxy resin, stirring for 1-2min, adding triethylamine, stirring for 1min, distilling under reduced pressure to remove acetone, cooling to 45 ℃, adding water and a mildew preventive, and stirring for 10-15min to obtain the aromatic waterborne polyurethane resin.
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Denomination of invention: An aromatic waterborne polyurethane resin and its preparation method Granted publication date: 20230926 Pledgee: Anhui Dongzhi Rural Commercial Bank Co.,Ltd. Pledgor: Anhui Shengda Biopharmaceutical Co.,Ltd. Registration number: Y2024980017998 |