CN115417972B - Aromatic aqueous polyurethane resin and preparation method thereof - Google Patents
Aromatic aqueous polyurethane resin and preparation method thereof Download PDFInfo
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- CN115417972B CN115417972B CN202211228101.5A CN202211228101A CN115417972B CN 115417972 B CN115417972 B CN 115417972B CN 202211228101 A CN202211228101 A CN 202211228101A CN 115417972 B CN115417972 B CN 115417972B
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- stirring
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- heating
- polyurethane resin
- aromatic
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 40
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 34
- 229920000570 polyether Polymers 0.000 claims abstract description 34
- 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 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 239000003054 catalyst 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 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 34
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-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 15
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- 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 14
- 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
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 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
- 239000002994 raw material Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007792 addition Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 239000000243 solution Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002649 leather substitute Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000463 material 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
- 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
- 239000000706 filtrate Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000001105 regulatory effect Effects 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
- 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
- 230000000694 effects Effects 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
- 238000012360 testing method Methods 0.000 description 2
- 229940124543 ultraviolet light absorber Drugs 0.000 description 2
- 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 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 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
- WIVPMSKYOVHIMW-UHFFFAOYSA-N benzene 2,4-diisocyanato-1-methylbenzene Chemical compound CC=1C(N=C=O)=CC(N=C=O)=CC1.C1=CC=CC=C1 WIVPMSKYOVHIMW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification 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
- 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
- 230000001681 protective effect Effects 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—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 aqueous polyurethane resin and a preparation method thereof, belonging to the technical field of aqueous polyurethane resin preparation, and the preparation method comprises the following steps: dehydrating fluorine-containing polyether polyol, adding aromatic isocyanate, charging nitrogen, heating to 88-90 ℃, preserving heat, stirring, reacting for 2h, cooling to 50 ℃, adding acetone, yellowing-resistant auxiliary agent, catalyst, dimethylolpropionic acid, trimethylol propane and methyl propylene glycol, heating to 55 ℃, stirring, reacting for 4-5h, adding epoxy resin, stirring, adding triethylamine, distilling under reduced pressure to remove acetone, cooling to 45 ℃, adding water and mildew preventive, and stirring to obtain the aromatic water-based 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
With the enhancement of environmental awareness, the aqueous polyurethane resin is more and more popular, the aqueous polyurethane resin is prepared from aliphatic isocyanate and polyalcohol, the method has the advantages of simple process, easy control of reaction, stable quality and good yellowing resistance of the product, but because the aliphatic isocyanate is high in price, the product cost is high, the polyurethane resin used for the synthetic leather is aromatic aqueous polyurethane resin, the product is prepared from aromatic isocyanate, the product is high in wear resistance and good in solvent resistance, the aromatic isocyanate contains benzene rings, under the irradiation of ultraviolet light, the benzene rings absorb the energy of ultraviolet light and are easily isomerized to form a quinone structure to yellow, meanwhile, the synthetic leather also absorbs the moisture in the air, under the action of the ultraviolet light, the degradation and isomerization of the polyurethane resin are accelerated, so that the polyurethane resin is more easily yellowing, and in order to overcome the factor, the ultraviolet light absorbers are often added into the aromatic aqueous polyurethane resin, but the ultraviolet light absorbers are easy to migrate and separate out, and the effect is limited, so that the problem that the aromatic polyurethane resin with good yellowing resistance effect can not be improved under the water is the current technical problem.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention provides an aromatic waterborne polyurethane resin and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
an aromatic aqueous 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 aqueous polyurethane resin is prepared by the following steps:
vacuum dehydrating fluorine-containing polyether polyol at 110 ℃ for 0.5h in a reaction kettle, then cooling to 60 ℃, adding aromatic isocyanate, charging nitrogen, heating to 88-90 ℃, carrying out heat preservation and stirring reaction for 2h, cooling to 50 ℃, adding acetone, yellowing-resistant auxiliary agent, KH-550 silane coupling agent, catalyst, dimethylolpropionic acid, trimethylolpropane and methyl propylene glycol, heating to 55 ℃, carrying out stirring 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 mildew preventive, and stirring for 10-15min to obtain aromatic water-based polyurethane resin.
Further, the fluoropolyether polyol comprises the steps of:
adding hexafluorobisphenol A and double metal cyanide complex catalyst (DMC catalyst) into a reaction kettle, replacing air in the kettle with nitrogen, vacuumizing, heating to 130 ℃, keeping the temperature for 1h, dropwise adding propylene oxide under negative pressure, raising the pressure in the kettle to 0.1-0.15MPa, carrying out induction reaction at the temperature of 130-150 ℃ for 10-15min, dropwise adding propylene oxide again after the induction reaction is finished, controlling the dropwise adding speed to be 1-2 drops/sec, keeping the temperature at 135 ℃ for 1h after the dropwise adding is finished, vacuumizing, cooling to 90 ℃, adding polyether antioxidant, and stirring uniformly to obtain fluorine-containing polyether polyol;
wherein the mass ratio of the hexafluorobisphenol A to the propylene oxide is 0.5:10-11.5, the mass ratio of the first epoxypropane to the second epoxypropane is 15-18:82-85, wherein the dosage of the double metal cyanide complex catalyst is that the mass of hexafluorobisphenol A and the mass of propylene oxide are 0.035-0.05%, the polyether antioxidant is that the mass of hexafluorobisphenol A and the mass of propylene oxide are 0.15-0.5%, the polyether antioxidant is purchased from Shanghai Qikk fluorosilicone material limited company, one or more selected from Chic PU 3325 polyether antioxidant, chic PU 5057 polyether antioxidant and Chic PU 3318 polyether antioxidant are mixed according to any proportion, the hexafluorobisphenol A is taken as an initiator, the double metal cyanide complex catalyst catalyzes the ring-opening polymerization of propylene oxide to obtain 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 capability in ultraviolet light, so that the possibility of damaging the C-F bond is extremely low in the visible ultraviolet light wave range, and the C-F bond with the high bond energy is introduced and the C-C bond with the lower bond energy plays a protective role in protecting the ultraviolet resistance of the product.
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 ℃, dropwise adding a DMF solution of 4-nitrophenol, controlling the dropwise adding speed to be 1-2 drops/second, regulating the pH to be 5-6 after the dropwise adding is finished, stirring and reacting at the temperature of 0-5 ℃ until the system acid and alkali are not changed, heating to 10 ℃, dropwise adding a DMF solution of 2, 4-dihydroxybenzophenone, heating to 35-40 ℃ after the dropwise adding is finished, regulating the pH to be 6-7, stirring and reacting until the pH is not changed, continuously heating to 60-70 ℃, adding 2, 6-tetramethylpiperidine amine, slowly steaming out acetone, regulating the pH of the system to be neutral, heating to 85-90 ℃, stirring and reacting until the pH of the system is unchanged, cooling to room temperature after the reaction is finished, pouring the reaction product into acetone, decompressing and filtering, repeatedly washing a filter cake with acetone, and drying to constant weight at 60 ℃ to obtain an intermediate product;
wherein, the pH is adjusted by 10% sodium hydroxide aqueous solution by mass fraction, the mole ratio of cyanuric chloride, 4-nitrophenol, 2, 4-dihydroxybenzophenone and 2, 6-tetramethylpiperidine amine is 1:1:1:1, carrying out elimination HCl reaction on cyanuric chloride, 4-nitrophenol, 2, 4-dihydroxybenzophenone and 2, 6-tetramethylpiperidine amine to obtain an intermediate product;
s2, adding an intermediate product, absolute ethyl alcohol and ethyl acetate into a reaction kettle, starting stirring, adding a palladium-carbon hydrogenation catalyst, heating until the mixture is refluxed and dropwise added with a hydrazine hydrate solution with the mass concentration of 85%, carrying out reflux reaction for 5-6 hours after the dropwise addition is finished, filtering while the mixture is hot, collecting filtrate, cooling to room temperature, carrying out suction filtration, washing a filter cake with deionized water, and drying to constant weight at 100 ℃ 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 in the intermediate product into amino under the action of palladium-carbon hydrogenation catalyst and hydrazine hydrate to obtain the yellowing-resistant auxiliary agent.
Further, the aromatic isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate, which are mixed according to any proportion.
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 a combination of two of kathon and tributyltin chloride.
The invention has the beneficial effects that:
1. the aromatic aqueous polyurethane resin provided by the invention has excellent mechanical properties and high yellowing resistance, and the epoxy resin is adopted to modify the polyurethane resin, so that the cohesion of polyurethane molecules is effectively improved, the adhesive force of a product is increased, and the polyurethane molecules are networked through crosslinking, so that the heat resistance of the product is improved.
2. According to the invention, the fluorine-containing polyether polyol is introduced into the aqueous 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, so that the heat resistance of the product is improved, the existence of the C-F bonds improves the stability of a main chain on one hand, the light aging resistance is improved, the surface energy of the material can be obviously reduced on the other hand, the water repellency of the material is improved, and the water knot resistance of the product is further enhanced.
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 groups, can improve the yellowing resistance of the product from the aspects of absorbing ultraviolet rays and capturing photoaging free radicals, can participate in polyurethane curing reaction, introduces the benzophenone structure and the hindered amine structure into the product through chemical bonds, and solves the problems of easy migration and precipitation of the traditional Huang Bianji.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The double metal cyanide complex catalyst of the examples was purchased from Huaian Baud polyurethane technologies Co.
Example 1
A fluoropolyether polyol comprising the steps of:
adding 0.5g of 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, dropwise adding 1.5g of alkylene oxide under a negative pressure state, then raising the pressure in the kettle to 0.1MPa, carrying out induction reaction at the temperature of 130 ℃ for 10min, dropwise adding 8.5g of propylene oxide again after the induction reaction is finished, controlling the dropwise adding speed to be 1 drop/sec, preserving heat for 1h at 135 ℃ after the dropwise adding is finished, vacuumizing and cooling to 90 ℃, adding polyether antioxidant, and stirring uniformly to obtain the fluorine-containing polyether polyol, wherein the double metal cyanide complex catalyst is prepared by adding 0.035% of the mass sum of hexafluorobisphenol A and propylene oxide, and 0.15% of the polyether antioxidant is prepared by adding Chic PU 3325 polyether antioxidant.
Example 2
A fluoropolyether polyol comprising the steps of:
adding 0.5g of 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, dropwise adding 2.07g of propylene oxide under a negative pressure state, then raising the pressure in the kettle to 0.15MPa, carrying out induction reaction at the temperature of 150 ℃ for 15min, dropwise adding 9.43g of propylene oxide again after the induction reaction is finished, controlling the dropwise adding speed to be 2 drops/sec, preserving heat for 1h at the temperature of 135 ℃ after the dropwise adding is finished, vacuumizing and cooling to 90 ℃, adding polyether antioxidant, and stirring uniformly to obtain the fluorine-containing polyether polyol, wherein the dosage of the double metal cyanide complex catalyst is hexafluorobisphenol A and propylene oxide mass sum 0.05%, the polyether antioxidant is hexafluorobisphenol A and propylene oxide mass sum 0.5%, and the polyether antioxidant is Chic PU 3325 polyether antioxidant.
Example 3
A yellowing-resistant 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 1 drop/second, adjusting the pH value to be 5 after the dropwise adding is finished, stirring the system at the temperature of 0 ℃ for reaction until the acidity and alkalinity are not changed, heating to 10 ℃, dropwise adding 20mL of DMF solution containing 0.025mol of 2, 4-dihydroxybenzophenone, heating to 35 ℃ after the dropwise adding is finished, adjusting the pH value to be 6, stirring the system until the pH value is not changed, continuously heating to 60 ℃, adding 0.025mol of 2, 6-tetramethylpiperidine amine, slowly steaming out acetone, adjusting the pH value of the system to be neutral, heating to 85 ℃, stirring the system until the pH value is not changed, cooling to room temperature after the reaction is finished, pouring the reaction product into acetone, decompressing and filtering, repeatedly washing a filter cake with acetone, and drying to constant weight at 60 ℃ to obtain 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 begins to dropwise add 4.3g of 85% hydrazine hydrate solution, carrying out reflux reaction for 5h after the dropwise addition is finished, filtering while the solution is hot, collecting filtrate, cooling to room temperature, carrying out suction filtration, washing a filter cake with deionized water, and drying at 100 ℃ until the weight is constant, thus obtaining the yellowing-resistant auxiliary agent.
Example 4
A yellowing-resistant 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, adjusting the pH value to be 6 after the dropwise adding is finished, stirring 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-dihydroxybenzophenone, heating to 40 ℃ after the dropwise adding is finished, adjusting the pH value to be 7, stirring until the pH value is not changed, continuously heating to 70 ℃, adding 0.025mol of 2, 6-tetramethylpiperidine amine, slowly steaming out acetone, adjusting the pH value of the system to be neutral, heating to 90 ℃, stirring until the pH value of the system is not changed, cooling to room temperature after the dropwise adding the reaction product into acetone, decompressing and filtering, repeatedly washing a filter cake with acetone, and drying at 60 ℃ until the constant weight to obtain 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 begins to dropwise add 4.8g of 85% hydrazine hydrate solution, carrying out reflux reaction for 6 hours after the dropwise addition is finished, filtering while the solution is hot, collecting filtrate, cooling to room temperature, carrying out suction filtration, washing a filter cake with deionized water, and drying at 100 ℃ until the weight is constant, thus obtaining the yellowing-resistant auxiliary agent.
Example 5
An aromatic aqueous polyurethane resin comprises the following raw materials in parts by weight: 400 parts of the fluorine-containing polyether polyol of the example 1, 200 parts of phenyltoluene 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 auxiliary of the example 3 and 4 parts of kathon;
the aromatic aqueous polyurethane resin is prepared by the following steps:
vacuum dehydrating fluorine-containing polyether polyol at 110 ℃ for 0.5h, cooling to 60 ℃, adding benzene toluene diisocyanate, charging nitrogen, heating to 88 ℃, maintaining the temperature, stirring for reacting for 2h, cooling to 50 ℃, adding acetone, yellowing-resistant auxiliary agent, KH-550 silane coupling agent, stannous octoate, dimethylolpropionic acid, trimethylolpropane and methyl propylene glycol, heating to 55 ℃, stirring for reacting for 4h, adding epoxy resin E-51, stirring for 1min, adding triethylamine, stirring for 1min, distilling under reduced pressure to remove acetone, cooling to 45 ℃, adding water and Kasong, stirring for 10min, and obtaining aromatic water-based polyurethane resin.
Example 6
An aromatic aqueous polyurethane resin comprises the following raw materials in parts by weight: 430 parts of the fluorine-containing polyether polyol of the 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 auxiliary of the example 4 and 4.5 parts of tributyltin chloride;
the aromatic aqueous polyurethane resin is prepared by the following steps:
vacuum dehydrating fluorine-containing polyether polyol at 110 ℃ for 0.5h in a reaction kettle, cooling to 60 ℃, adding diphenylmethane diisocyanate, charging nitrogen, heating to 88 ℃, maintaining the temperature, stirring for reacting for 2h, cooling to 50 ℃, adding acetone, dibutyltin dilaurate, yellowing-resistant auxiliary agent, KH-550 silane coupling agent, dimethylolpropionic acid, trimethylolpropane and methyl propylene glycol, heating to 55 ℃, stirring for reacting for 4.5h, adding epoxy resin E-51, stirring for 1min, adding triethylamine, stirring for 1min, distilling under reduced pressure to remove acetone, cooling to 45 ℃, adding water and tributyltin chloride, stirring for 13min, and obtaining the aromatic water-based polyurethane resin.
Example 7
An aromatic aqueous polyurethane resin comprises the following raw materials in parts by weight: 450 parts of a fluoropolyether 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, 51 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 resistance auxiliary of example 4 and 5 parts of tributyltin chloride;
the aromatic aqueous polyurethane resin is prepared by the following steps:
vacuum dehydrating fluorine-containing polyether polyol at 110 ℃ for 0.5h in a reaction kettle, then cooling to 60 ℃, adding naphthalene diisocyanate, charging nitrogen, heating to 90 ℃, keeping the temperature, stirring for reacting for 2h, cooling to 50 ℃, adding acetone, dibutyl tin dilaurate, KH-550 silane coupling agent, yellowing-resistant auxiliary agent, dimethylol propionic acid, trimethylolpropane and methyl propylene glycol, heating to 55 ℃, stirring for reacting for 5h, adding epoxy resin E-51, stirring for 1-2min, adding triethylamine, stirring for 1min, distilling under reduced pressure to remove acetone, cooling to 45 ℃, adding water and tributyltin chloride, and stirring for 15min to obtain aromatic water-based polyurethane resin.
Comparative example 1
The fluoropolyether polyol of example 5 was replaced with polytetramethylene ether glycol sold by Nanjing Kunn chemical Co., ltd. And the remaining materials and preparation method were the same as in example 5.
Comparative example 2
The yellowing-resistant auxiliary in example 6 is replaced by 2, 4-dihydroxybenzophenone, and the rest raw materials and the preparation method are the same as those in example 6.
Comparative example 3
The yellowing resistance auxiliary in example 7 is replaced by 2, 6-tetramethyl piperidine amine, and the rest raw materials and the preparation method are the same as those in example 7.
The polyurethane resins prepared in examples 5 to 7 and comparative examples 1 to 3 were scraped on a glass plate having a smooth surface by a squeegee, dried at 40℃for 24 hours and at 120℃for 1 hour to obtain resin films having a film thickness of 0.1mm, each set of resin films was left in deionized water at 50℃for 24 hours, the surface moisture was rapidly wiped off, and the water absorption (%) was calculated as water absorption (%) = (post-immersion mass-pre-immersion mass)/pre-immersion mass X100%, and the examples and comparative examples were polyurethane resins, PU white cement (Toguan City beautiful printing materials Co., ltd.) and DMF in a mass ratio of 60:12:40, transferring the same adhesive layer resin film to wet leather on release paper to prepare synthetic leather, placing a synthetic leather sample into an ultraviolet weather-proof box according to QB/T4672-2014 'detection of yellowing resistance of artificial leather synthetic leather test method', taking out after 300h of irradiation, and testing the color difference delta E of the sample before and after ultraviolet irradiation by a color difference meter, wherein the test result is shown in table 1:
TABLE 1
| Project | Water absorption (%) | Color difference delta 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, the polyurethane resins prepared in examples 5 to 7 have lower water absorption, smaller color difference DeltaE, and better yellowing resistance than those prepared in comparative examples 1 to 3, and are more suitable for the field of synthetic leather preparation.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (5)
1. The aromatic aqueous 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 comprises the following steps:
adding hexafluorobisphenol A and double metal cyanide complex catalyst into a reaction kettle, replacing air in the kettle with nitrogen, vacuumizing, heating to 130 ℃, preserving heat for 1h, dropwise adding propylene oxide under a negative pressure state, enabling the pressure in the kettle to rise to 0.1-0.15MPa, carrying out induction reaction for 10-15min at the temperature of 130-150 ℃, dropwise adding propylene oxide again after the induction reaction is finished, carrying out heat preservation reaction for 1h at 135 ℃ after the completion of the dropwise addition, vacuumizing, cooling to 90 ℃, adding polyether antioxidant, and uniformly stirring to obtain fluorine-containing polyether polyol;
the mass ratio of hexafluorobisphenol A to propylene oxide is 0.5:10-11.5, the mass ratio of the first epoxypropane to the second epoxypropane is 15-18:82-85;
the yellowing-resistant auxiliary agent is prepared by the following steps:
step S1, mixing cyanuric chloride and acetone, dropwise adding a DMF solution of 4-nitrophenol after stirring at 0 ℃, adjusting the pH value to 5-6 after the dropwise adding, stirring at 0-5 ℃ for reaction until the pH value of the system is unchanged, heating to 10 ℃, dropwise adding a DMF solution of 2, 4-dihydroxybenzophenone, heating to 35-40 ℃, adjusting the pH value to 6-7, stirring for reaction until the pH value is unchanged, continuously heating to 60-70 ℃, adding 2, 6-tetramethylpiperidine amine, slowly steaming out acetone, adjusting the pH value of the system to be neutral, heating to 85-90 ℃, and stirring for reaction until the pH value of the system is unchanged to obtain an intermediate product;
s2, mixing the intermediate product, absolute ethyl alcohol and ethyl acetate, adding a palladium-carbon hydrogenation catalyst under stirring, heating until the mixture is refluxed and dropwise added with a hydrazine hydrate solution with the mass concentration of 85%, and carrying out reflux reaction for 5-6 hours after the dropwise addition is finished to obtain a yellowing-resistant auxiliary agent;
the molar ratio of cyanuric chloride, 4-nitrophenol, 2, 4-dihydroxybenzophenone and 2, 6-tetramethyl piperidine amine is 1:1:1:1.
2. 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 of the sum of hexafluorobisphenol A and propylene oxide.
3. The aromatic aqueous polyurethane resin according to claim 1, wherein the polyether antioxidant is 0.15-0.5% of the sum of the mass of hexafluorobisphenol A and the mass of propylene oxide.
4. The aromatic aqueous polyurethane resin according to claim 1, 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.
5. 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, charging nitrogen, heating to 88-90 ℃, preserving heat, stirring, reacting for 2h, cooling to 50 ℃, adding acetone, yellowing-resistant auxiliary agent, KH-550 silane coupling agent, 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, removing acetone by reduced pressure distillation, cooling to 45 ℃, adding water and mildew preventive, stirring for 10-15min, and obtaining the aromatic water-based 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 |