CN113788925A - Waterborne polyurethane resin and preparation method and application thereof - Google Patents
Waterborne polyurethane resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN113788925A CN113788925A CN202111227432.2A CN202111227432A CN113788925A CN 113788925 A CN113788925 A CN 113788925A CN 202111227432 A CN202111227432 A CN 202111227432A CN 113788925 A CN113788925 A CN 113788925A
- Authority
- CN
- China
- Prior art keywords
- dimer acid
- polyester polyol
- polyurethane resin
- combination
- acid polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 103
- 239000000539 dimer Substances 0.000 claims abstract description 89
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 69
- 239000002994 raw material Substances 0.000 claims abstract description 41
- 239000004970 Chain extender Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000002649 leather substitute Substances 0.000 claims abstract description 17
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- 239000013067 intermediate product Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229920002635 polyurethane Polymers 0.000 claims description 22
- 239000004814 polyurethane Substances 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- 229920005862 polyol Polymers 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- KCLIFOXATBWLMW-UHFFFAOYSA-M sodium;ethane-1,2-diamine;ethanesulfonate Chemical compound [Na+].NCCN.CCS([O-])(=O)=O KCLIFOXATBWLMW-UHFFFAOYSA-M 0.000 claims description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical group 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012760 heat stabilizer Substances 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims description 2
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- ZWROCMXAXYCEFC-UHFFFAOYSA-N O(P(O)OP(O)O)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O Chemical compound O(P(O)OP(O)O)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O ZWROCMXAXYCEFC-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 claims description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 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 3
- 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 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing Methods 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1607—Degradability
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1685—Wear resistance
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- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1692—Weather resistance
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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Abstract
The invention provides an aqueous polyurethane resin and a preparation method and application thereof, wherein the preparation raw material of the aqueous polyurethane resin comprises the combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst; the raw materials for preparing the dimer acid polyester polyol comprise the combination of dimer acid, dihydric alcohol and a composite stabilizer; the composite stabilizer is added into the raw materials for preparing the dimer acid polyester polyol, so that the acidity of the dimer acid polyester polyol is lower, and the molecular weight distribution of the dimer acid polyester polyol is narrower; the dimer acid polyester polyol is further added into the raw materials for preparing the waterborne polyurethane resin, and a dimer acid molecular chain is introduced into the resin, so that the waterborne polyurethane resin has excellent hydrolysis resistance, weather resistance, wear resistance, heat resistance and mechanical properties; the curing agent can overcome the defect of low curing speed, has the characteristics of high transparency, high brightness and good adhesive force after film forming, and meets the requirements of the synthetic leather field.
Description
Technical Field
The invention belongs to the technical field of polyurethane synthesis, and particularly relates to a waterborne polyurethane resin and a preparation method and application thereof.
Background
The green and environment-friendly technology has become one of the most concerned topics of people in the world nowadays and also becomes an important index for the development of social economy. At present, in the field of waterborne polyurethane synthesis, the used raw materials are generally derived from petroleum-based non-renewable resources. In order to further protect the natural environment and guarantee the sustainable development of the social economy, the dimer acid derived from renewable resources is a high-quality raw material for replacing adipic acid, and has important application in the field of synthesis of waterborne polyurethane.
Dimer acid has a unique molecular structure, and is increasingly applied to the field of high polymer materials. Polyester polyol with high relative molecular mass, which is synthesized by taking dimer acid, short-molecule diol and the like as raw materials, is used for synthesizing aqueous polyurethane resin, and has good flexibility and higher strength. Dimer acid polyester diols having relatively small molecular weight, which are flexible and rigid, have good solubility, and can impart excellent mechanical properties and thermal stability to polyurethane materials, have been used to prepare polyurethane-urea aqueous dispersions, polyurethane foams, polymeric surfactants, and the like.
CN113265901A discloses a dimer acid-based waterborne polyurethane surface sizing agent, a preparation method and application thereof, belonging to the technical field of surface sizing agent preparation. Mixing dimer acid polyester diol, polycaprolactone diol and diisocyanate for prepolymerization reaction; then adding a hydrophilic chain extender to carry out chain extension reaction; and adding triethylamine for neutralization reaction, and finally adding deionized water for emulsification to obtain the dimer acid-based waterborne polyurethane surface sizing agent. The method not only realizes the high-value utilization of the dimer acid in the field of green environment-friendly coatings, but also provides an environment-friendly, sustainable and economic method for improving the waterproof and oil-proof performance of paper, and the prepared dimer acid-based waterborne polyurethane emulsion can be used as a paper surface sizing agent to obviously improve the waterproof, oil-proof and mechanical properties of paper.
However, since the dimer acid polyester polyol used in the prior art has a wide molecular weight distribution and yet needs to be further reduced in chromaticity and acid value, the waterborne polyurethane prepared by using the dimer acid polyester polyol as a raw material has poor properties, and is difficult to be applied in a large range in the field of synthetic leather.
Therefore, an object of the present invention is to provide an aqueous polyurethane resin which is produced from a dimer acid polyester polyol and has excellent weather resistance, abrasion resistance, heat resistance and mechanical properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the waterborne polyurethane resin and the preparation method and the application thereof, wherein the preparation raw material of the waterborne polyurethane resin comprises the combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst; the raw materials for preparing the dimer acid polyester polyol comprise dimer acid, dihydric alcohol and a composite stabilizer; the color and acid value of the dimer acid polyester polyol prepared by using the dimer acid, the dihydric alcohol and the composite stabilizer as raw materials are low, and the comprehensive performance of the waterborne polyurethane resin prepared by using the dimer acid polyester polyol as the raw materials is excellent.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an aqueous polyurethane resin, wherein the raw materials for preparing the aqueous polyurethane resin comprise a combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst;
the raw materials for preparing the dimer acid polyester polyol comprise dimer acid, dihydric alcohol and a composite stabilizer.
The preparation raw materials of the waterborne polyurethane resin provided by the invention comprise a combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst; the raw materials for preparing the dimer acid polyester polyol comprise dimer acid, dihydric alcohol and a composite stabilizer; the dimer acid is derived from renewable resources, so that the environment is protected, and the application of the renewable resources and the renewability of the polyurethane resin are promoted; the addition of the composite stabilizer can limit the generation of byproducts in the whole preparation process of the dimer acid polyester polyol, so that the prepared dimer acid polyester polyol has narrower molecular mass distribution and higher yield; the prepared waterborne polyurethane resin can overcome the defects of low room temperature curing speed, poor water resistance, weather resistance, wear resistance, heat resistance, mechanical property and the like of the traditional waterborne polyurethane; and the paint has the characteristics of high brightness and good adhesive force after film forming, and can meet the requirements in some special application fields.
In the present invention, the catalyst may be selected from BICAT8118 available from leading chemicals in the united states.
Preferably, the mass percentage of the dimer acid polyester polyol in the raw materials for preparing the aqueous polyurethane resin is 10-40%, for example, 15%, 20%, 25%, 30%, 35% or 40%.
Preferably, the number average molecular weight of the dimer acid polyester polyol is 1000 to 5000, such as 1500, 2000, 2500, 3000, 3500, 4000 or 4500.
Preferably, the raw materials for preparing the dimer acid polyester polyol comprise the following components in parts by weight:
wherein the diol may be 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or 45 parts by weight, or the like.
The dimer acid may be 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, or the like.
The catalyst may be 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, or 0.045 parts by weight, or the like.
The composite stabilizer may be 0.005 parts by weight, 0.007 parts by weight, 0.009 parts by weight, 0.011 parts by weight, 0.013 parts by weight, 0.015 parts by weight, 0.017 parts by weight, 0.019 parts by weight, 0.02 parts by weight, 0.023 parts by weight, 0.026 parts by weight, 0.029 parts by weight or the like.
As a preferred technical scheme, the raw materials for preparing the dimer acid polyester polyol adopted by the invention comprise the combination of specific parts of dihydric alcohol, dimer acid, a catalyst and a composite stabilizer; by adding the composite stabilizer in a specific part in the preparation raw materials, the generation of byproducts in the whole preparation process of the dimer acid polyester polyol can be limited; the addition of the composite stabilizer can reduce the oxidation of dihydric alcohol in the esterification stage; on the other hand, the oxidation of the dimer acid in the polycondensation stage can be reduced, so that the generation of byproducts in the whole preparation process is less, and finally the dimer acid polyester polyol with low acid value and low chroma is obtained; the dimer acid polyester polyol prepared by combining the preparation raw materials has narrower molecular mass distribution and higher yield, so that the dimer acid polyester polyol is more suitable for synthesis of aqueous polyurethane resin.
Preferably, the diol comprises any one of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol or 1, 6-hexanediol, or a combination of at least two thereof.
Preferably, the catalyst comprises any one of or a combination of at least two of tetraisopropyl titanate, tetra-n-butyl titanate, tetra-tert-butyl titanate, stannous octoate, dibutyltin dilaurate, bismuth laurate, zinc oxide, or antimony trioxide.
Preferably, the composite stabilizer comprises a combination of a phosphate-based heat stabilizer and a phosphite-based heat oxygen stabilizer.
Preferably, the phosphate-based heat stabilizer comprises any one of triphenyl phosphate, triethyl methylphosphonate or triethyl phosphonoacetate or a combination of at least two of the foregoing.
Preferably, the phosphite thermal oxygen stabilizer includes any one of triphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite or tetrakis (2, 4-di-t-butylphenol) -4,4' -biphenylyl diphosphite or a combination of at least two thereof.
Preferably, the raw materials for preparing the dimer acid polyester polyol also comprise other dibasic acid.
Preferably, the other dibasic acid comprises any one of succinic acid, glutaric acid, adipic acid, azelaic acid or sebacic acid or a combination of at least two thereof.
The "other dibasic acid" in the present invention means a dibasic acid other than the dimer acid; for example, the other dibasic acid may include any one of succinic acid, glutaric acid, adipic acid, azelaic acid, or sebacic acid, or a combination of at least two thereof.
Preferably, the content of the other dibasic acid in the raw materials for preparing the dimer acid polyester polyol is 0 to 50 parts by weight and is not equal to 0, such as 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight or 45 parts by weight.
As a preferred embodiment of the present invention, the dimer acid polyester polyol of the present invention can be prepared by a method comprising the steps of:
(A1) under the protection of inert gas, reacting dihydric alcohol, dimer acid, a composite stabilizer and optionally other dibasic acids at 130-160 ℃ for 3-120 min, heating to 210-250 ℃ at the temperature rise speed of 5-30 ℃/h, and carrying out esterification dehydration reaction for 3-5 h to obtain an intermediate product;
(A2) and (C) mixing the intermediate product obtained in the step (A1) with a catalyst, preserving the temperature at 210-250 ℃ for 30-180 min, and carrying out distillation polycondensation reaction under-0.1-0 Mpa for 2-6 h to obtain the dimer acid polyester polyol with the hydroxyl value of 30-120 mgKOH/g and the acid value of 0.1-1 mgKOH/g.
Preferably, the mass ratio of the dimer acid polyester polyol to the diisocyanate is (0.5-2: 1), such as 0.7:1, 0.9:1, 1.1:1, 1.3:1, 1.5:1, 1.7:1 or 1.9: 1.
Preferably, the diisocyanate includes any one or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or tetramethylxylylene diisocyanate, and more preferably any one or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.
Preferably, the mass ratio of the dimer acid polyester polyol to the chain extender is 5-10: 1, such as 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1 or 9.5: 1.
Preferably, the chain extender comprises a hydrophilic chain extender.
Preferably, the hydrophilic chain extender comprises any one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid or sodium ethylenediamine ethanesulfonate or a combination of at least two of the same.
Preferably, the chain extender comprises an alcohol chain extender.
Preferably, the alcohol chain extender comprises any one of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexylene glycol, 3-methyl-1, 5-pentanediol or ethanolamine or a combination of at least two thereof.
Preferably, the chain extender further comprises an amine chain extender.
Preferably, the amine chain extender comprises ethylene diamine.
Preferably, the mass ratio of the catalyst to the dimer acid polyester polyol is 0.00001-0.00005: 1, such as 0.000015:1, 0.00002:1, 0.000025:1, 0.00003:1, 0.000035:1, 0.00004:1 or 0.000045: 1.
Preferably, the raw materials for preparing the aqueous polyurethane resin also comprise any one or a combination of at least two of a neutralizer, a solvent or other polyester polyols.
Preferably, the neutralizing agent comprises any one of triethylamine, ammonia water, N-methylmorpholine, N-ethylmorpholine, N-methyldiethanolamine or NaOH or a combination of at least two of them.
Preferably, the solvent comprises acetone and/or butanone.
Preferably, the other polyol comprises any one of or a combination of at least two of a tetrahydrofuran ether glycol, a polycarbonate glycol or a polyester polyol.
Preferably, the number average molecular weight of the other polyol is 500 to 4000, such as 1000, 1500, 2000, 2500, 3000, 3500 or 4000.
Preferably, the mass percentage of the dimer acid polyester polyol in all polyols in the raw materials for preparing the aqueous polyurethane resin is 50-100% and is not equal to 100%, such as 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%.
In a second aspect, the present invention provides a method for preparing the waterborne polyurethane according to the first aspect, wherein the method comprises the following steps:
(1) mixing dimer acid polyester polyol, optional other polyol, optional chain extender and optional catalyst, and adding diisocyanate for reaction to obtain an initial product;
(2) mixing the initial product obtained in the step (1), a chain extender and an optional solvent, and adding a catalyst to react to obtain an intermediate product;
(3) and (3) mixing the intermediate product obtained in the step (2), an optional solvent and an optional neutralizer, adding deionized water for dispersion, adding a chain extender for reaction, and removing the solvent to obtain the waterborne polyurethane resin.
Preferably, the reaction temperature in step (1) is 70-95 ℃, such as 72 ℃, 74 ℃, 76 ℃, 79 ℃, 82.5 ℃, 84 ℃, 86.5 ℃, 89 ℃, 92.5 ℃, 93 ℃, 93.5 ℃, 94 ℃ or 94.5 ℃.
Preferably, the reaction of step (1) is carried out under atmospheric conditions.
Preferably, the reaction time in step (1) is 2-4 h, such as 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h or 3.8 h.
Preferably, the temperature of the mixing in step (2) is 90-95 ℃, such as 90.5 ℃, 91 ℃, 91.5 ℃, 92 ℃, 92.5 ℃, 93 ℃, 93.5 ℃, 94 ℃ or 94.5 ℃.
Preferably, the mixing time in step (2) is 2-3 h, such as 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h or 2.9 h.
Preferably, the temperature of the reaction in step (2) is 60 to 65 ℃, such as 60.5 ℃, 61 ℃, 61.5 ℃, 62 ℃, 62.5 ℃, 63 ℃, 63.5 ℃, 64 ℃ or 64.5 ℃.
Preferably, the reaction time in the step (2) is 2-3 h, such as 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h or 2.9 h.
Preferably, the reaction in step (3) is carried out at a temperature of not higher than 40 deg.C, such as 39 deg.C, 38 deg.C, 37 deg.C, 36 deg.C, 35 deg.C, 30 deg.C, 25 deg.C, 20 deg.C, 15 deg.C, 10 deg.C or 5 deg.C, etc.
Preferably, the solvent removal in step (3) is carried out under a vacuum of-0.09 to-0.1 MPa (e.g., -0.08, -0.07, -0.06, -0.05, -0.04, -0.03, -0.02, or-0.01, etc.).
As a preferable technical scheme of the invention, the preparation method of the waterborne polyurethane resin comprises the following steps:
(1) mixing dimer acid polyester polyol, optionally other polyols, optionally a chain extender and optionally a catalyst, adding diisocyanate, and reacting at normal pressure and 70-95 ℃ for 2-4 h to obtain an initial product;
(2) mixing the initial product obtained in the step (1), a chain extender and an optional solvent at 90-95 ℃ for 2-3 h, adding a catalyst, and reacting at 90-95 ℃ for 2-3 h to obtain an intermediate product;
(3) mixing the intermediate product obtained in the step (2), an optional solvent and an optional neutralizer at the temperature of not higher than 40 ℃, adding deionized water for dispersion, adding a chain extender for reaction, and removing the solvent under the condition of-0.09 to-0.1 MPa to obtain the waterborne polyurethane resin.
In a third aspect, the invention provides a use of the aqueous polyurethane resin according to the first aspect in synthetic leather.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation raw materials of the waterborne polyurethane resin provided by the invention comprise a combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst; the raw materials for preparing the dimer acid polyester polyol comprise the combination of dimer acid, dihydric alcohol and a composite stabilizer; the raw material for preparing the waterborne polyurethane resin takes dimer acid polyester polyol extracted from renewable resources as a raw material, and is beneficial to promoting the application of the renewable resources and the renewability of the waterborne polyurethane resin.
(2) According to the waterborne polyurethane resin provided by the invention, dimer acid molecular chains are introduced into polyurethane molecular chains and resin components, so that the waterborne polyurethane resin has excellent hydrolysis resistance, weather resistance, wear resistance, heat resistance and mechanical properties; the waterborne polyurethane resin overcomes the defects of low room-temperature curing speed, poor water resistance and mechanical property and the like of the traditional waterborne polyurethane, has the characteristics of high brightness and good adhesive force after film forming, and can meet the requirements in some special application fields.
(3) The waterborne polyurethane resin provided by the invention has good comprehensive performance, has the advantages of environmental friendliness, no toxicity, no harm, safe transportation and the like, and belongs to an environment-friendly polyurethane product.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the waterborne polyurethane resin comprises the following steps:
(1) stirring 150g of dimer acid polyester polyol (with a number average molecular weight of 2000), 150g of polytetrahydrofuran ether glycol (with a number average molecular weight of 2000), 5g of DMPA and 0.1g of catalyst BICAT8118 at 50 ℃ for 20min, adding 100g of dicyclohexylmethane diisocyanate and 20g of 1, 6-hexamethylene diisocyanate, and reacting at normal pressure and 85 ℃ for 2.5h to obtain an initial product;
(2) mixing the initial product obtained in the step (1), 6g of methyl propylene glycol, 3g of ethanolamine and 150g of acetone at 62 ℃ for 2h, adding 0.1g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;
(3) mixing the intermediate product obtained in the step (2), 150g of acetone and 3.76g of triethylamine at 40 ℃ for 5min, adding 18g of 50% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt (A-95) for reaction for 30min, adding 677g of water for high-speed dispersion, immediately adding 4.5g of ethylenediamine for reaction for 30min after dispersion is finished, and removing the acetone at 50 ℃ and-0.1 MPa for 30min to obtain the waterborne polyurethane resin.
Example 2
The preparation method of the waterborne polyurethane resin comprises the following steps:
(1) stirring 300g of dimer acid polyester polyol (with the number average molecular weight of 2000), 5g of DMPA and 0.1g of catalyst BICAT8118 at 50 ℃ for 20min, adding 100g of dicyclohexylmethane diisocyanate and 20g of 1, 6-hexamethylene diisocyanate, and reacting at normal pressure and 80 ℃ for 2.5h to obtain an initial product;
(2) mixing the initial product obtained in the step (1), 6g of methyl propylene glycol, 3g of ethanolamine and 150g of acetone at 62 ℃ for 2h, adding 0.1g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;
(3) and (3) mixing the intermediate product obtained in the step (2), 150g of acetone and 3.76g of triethylamine at 40 ℃ for 5min, adding 18g of 50% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt (A-95) for reaction for 30min, adding 677g of water for high-speed dispersion, immediately adding 4.5g of ethylenediamine for reaction for 30min after the dispersion is finished, and removing the acetone at 50 ℃ and-0.09 MPa for 30min to obtain the waterborne polyurethane resin.
Example 3
The preparation method of the waterborne polyurethane resin comprises the following steps:
(1) stirring 190g of dimer acid polyester polyol (number average molecular weight of 3000), 80g of polycarbonate diol (number average molecular weight of 2000), 40g of polypropylene oxide ether glycol (number average molecular weight of 2000) and 0.1g of catalyst BICAT8118 at 50 ℃ for 20min, adding 100g of isophorone diisocyanate and 20g of 1, 6-hexamethylene diisocyanate, and reacting at normal pressure and 85 ℃ for 2.5h to obtain an initial product;
(2) mixing the initial product obtained in the step (1), 5g of DMPA, 7g of 1, 6-hexanediol and 150g of acetone at 62 ℃ for 2h, adding 0.1g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;
(3) and (3) mixing the intermediate product obtained in the step (2), 150g of acetone and 3.76g of triethylamine at 40 ℃ for 5min, adding 18g of 50% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt (A-95) to react for 30min, adding 710g of water to disperse at high speed, immediately adding 6.87g of ethylenediamine to react for 30min after the dispersion is finished, and removing the acetone for 30min at 50 ℃ and-0.09 MPa to obtain the waterborne polyurethane resin.
Example 4
The preparation method of the waterborne polyurethane resin comprises the following steps:
(1) stirring 150g of dimer acid polyester polyol (with the number average molecular weight of 3000), 80g of polycarbonate diol (with the number average molecular weight of 2000), 80g of polypropylene oxide ether glycol (with the number average molecular weight of 2000) and 0.1g of catalyst BICAT8118 at 50 ℃ for 20min, adding 100g of isophorone diisocyanate and 20g of 1, 6-hexamethylene diisocyanate, and reacting at normal pressure and 85 ℃ for 2.5h to obtain an initial product;
(2) mixing the initial product obtained in the step (1), 5g of DMPA, 7g of 1, 6-hexanediol and 150g of acetone at 62 ℃ for 2h, adding 0.1g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;
(3) and (3) mixing the intermediate product obtained in the step (2), 150g of acetone and 3.76g of triethylamine at 40 ℃ for 5min, adding 16g of a 50% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt (A-95) to react for 30min, adding 710g of water to disperse at a high speed, immediately adding 6.87g of ethylenediamine to react for 30min after the dispersion is finished, and removing the acetone at 50 ℃ and-0.09 MPa for 30min to obtain the waterborne polyurethane resin.
Example 5
The preparation method of the waterborne polyurethane resin comprises the following steps:
(1) stirring 210g of dimer acid polyester polyol (with the number average molecular weight of 3000), 100g of polycarbonate diol (with the number average molecular weight of 2000) and 2g of antioxidant Chinox 1010 at 50 ℃ for 20min, adding 105g of toluene diisocyanate, and reacting at normal pressure and 80 ℃ for 2.5h to obtain an initial product;
(2) mixing the initial product obtained in the step (1), 2g of trimethylolpropane, 8g of DMPA and 18g of methyl propylene glycol at 60 ℃ for 2h, adding 0.2g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;
(3) and (3) mixing the intermediate product obtained in the step (2), 100g of acetone and 6.03g of triethylamine at 40 ℃ for 5min, then adding 683g of water for high-speed dispersion, immediately adding 3g of ethylenediamine and 2g of hydrazine hydrate for reaction for 30min after the dispersion is finished, and removing the acetone at 50 ℃ and-0.09 Mpa for 30min to obtain the waterborne polyurethane resin.
Example 6
The preparation method of the waterborne polyurethane resin comprises the following steps:
(1) stirring 210g of dimer acid polyester polyol (with the number average molecular weight of 3000), 100g of polytetrahydrofuran diol (with the number average molecular weight of 2000) and 2g of Chinox 1010 at 50 ℃ for 20min, adding 80g of toluene diisocyanate and 30g of diphenylmethane 4, 4-diisocyanate, and reacting at normal pressure and 80 ℃ for 2.5h to obtain an initial product;
(2) mixing the initial product obtained in the step (1), 10g of DMPA, 150g of acetone and 23g of hexanediol at 60 ℃ for 2h, adding 0.2g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;
(3) and (3) mixing the intermediate product obtained in the step (2), 100g of acetone and 7.54g of triethylamine at 40 ℃ for 5min, then adding 702g of water for high-speed dispersion, immediately adding 2.7g of ethylenediamine and 2g of hydrazine hydrate for reaction for 30min after the dispersion is finished, and removing the acetone at 50 ℃ and under the condition of-0.09 Mpa for 30min to obtain the waterborne polyurethane resin.
Example 7
The preparation method of the waterborne polyurethane resin comprises the following steps:
(1) stirring 200g of dimer acid polyester polyol (number average molecular weight of 3000), 80g of polycarbonate diol (number average molecular weight of 2000), 14g of polyethylene glycol monomethyl ether (number average molecular weight of 1000) and 0.1g of catalyst BICAT8118 at 50 ℃ for 20min, adding 90g of isophorone diisocyanate and 31g of 1, 6-hexamethylene diisocyanate, and reacting at normal pressure and 85 ℃ for 2.5h to obtain an initial product;
(2) mixing the initial product obtained in the step (1), 4g of ethanolamine, 150g of acetone and 21g of 1.4-butanediol at 62 ℃ for 2h, adding 0.1g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;
(3) and (3) reacting the intermediate product obtained in the step (2) with 20g of 50% aqueous solution of ethylenediamine ethanesulfonic acid sodium salt (A-95) at 40 ℃ for 30min, then adding 678g of water for high-speed dispersion, immediately adding 2g of ethylenediamine for reacting for 30min after the dispersion is finished, and removing acetone for 30min at 50 ℃ and-0.09 Mpa to obtain the waterborne polyurethane resin.
Example 8
The preparation method of the waterborne polyurethane resin comprises the following steps:
(1) stirring 200g of dimer acid polyester polyol (with the number average molecular weight of 4000), 110g of polytetrahydrofuran ether glycol (with the number average molecular weight of 2000) and 14g of polyethylene glycol monomethyl ether (with the number average molecular weight of 1000) at 50 ℃ for 20min, adding 2g of Chinox 1010, 80g of toluene diisocyanate and 40g of diphenylmethane 4, 4-diisocyanate, and reacting at normal pressure and 80 ℃ for 2.5h to obtain an initial product;
(2) mixing the initial product obtained in the step (1), 10g of DMPA, 20g of 1, 4-butanediol, 150g of acetone and 2g of trimethylolpropane at 60 ℃ for 2h, adding 0.2g of catalyst BICAT8118, and reacting at 62 ℃ for 2h to obtain an intermediate product;
(3) and (3) mixing the intermediate product obtained in the step (2), 100g of acetone and 7.54g of triethylamine at 40 ℃ for 5min, adding 723g of water for high-speed dispersion, immediately adding 30g of amino-terminated silicone oil and 2g of ethylenediamine for reaction for 30min after the dispersion is finished, and removing the acetone at 50 ℃ and under the condition of-0.09 Mpa for 30min to obtain the waterborne polyurethane resin.
Comparative example 1
An aqueous polyurethane resin is JF-PDY-850H available from Huafeng corporation.
Comparative example 2
An aqueous polyurethane resin which is different from example 1 in that no dimer acid polyester polyol is added in step (1) and the amount of polytetrahydrofuran ether glycol added is 300g, and the other conditions and steps are the same as those in example 1.
Comparative example 3
An aqueous polyurethane resin which is different from example 1 in that step (1) replaces 150g of dimer acid polyester polyol and 150g of polytetrahydrofuran ether glycol with 300g of polycarbonate glycol, and the other conditions and steps are the same as those of example 1.
And (3) performance testing:
(1) 100% modulus, breaking strength and elongation: naturally air-drying the waterborne polyurethane resin into a resin film with the thickness of about 1mm, baking the resin film for 30min at the temperature of 120 ℃, cutting the resin film into a sample piece with the thickness of 2.5 multiplied by 3.5cm, clamping the sample piece on an Shimadzu electronic universal test machine for testing, wherein the model of the machine is as follows: AGS-X-10kN, Shimadzu instruments Inc.
The aqueous polyurethanes obtained in examples 1 to 8 and comparative examples 1 to 3 were tested according to the test method (1) described above, and the test results are shown in table 1:
TABLE 1
| 100% modulus/MPa | Breaking strength/MPa | Elongation/percent | |
| Example 1 | 3.3 | 47 | 730 |
| Example 2 | 3.6 | 53 | 760 |
| Example 3 | 4.1 | 51 | 740 |
| Example 4 | 4.0 | 49 | 760 |
| Example 5 | 3.5 | 54 | 820 |
| Example 6 | 3.4 | 59 | 790 |
| Example 7 | 4.5 | 48 | 720 |
| Example 8 | 4.3 | 52 | 740 |
| Comparative example 1 | 4.8 | 28 | 590 |
| Comparative example 2 | 3.1 | 38 | 860 |
| Comparative example 3 | 5.2 | 58 | 620 |
As can be seen from the data in table 1: the modulus, the breaking strength and the elongation of the waterborne polyurethane resin prepared by using the dimer acid polyester polyol as the raw material are between those of the waterborne polyurethanes provided in the comparative examples 2 and 3, which shows that the modulus, the breaking strength and the elongation of the waterborne polyurethane provided by the invention are relatively balanced, and the physical property requirement of the synthetic leather fabric is met.
Preparing to-be-detected waterborne polyurethane resin synthetic leather: taking 100g of the waterborne polyurethane resin obtained in each of examples 1-8 and comparative examples 1-3, adding 8g of waterborne color paste, and thickening the waterborne color paste to the viscosity of about 5000cps by using a thickening agent; defoaming for 30min by using a washing machine, coating release paper with the thickness of about 0.2mm by blade coating, and drying in an oven at about 100 ℃ for 10min to obtain a waterborne polyurethane film; and (2) performing blade coating on the prepared waterborne polyurethane film by using the prepared waterborne middle layer foaming resin (JF-PDY-519 HY manufactured by Huafeng corporation) with the thickness of 0.35mm, completely drying in an oven at 120 ℃, then coating a layer of waterborne adhesive (JF-PDY-P521H manufactured by Huafeng corporation) on the surface of the waterborne middle layer foaming resin, wherein the blade coating thickness is 0.15mm, finally attaching the Huafeng FA microfiber substrate, drying and removing release paper to obtain the waterborne polyurethane resin synthetic leather to be measured.
(2) Folding endurance at 25 ℃: cutting the to-be-tested waterborne polyurethane resin synthetic leather into a sample piece with the thickness of 7 multiplied by 4.5cm, clamping the sample piece on a normal-temperature folding-resistant machine for testing, wherein the model of the machine is as follows: GT-7071-BN, high-speed rail detection instruments (Dongguan), Inc.
(3) Folding endurance at-15 ℃: cutting the to-be-tested waterborne polyurethane resin synthetic leather into a sample piece with the thickness of 7 multiplied by 4.5cm, clamping the sample piece on a low-temperature bending machine, setting the temperature to be-15 ℃, and testing. The machine model is as follows: GT-7006-V30, high-speed rail detection instruments (Dongguan), Inc.
(4) Wear resistance: cutting the waterborne polyurethane resin synthetic leather to be measured into a wafer with the diameter of 11cm, clamping the sample wafer on a machine, setting a grinding wheel to be H-18, setting the weight to be 750 grams, and setting the model of the machine: GT-7012-T, high-speed rail detection instruments (Dongguan), Inc.
(5) Anti-sticking property: putting the waterborne polyurethane resin synthetic leather to be measured on a clean glass plate, covering a layer of glass plate on the waterborne polyurethane resin synthetic leather, pressing a 3Kg weight, placing the glass plate in a 60 ℃ oven, and taking out the glass plate after 1 hour; cut out into strips of 3cm width and tested in tension in a tensile machine. A machine: shimadzu electronic universal tester, model: AGS-X-10 kN.
(6) And (3) jungle aging: putting the waterborne polyurethane resin synthetic leather to be measured on a clean glass plate, covering a layer of glass plate on the waterborne polyurethane resin synthetic leather, pressing a 3Kg weight, placing the glass plate in a 60 ℃ oven, and taking out the glass plate after 1 hour; cut into a sample strip with the width of 3cm, clamped on a constant temperature and humidity machine according to the specification, set the temperature at 70 ℃ and the humidity at 95%, and tested. The machine model is as follows: MHX-225QK, Shanghai Taichi science and technology, Inc.
The prepared waterborne polyurethane synthetic leather to be tested is tested according to the test methods (2) to (6), and the test results are shown in table 2:
TABLE 2
As can be seen from the data in table 2: the synthetic leather prepared by the waterborne polyurethane synthesized by using the dimer acid polyester polyol as the raw material has obviously improved normal-low temperature bending, abrasion resistance and anti-sticking property.
Specifically, the normal-temperature folding resistance of the synthetic leather prepared from the waterborne polyurethane obtained in the embodiments 1 to 8 is 31 to 38 ten thousand; the low-temperature folding resistance is 5.5-8 ten thousand; the wear resistance is 900-1250 Kg; the anti-adhesion test is free of adhesion or slight adhesion; and (5) carrying out jungle aging test for 3-4.5 weeks.
Comparing example 1 with comparative examples 1 to 3, it can be found that the weather resistance, wear resistance, anti-sticking property and jungle aging test result of the waterborne polyurethane synthesized without adding dimer acid polyester polyol as a raw material are poor.
The applicant states that the invention is illustrated by the above examples to a waterborne polyurethane and its preparation method and application, but the invention is not limited to the above examples, i.e. it does not mean that the invention must be implemented by means of the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The waterborne polyurethane resin is characterized in that raw materials for preparing the waterborne polyurethane resin comprise a combination of dimer acid polyester polyol, diisocyanate, a chain extender and a catalyst;
the raw materials for preparing the dimer acid polyester polyol comprise the combination of dimer acid, dihydric alcohol and a composite stabilizer.
2. The aqueous polyurethane resin according to claim 1, wherein the mass percentage of the dimer acid polyester polyol in the raw materials for preparing the aqueous polyurethane resin is 10-40%;
preferably, the number average molecular weight of the dimer acid polyester polyol is 1000-5000;
preferably, the raw materials for preparing the dimer acid polyester polyol comprise the following components in parts by weight:
preferably, the diol comprises any one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol or 1, 6-hexanediol or a combination of at least two thereof;
preferably, the catalyst comprises any one or a combination of at least two of tetraisopropyl titanate, tetra-n-butyl titanate, tetra-tert-butyl titanate, stannous octoate, dibutyltin dilaurate, bismuth laurate, zinc oxide or antimony trioxide;
preferably, the composite stabilizer comprises a combination of a phosphate-based heat stabilizer and a phosphite-based heat oxygen stabilizer;
preferably, the phosphate-based heat stabilizer comprises any one of triphenyl phosphate, triethyl methylphosphonate or triethyl phosphonoacetate or a combination of at least two of the foregoing;
preferably, the phosphite thermal oxygen stabilizer comprises any one of triphenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite or tetrakis (2, 4-di-tert-butylphenol) -4,4' -biphenylyl diphosphite or a combination of at least two thereof;
preferably, the raw materials for preparing the dimer acid polyester polyol also comprise other dibasic acid;
preferably, the other dibasic acid comprises any one of succinic acid, glutaric acid, adipic acid, azelaic acid or sebacic acid or a combination of at least two thereof;
preferably, the content of other dibasic acids in the raw materials for preparing the dimer acid polyester polyol is 0-50 parts by weight and is not equal to 0.
3. The aqueous polyurethane resin according to claim 1 or 2, wherein the mass ratio of the dimer acid polyester polyol to the diisocyanate is (0.5-2): 1;
preferably, the diisocyanate includes any one or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or tetramethylxylylene diisocyanate, and more preferably any one or a combination of at least two of hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.
4. The aqueous polyurethane resin according to any one of claims 1 to 3, wherein the mass ratio of the dimer acid polyester polyol to the chain extender is (5-10): 1;
preferably, the chain extender comprises a hydrophilic chain extender;
preferably, the hydrophilic chain extender comprises any one or a combination of at least two of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid or sodium ethylenediamine ethanesulfonate;
preferably, the chain extender comprises an alcohol chain extender;
preferably, the alcohol chain extender comprises any one of ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, 3-methyl-1, 5-pentanediol or ethanolamine or a combination of at least two thereof;
preferably, the chain extender further comprises an amine chain extender;
preferably, the amine chain extender comprises ethylene diamine.
5. The aqueous polyurethane resin according to any one of claims 1 to 4, wherein the mass ratio of the catalyst to the dimer acid polyester polyol is (0.00001 to 0.00005): 1.
6. The aqueous polyurethane resin according to any one of claims 1 to 5, wherein the raw materials for the preparation of the aqueous polyurethane resin further comprise any one or a combination of at least two of a neutralizer, a solvent or other polyols;
preferably, the neutralizing agent comprises any one or a combination of at least two of triethylamine, ammonia water, N-methylmorpholine, N-ethylmorpholine, N-methyldiethanolamine or NaOH;
preferably, the solvent comprises acetone and/or butanone;
preferably, the other polyol comprises any one of or a combination of at least two of tetrahydrofuran ether glycol, polycarbonate glycol or polyester polyol;
preferably, the number average molecular weight of the other polyhydric alcohol is 500-4000;
preferably, the mass percentage of the dimer acid polyester polyol in all polyols in the raw materials for preparing the aqueous polyurethane resin is 50-100% and is not equal to 100%.
7. A preparation method of the waterborne polyurethane as described in any one of claims 1 to 6, wherein the preparation method comprises the following steps:
(1) mixing dimer acid polyester polyol, optional other polyol, optional chain extender and optional catalyst, and adding diisocyanate for reaction to obtain an initial product;
(2) mixing the initial product obtained in the step (1), a chain extender and an optional solvent, and adding a catalyst to react to obtain an intermediate product;
(3) and (3) mixing the intermediate product obtained in the step (2), an optional solvent and an optional neutralizer, adding deionized water for dispersion, adding a chain extender for reaction, and removing the solvent to obtain the waterborne polyurethane resin.
8. The preparation method according to claim 7, wherein the temperature of the reaction in the step (1) is 70-95 ℃;
preferably, the reaction of step (1) is carried out under normal pressure conditions;
preferably, the reaction time in the step (1) is 2-4 h;
preferably, the temperature of the mixing in the step (2) is 90-95 ℃;
preferably, the mixing time in the step (2) is 2-3 h;
preferably, the temperature of the reaction in the step (2) is 60-65 ℃;
preferably, the reaction time in the step (2) is 2-3 h.
9. The method according to claim 7 or 8, wherein the temperature of the reaction of step (3) is not higher than 40 ℃;
preferably, the solvent removal in the step (3) is carried out under the condition that the vacuum degree is-0.09 to-0.1 MPa.
10. Use of the aqueous polyurethane resin according to any one of claims 1 to 6 in synthetic leather.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196368A (en) * | 2021-12-24 | 2022-03-18 | 广州市盛邦康体场地材料有限公司 | Water-based environment-friendly adhesive and water-permeable runway material prepared from same |
| CN117384476A (en) * | 2023-11-23 | 2024-01-12 | 东莞市特普优环保新材料有限公司 | TPU waterproof film and preparation method thereof |
| CN117551254A (en) * | 2023-11-14 | 2024-02-13 | 齐鲁工业大学(山东省科学院) | A kind of high-strength paper-based packaging material and preparation method thereof |
| WO2024152495A1 (en) * | 2023-01-16 | 2024-07-25 | 浙江华峰合成树脂有限公司 | Hydroxyl composition for preparing bio-based polyurethane and bio-based polyurethane |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4170612A (en) * | 1978-04-13 | 1979-10-09 | National Starch And Chemical Corporation | Pressure sensitive adhesive compositions |
| JP2000281887A (en) * | 1999-04-01 | 2000-10-10 | Du Pont Toray Co Ltd | Thermoplastic copolymerized polyester resin composition |
| JP2001323156A (en) * | 2000-05-15 | 2001-11-20 | Kuraray Co Ltd | Thermoplastic polyurethane resin composition and polyurethane elastic fiber comprising the same |
| JP2008133407A (en) * | 2006-10-31 | 2008-06-12 | Dic Corp | Method for producing polyester resin |
| CN102127202A (en) * | 2010-11-30 | 2011-07-20 | 中科院广州化学有限公司 | High-hydrolysis-resistance aqueous polyurethane having dimer acid structural unit and preparation method thereof |
| CN104497258A (en) * | 2014-12-16 | 2015-04-08 | 安徽灵达化工科技有限公司 | Super-elastic wear-resisting waterborne polyurethane resin and composition and application of super-elastic wear-resisting waterborne polyurethane resin and composition |
| CN105218792A (en) * | 2015-10-16 | 2016-01-06 | 广东大盈化工有限公司 | Environment-friendly type polyester polyvalent alcohol and preparation method thereof |
| US20170129991A1 (en) * | 2014-10-29 | 2017-05-11 | Lotte Fine Chemical Co., Ltd. | Method for producing biodegradable polyester resin and biodegradable resin produced therefrom |
| CN112661947A (en) * | 2020-12-22 | 2021-04-16 | 上海华峰新材料研发科技有限公司 | Polyester polyol and preparation method and application thereof |
-
2021
- 2021-10-21 CN CN202111227432.2A patent/CN113788925A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4170612A (en) * | 1978-04-13 | 1979-10-09 | National Starch And Chemical Corporation | Pressure sensitive adhesive compositions |
| JP2000281887A (en) * | 1999-04-01 | 2000-10-10 | Du Pont Toray Co Ltd | Thermoplastic copolymerized polyester resin composition |
| JP2001323156A (en) * | 2000-05-15 | 2001-11-20 | Kuraray Co Ltd | Thermoplastic polyurethane resin composition and polyurethane elastic fiber comprising the same |
| JP2008133407A (en) * | 2006-10-31 | 2008-06-12 | Dic Corp | Method for producing polyester resin |
| CN102127202A (en) * | 2010-11-30 | 2011-07-20 | 中科院广州化学有限公司 | High-hydrolysis-resistance aqueous polyurethane having dimer acid structural unit and preparation method thereof |
| US20170129991A1 (en) * | 2014-10-29 | 2017-05-11 | Lotte Fine Chemical Co., Ltd. | Method for producing biodegradable polyester resin and biodegradable resin produced therefrom |
| CN104497258A (en) * | 2014-12-16 | 2015-04-08 | 安徽灵达化工科技有限公司 | Super-elastic wear-resisting waterborne polyurethane resin and composition and application of super-elastic wear-resisting waterborne polyurethane resin and composition |
| CN105218792A (en) * | 2015-10-16 | 2016-01-06 | 广东大盈化工有限公司 | Environment-friendly type polyester polyvalent alcohol and preparation method thereof |
| CN112661947A (en) * | 2020-12-22 | 2021-04-16 | 上海华峰新材料研发科技有限公司 | Polyester polyol and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨波等: ""稳定剂及其在聚酯生产中的应用"", 《化纤与纺织技术》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196368A (en) * | 2021-12-24 | 2022-03-18 | 广州市盛邦康体场地材料有限公司 | Water-based environment-friendly adhesive and water-permeable runway material prepared from same |
| WO2024152495A1 (en) * | 2023-01-16 | 2024-07-25 | 浙江华峰合成树脂有限公司 | Hydroxyl composition for preparing bio-based polyurethane and bio-based polyurethane |
| CN117551254A (en) * | 2023-11-14 | 2024-02-13 | 齐鲁工业大学(山东省科学院) | A kind of high-strength paper-based packaging material and preparation method thereof |
| CN117384476A (en) * | 2023-11-23 | 2024-01-12 | 东莞市特普优环保新材料有限公司 | TPU waterproof film and preparation method thereof |
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