CN103724574A - Preparation method of non-ionic waterborne polyurethane-polyacrylate composite emulsion for leather finishing - Google Patents
Preparation method of non-ionic waterborne polyurethane-polyacrylate composite emulsion for leather finishing Download PDFInfo
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- CN103724574A CN103724574A CN201310652019.XA CN201310652019A CN103724574A CN 103724574 A CN103724574 A CN 103724574A CN 201310652019 A CN201310652019 A CN 201310652019A CN 103724574 A CN103724574 A CN 103724574A
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- composite emulsion
- polyurethane
- aqueous polyurethane
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- 239000000839 emulsion Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010985 leather Substances 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000004945 emulsification Methods 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000004814 polyurethane Substances 0.000 claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 31
- 229940070721 polyacrylate Drugs 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 26
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 25
- 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 24
- 239000003643 water by type Substances 0.000 claims description 24
- 241000047703 Nonion Species 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 16
- -1 small molecules amine Chemical class 0.000 claims description 15
- 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 14
- 150000002009 diols Chemical class 0.000 claims description 14
- 238000010907 mechanical stirring Methods 0.000 claims description 14
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 13
- 229920000151 polyglycol Polymers 0.000 claims description 13
- 239000010695 polyglycol Substances 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 11
- 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 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- 239000004159 Potassium persulphate Substances 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 235000019394 potassium persulphate Nutrition 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims 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 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- AJDTZVRPEPFODZ-PAMPIZDHSA-J [Sn+4].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O Chemical compound [Sn+4].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O AJDTZVRPEPFODZ-PAMPIZDHSA-J 0.000 claims description 2
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N tetramethylbenzene Natural products CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-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
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 18
- 229920005989 resin Polymers 0.000 abstract description 18
- 239000006185 dispersion Substances 0.000 abstract description 7
- 150000001450 anions Chemical class 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 125000002091 cationic group Chemical group 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 229920000768 polyamine Polymers 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 238000005070 sampling Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- 238000004049 embossing Methods 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 150000003673 urethanes Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 1
- 241001125620 Dermochelys coriacea Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
The invention relates to a preparation method of non-ionic waterborne polyurethane-polyacrylate composite emulsion for leather finishing. The preparation method comprises the following steps: after low polymer dihydric alcohol, diisocyanate and a hydrophilia chain extender are stirred for reaction, cooling to indoor temperature and adding an acrylate monomer and a certain amount of a solvent for reducing viscosity; adding water for emulsification under the high-speed dispersion; then adding a micromolecule polyamine chain extender to conduct chain extension in water to obtain an acrylate monomer-polyurethane waterborne dispersing emulsion; then introducing nitrogen, heating, dropwise adding a water solution containing an initiator to trigger seeding emulsion polymerization, and continuously keeping warm to obtain the composite emulsion. The composite emulsion prepared by the invention has the advantages of low viscosity, good permeability, emulsion stability, freeze-thaw resistance, hydrolytic resistance, and excellent electrolyte resistance and acid-base resistance property, can be used for compounding with anion resin and further with cationic resin, has an excellent knurling setting property, and is particularly suitable for being used as a leather finishing agent.
Description
Technical field
The invention belongs to leather finish macromolecular material production technical field, being specifically related to a kind of side chain is the preparation method of the non-ion aqueous polyurethane-poly acrylate composite emulsion of repetition oxyethyl group structure.
Background technology
Aqueous polyurethane is used widely in fields such as coating, tackiness agent, leather finish and ink with its low VOC content and excellent performance.The dispersion of urethane in water realizes by outer emulsion process or internal emulsification method.Outer emulsion process because technology controlling and process is strict, stability of emulsion is poor, easy precipitation, water-resistance property of coating be very poor and seldom use.The standby polyaminoester emulsion of internal emulsification legal system can be divided into again ionic and non-ionic type according to the kind of hydrophilic monomer.Ionic aqueous polyurethane emulsion, owing to introducing ionic group on molecular structure, therefore emulsion to soda acid, ionogen and low-temperature phase to sensitivity, and neutralizing agent triethylamine usually makes emulsion with ammonia taste, and ionic just because of resin, make resin can only with nonionic or composite with resin or the dispersible pigment color paste of self same ion, limited the use range of ionic resin.And non-ionic resin is inclined to without ion due to itself, both can be composite with anionic materials, also can be composite with cationic materials, when composite resin, there is suitability widely, can make up the shortcoming of ionic resin.Non-ionic polyurethane often reaches hydrophilic object by introduce the ethylene oxide unit repeating on main chain or side chain.Chinese patent CN 200910144800.X proposes a kind of method of preparing side-chain non-ion aqueous polyurethane emulsion, under drying nitrogen protection, by oligomer polyol, isocyanic ester adds in reaction vessel, under mechanical stirring, control temperature reacts after 2-3 hour at 80 ℃-100 ℃, reduce system temperature to 40 ℃-60 ℃, add chainextender, with the wetting ability chainextender that repeats oxyethyl group, linking agent, solvent and catalyzer, continue reaction, in the performed polymer that question response generates, isocyanate group-NCO content no longer changes, be cooled to again room temperature, under high speed dispersion, add water and carry out emulsification, and its underpressure distillation is sloughed to solvent, obtain side-chain non-ion aqueous polyurethane emulsion.The side-chain non-ion aqueous polyurethane emulsion of preparation has high solids content and low viscosity, excellent stability of emulsion, and hydrolytic resistance preferably, excellent electrolyte-resistant, acidproof, alkali resistance, can be used for textile finishing coating-forming agent and hide finishes.
But the resin of preparing due to the method is simple urethane resin, therefore cannot avoid the shortcomings such as the intrinsic water-fast weathering resistance of aqueous polyurethane, embossing constancy.
Polyacrylic ester is soluble in acetone, ethyl acetate, benzene and methylene dichloride, and water insoluble.Polyacrylic ester can form good luster and water-fast film has excellent weathering resistance, chemical-resistant and high hardness and gloss, but wear resistance, winter hardiness and adhesivity are poor, and tensile strength is not high, can be used as pressure-sensitive adhesive and thermo-sensitivity binding agent.Can find out, urethane and acrylate respectively have relative merits, and urethane has excellent elasticity, wear resistance, toughness, sticking power and outstanding low temperature resistant flexibility, but aspect weathering resistance, water tolerance, alkali resistance and embossing constancy Shortcomings; And polyacrylic ester has good weathering resistance, water tolerance, alkali resistance and embossing constancy, but elasticity and wear no resistance, hot sticky cold crisp.Therefore,, in order to make up the shortcoming of two kinds of resins, people are in addition compound by these two kinds of resins, to bring into play both advantages.The patent application relevant to polyurethane-polyacrylate composite emulsion at present mainly contains:
1, application number 200480020225.8; denomination of invention " waterborne self-crosslinkable polyurethane dispersions and urethane: acrylic hybrid dispersions "; relate to a kind of comprising as independent particle or as the hybrid polymer thing dispersion of functionalized polyurethane polymkeric substance (A) and the functional vinyl polymkeric substance (B) of composite particles; wherein polyether polyols with reduced unsaturation is prepared in the agglomerated solvent of high boiling point oxidation, and described solvent does not contain with the functional group of isocyanate reaction and still retains after water-dispersion.The mode of its acrylic hybrid dispersions by blend be compound to urethane and polyacrylic ester, but the synergistic effect that in the composite emulsion that the method makes, urethane and polyacrylic ester strengthen is mutually inadequate, and the poor stability of blend.
2, Chinese patent CN 200310112355.1, relates to core-shell particles and method for making and application that a kind of Acrylated urethanes is core main body.This core-shell particles, take the multipolymer of Acrylated urethanes monomer and esters of acrylic acid soft monomer as core, then in grafting outward, esters of acrylic acid hard monomer is shell.Its method for making comprises the steps: 1), prepare Acrylated urethanes; 2), reemulsification, obtain the Acrylated urethanes emulsion of water-based; 3), A: add esters of acrylic acid soft monomer in above-mentioned emulsion, react to obtain seed emulsion; B: add esters of acrylic acid hard monomer to react to obtain core-shell emulsion in above-mentioned seed emulsion; 4), use sodium chloride saturated solution breakdown of emulsion, freezing, suction filtration, washing, dry, grind, obtain the core-shell particles that Acrylated urethanes is core main body.Core-shell particles can be used as toughner in epoxy resin and can not cause second-order transition temperature to reduce by a relatively large margin, has good interface compatibility with epoxy resin, and the method for making tool feature of environmental protection.By waterborne polyurethane-acrylate emulsion prepared by seed emulsion polymerization method, for the modification of epoxy resin.The method is mainly used for preparing anion polyurethane-acrylate composite emulsion.
Above patent information shows, resin prepared by above-mentioned two kinds of methods is all ionic emulsion, and is mainly negatively charged ion system, in the particularly composite less stable in upper leather back cover cationic system used of leather.Therefore be necessary that the compatibilities such as synthetic one and ionic resin, auxiliary agent are good, there is nonionic and composite attribute simultaneously, and have the leather nonionic polyurethane-acrylate composite emulsion of urethane and acrylate advantage concurrently.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of non-ion aqueous polyurethane-poly acrylate composite emulsion, composite emulsion obtained by this method has good stability, acid and alkali-resistance and ionogen, the feature that embossing constancy is good, is particularly useful for doing hide finishes.
For achieving the above object, the technical solution used in the present invention is as follows:
A preparation method for non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish, is characterized in that processing step is as follows:
1) preparation of acrylate-polyurethane seed emulsion
A is by polymer diatomic alcohol vacuum hydro-extraction processing in advance, get 25～42 parts, get again 0.06～0.2 part of 10～20 parts of vulcabond, 23～29 parts of nonionic hydrophilic chain extenders, catalyzer and add in reaction vessel, under mechanical stirring, in 70～100 ℃ of reactions 2～5 hours;
B is cooled to room temperature by the reactant of steps A, adds 19～29 parts of acrylate monomers, 10～15 parts of solvents, stirs 15～30 minutes, makes prepolymer dissolve viscosity reduction;
C, under high shear, adds 240 parts of 10 ℃ of deionized waters below, emulsification 5～20 minutes;
D finally adds containing 10～25 parts of the aqueous solution of 0.12～3 part of small molecules amine chainextender, continues to stir 1～2 hour, obtains acrylate-polyurethane seed emulsion;
2) preparation of polyurethane-polyacrylate composite emulsion
Get seed emulsion prepared by the D step of step 1); pass into protection nitrogen; be warming up to 70～90 ℃; dropping is dissolved in by 0.05～0.15 part of initiator the aqueous solution that 48 parts of water form; and dropwised in 2 hours; continue insulation 2～3 hours, obtain polyurethane-polyacrylate composite emulsion product.
In steps A
Described polymer diatomic alcohol is one or more in Polyoxypropylene diol, PCDL, polycaprolactone dibasic alcohol, polyester diol, and number-average molecular weight is 1000～4000.
Described vulcabond is isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), 4,4-dicyclohexyl methane diisocyanate (HMDI), cyclohexanedimethyleterephthalate vulcabond, tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), 1, one or more in 5-naphthalene diisocyanate, xylylene diisocyanate, tetramethyl-benzene dimethyl vulcabond.
Described nonionic hydrophilic chain extender refers to TriMethylolPropane(TMP) poly glycol monomethyl ether, and number-average molecular weight is 1000～2000, and structural formula is as follows:
Described catalyzer is selected organic tin catalyzer or organo-bismuth class catalyzer, and organic tin catalyzer comprises dibutyl tin acetate, dialkyl tin dimaleate, dibutyl tin laurate or stannous octoate etc.; Organo-bismuth class catalyzer is selected from the BiCAT organo-bismuth Polyurethane catalyzer that the leading chemical company of the U.S. is produced, as BiCAT 88%Bi 8%Zn, BiCATZ19%Zn, BiCAT8118 16%Bi, BiCAT3228 22%Zn, BiCAT8108 20%Bi, BiCAT8220 24%Bi, BiCAT8106 20%Bi, BiCATH28%Bi etc.
In step B
Described acrylate monomer is a kind of or its arbitrary combination in C1～C18 ester of methacrylic acid, acrylic acid C1～C18 ester, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, ethylene glycol dimethacrylate or glycol diacrylate.
Described solvent is acetone or butanone.
Small molecules amine chainextender described in step D is one or more in hydrazine hydrate, quadrol, butanediamine, hexanediamine, different Fo Er diamines (IPDA), dimethylene amido benzene (Xylenediamine), polyether diamine, diethylenetriamine or triethylene tetramine.
Step 2) described in initiator be Potassium Persulphate, Sodium Persulfate or ammonium persulphate etc.
Special instruction, the content of the each component of the present invention is mass fraction.
Useful technique effect of the present invention is mainly reflected in the following aspects:
1, the present invention has proposed a kind of method of seed emulsion polymerization for the preparation of nonionic polyurethane-poly acrylate composite emulsion of utilizing first in leather finish field.The present invention carries out IPN polymerization by introduce polyacrylic ester in non-ionic polyurethane emulsion, the emulsion obtaining has the two-fold advantage of urethane resin and acrylic resin concurrently in mechanical property, be that dry film has good mechanical property, also there is good embossing constancy and feel, solid content reaches 25%, is particularly useful for leather finish field.
2, non-ion aqueous polyurethane-polyacrylic ester that prepared by the present invention is the compound resin using water as dispersion medium, do not need additional emulsifying agent, in the time of the water tolerance of raising emulsion and stability, also improved the freeze-thaw resistance of emulsion, and reduced cost simultaneously.
3, the compound resin that prepared by the present invention is non-ionic resin, thereby emulsion is insensitive to various environmental factorss such as acid, alkali and ionogen, and there is low viscosity and good permeability, both can be composite with nonionic, resin anion(R.A) and material, also can be composite with resin cation (R.C.) and material, therefore there is wider composite suitability.
4, the present invention can be by regulating the content of hydrophilic monomer, the relative content of polyurethane/polyacrylate, the parameters such as the kind of oligopolymer dibasic alcohol and acrylate monomer and small molecule chain extender and content, obtain the film of various different mechanical properties, to adapt to different requirements.
5, the each processing step of the present invention cooperatively interacts and acts on each other, and under the raw material composition and the control of relevant parameter condition of specific proportioning, effectively realized the synthetic of nonionic polyurethane-poly acrylate composite emulsion, there is good stability, acid and alkali-resistance and ionogen, the superior technique effect that embossing constancy is good, is particularly useful for doing hide finishes.
The embodiment of form by the following examples, is described in further detail foregoing of the present invention again.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following examples, all technique means realizing based on foregoing of the present invention all belong to scope of the present invention.
Embodiment
The related raw material of following examples is as follows:
Isophorone diisocyanate (IPDI);
1,6-hexamethylene diisocyanate (HDI);
4,4-dicyclohexyl methane diisocyanate (HMDI);
Number-average molecular weight is 1000, and hydroxyl value is the TriMethylolPropane(TMP) poly glycol monomethyl ether (Bai Situo, Ymer N120) of 110 mg KOH/g;
Dibutyl tin laurate; Organo-bismuth BiCAT 8118;
Methyl methacrylate; Butyl acrylate; Ethyl propenoate; Isooctyl acrylate monomer;
Hydrazine hydrate; Triethylene tetramine (TETA);
Acetone;
Number-average molecular weight is 2000, hydroxyl value is the Polyoxypropylene diol of 56 mg KOH/g, industrial goods;
Number-average molecular weight is 1000, hydroxyl value is the Polyoxypropylene diol of 112 mg KOH/g, industrial goods;
Number-average molecular weight is 2000, hydroxyl value is the PCDL of 53～59 mg KOH/g, industrial goods; Polyester diol: Bai Situo Oxymer M112, NIPPOLLAN 963, Bai Situo CAPA2101A;
Number-average molecular weight is 1000, hydroxyl value is the PCDL of 104～120 mg KOH/g, industrial goods;
Number-average molecular weight is 1000, and hydroxyl value is the polycaprolactone dibasic alcohol of 112 mg KOH/g;
Potassium sulfate, Sodium Persulfate, ammonium persulphate.
embodiment 1
By the number-average molecular weight after vacuum hydro-extraction, be 2000, hydroxyl value is Polyoxypropylene diol 10.0 g of 56 mg KOH/g, isophorone diisocyanate 4.0 g, TriMethylolPropane(TMP) poly glycol monomethyl ether 9.2 g, catalyzer dibutyl tin laurate 0.024 g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 3 hours at 85 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0076 mol) or when following, system temperature is down to room temperature, add butyl acrylate 3.60 g, methyl methacrylate 4.00 g, acetone 4 g, continue to stir 15～30 minutes, under 950 rpm high shear forces, add 26 g deionized waters, emulsification 2min, add again 70 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 0.24 g hydrazine hydrate (massfraction 80%) and 4 g water, react after 1～2 hour, then pass into nitrogen, be warming up to 75 ℃, in 2 hours, drip the mixed solution being formed by 0.02 g Potassium Persulphate and 19.2 g water, continue insulation 2～3 hours, obtain solid content and be about non-ionic water polyurethane-poly acrylate composite emulsion product of 20%.（PU=23.416g，PA=7.6g，PUA=31.016g）
comparative example 1
By the number-average molecular weight after vacuum hydro-extraction, be 2000, hydroxyl value is the Polyoxypropylene diol 17.41g of 56 mg KOH/g, isophorone diisocyanate 5.37g, TriMethylolPropane(TMP) poly glycol monomethyl ether 5.82g, catalyzer dibutyl tin laurate 0.025g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 3 hours at 85 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0194 mol) or when following, system temperature is down to room temperature, add acetone 4g, continue to stir 15～30 minutes, under 950 rpm high shear forces, add 27.4 g deionized waters, emulsification 2min, add again 54.8 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 0.61g hydrazine hydrate (massfraction 80%) and 4 g water, reaction 1～2h, obtain solid content and be about 25% non-ionic water polyurethane product emulsion.
comparative example 2
By the number-average molecular weight after vacuum hydro-extraction, be 2000, hydroxyl value is the Polyoxypropylene diol 15.40g of 56 mg KOH/g, isophorone diisocyanate 5.37g, dimethylol propionic acid 0.91g, catalyzer dibutyl tin laurate 0.025g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 3 hours at 85 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0194 mol) or when following, system temperature is down to room temperature, add acetone 4 g, stir 15 minutes, add triethylamine 0.69g, react 15 minutes, under 950 rpm high shear forces, add 21.2 g deionized waters, emulsification 2 min, add again 42.4 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 0.61 g hydrazine hydrate (massfraction 80%) and 4 g water, reaction 1～2 h, obtain solid content and be about 25% anion aqueous polyurethane product emulsion.
the product performance of embodiment 1, comparative example 1, comparative example 2 are by following 1)～5) test
1) mensuration of water-intake rate: fully dry glued membrane sample is cut into the square of 20 mm × 20 mm, claims that quality is designated as W
1, be placed in deionized water, soak after 24 h and take out, weigh after sucking surface-moisture with filter paper, be designated as W
2, be calculated as follows:
Water-intake rate (%)=[(W
2-W
1)/W
1] × 100%
2) mensuration of emulsion acid and alkali-resistance, salt tolerance: by the hydrochloric acid of a certain amount of 5 wt%, regulate emulsion pH=1, observe stability of emulsion; 10% sodium chloride solution is slowly added drop-wise in emulsion, observes stability of emulsion;
3) mensuration of freeze-thaw resistance: emulsion is placed in to-10 ℃ of freezing 12h of environment, being heated to 50 degree thawings, repeats 3 times, observe stability of emulsion;
4) mensuration of tensile strength: glued membrane is made to the dumbbell shaped of 30 mm × 3 mm, used XLM-Intelligent electronic tensil testing machine to test its tensile strength, draw speed is 150 mm/min;
5) test of embossing shaping performance.
The performance test results sees the following form
As can be seen from the above table, the embodiment of the present invention 1 product is with respect to comparative example 2(anion aqueous polyurethane product emulsion), there is better acid and alkali-resistance, salt tolerant, freeze-thaw resistance, and good stability; And with respect to comparative example 1, showing as again water tolerance increases, embossing constancy is good, and tensile strength improves, and product of the present invention has more good over-all properties, is especially suitable as hide finishes and uses.
embodiment 2
By the number-average molecular weight after vacuum hydro-extraction, be 2000, hydroxyl value is the PCDL PCD 16.8g of 53～59 mg KOH/g, isophorone diisocyanate 8.0 g, TriMethylolPropane(TMP) poly glycol monomethyl ether 11.6 g, catalyzer dibutyl tin laurate 0.08 g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 3 hours at 85 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0321 mol) or when following, system temperature is down to room temperature, add butyl acrylate 6.6 g, methyl methacrylate 5.0 g, acetone 6 g, continue to stir 15～30 minutes, under 950 rpm high shear forces, add 26 g deionized waters, emulsification 2min, add again 70 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 1.00 g hydrazine hydrates (massfraction 80%) and 10 g water, react after 1～3 hour, then pass into nitrogen, be warming up to 75 ℃, in 2 hours, drip the mixed solution being formed by 0.06 g Potassium Persulphate and 19.2 g water, continue insulation 2～3 hours, obtain non-ionic water polyurethane-poly acrylate composite emulsion product.
embodiment 3
By the number-average molecular weight after vacuum hydro-extraction, be 1000, hydroxyl value is Polyoxypropylene diol 8.62 g of 112 mg KOH/g, isophorone diisocyanate 6.75 g, TriMethylolPropane(TMP) poly glycol monomethyl ether 9.59 g, catalyzer dibutyl tin laurate 0.025g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 3 hours at 85 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0244 mol) or when following, system temperature is down to room temperature, add butyl acrylate 5.24g, methyl methacrylate 1.13g, acetone 4g, continue to stir 15～30 minutes, under 950 rpm high shear forces, add 27 g deionized waters, emulsification 2 min, add again 53 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 0.76 g hydrazine hydrate (massfraction 80%) and 4 g water, react after 1～3 hour, then pass into nitrogen, be warming up to 75 ℃, in 2 hours, drip the mixed solution containing 0.019 g Potassium Persulphate and 16 g water, continue insulation 2～3 hours, obtain non-ionic water polyurethane-poly acrylate composite emulsion product.
embodiment 4
By the number-average molecular weight after vacuum hydro-extraction, be 2000, hydroxyl value is Polyoxypropylene diol 13.19 g of 56 mg KOH/g, isophorone diisocyanate 5.40 g, TriMethylolPropane(TMP) poly glycol monomethyl ether 8.00 g, catalyzer dibutyl tin laurate 0.025g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 3 hours at 85 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0194 mol) or when following, system temperature is down to room temperature, add butyl acrylate 3.95 g, methyl methacrylate 0.85 g, acetone 4 g, continue to stir 15～30 minutes, under 950 rpm high shear forces, add 27 g deionized waters, emulsification 2 min, add again 53 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 0.61 g hydrazine hydrate (massfraction 80%) and 4 g water, react after 1～3 hour, then pass into nitrogen, be warming up to 75 ℃, in 2 hours, drip the mixed solution being formed by 0.019 g Potassium Persulphate and 16 g water, continue insulation 2～3 hours, obtain non-ionic water polyurethane-poly acrylate composite emulsion product.
embodiment 5
By the number-average molecular weight after vacuum hydro-extraction, be 2000, hydroxyl value is Polyoxypropylene diol 14.31 g of 56 mg KOH/g, 1, 6-hexamethylene diisocyanate 4.24 g, TriMethylolPropane(TMP) poly glycol monomethyl ether 7.99 g, catalyzer dibutyl tin laurate 0.025g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 3 hours at 85 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0202 mol) or when following, system temperature is down to room temperature, add butyl acrylate 2.40 g, methyl methacrylate 2.40 g, acetone 3 g, continue to stir 15～30 minutes, under 950 rpm high shear forces, add 27 g deionized waters, emulsification 2 min, add again 53 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 0.63 g hydrazine hydrate (massfraction 80%) and 4 g water, react after 1～3 hour, then pass into nitrogen, be warming up to 75 ℃, in 2 hours, drip the mixed solution being formed by 0.014 g Potassium Persulphate and 16 g water, continue insulation 2～3 hours, obtain non-ionic water polyurethane-poly acrylate composite emulsion product.
embodiment 6
By the number-average molecular weight after vacuum hydro-extraction, be 2000, hydroxyl value is Polyoxypropylene diol 15.09 g of 56 mg KOH/g, 1, 6-hexamethylene diisocyanate 3.67 g, TriMethylolPropane(TMP) poly glycol monomethyl ether 8.04 g, catalyzer dibutyl tin laurate 0.025g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 3 hours at 85 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0161 mol) or when following, system temperature is down to room temperature, add butyl acrylate 2.40 g, methyl methacrylate 2.40 g, acetone 3 g, continue to stir 15～30 minutes, under 950 rpm high shear forces, add 27 g deionized waters, emulsification 2 min, add again 53 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 0.39 g hydrazine hydrate (massfraction 80%) and 4 g water, react after 1～3 hour, then pass into nitrogen, be warming up to 75 ℃, in 2 hours, drip the mixed solution being formed by 0.014 g Potassium Persulphate and 16 g water, continue insulation 2～3 hours, obtain non-ionic water polyurethane-poly acrylate composite emulsion product.
embodiment 7
By the number-average molecular weight after vacuum hydro-extraction for being 1000, hydroxyl value is PCDL 4.97 g of 104～120 mg KOH/g, 4, 4-dicyclohexyl methane diisocyanate 6.34 g, TriMethylolPropane(TMP) poly glycol monomethyl ether 9.55 g, catalyzer dibutyl tin laurate 0.025 g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 5 hours at 70 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0194 mol) or when following, system temperature is down to room temperature, add ethyl propenoate 6.37 g, acetone 4g, continue to stir 15～30 minutes, under 950 rpm high shear forces, add 27 g deionized waters, emulsification 2min, add again 53 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 0.61 g hydrazine hydrate (massfraction 80%) and 4 g water, react after 1～2 hour, then pass into nitrogen, be warming up to 80 ℃, in 2 hours, drip the mixed solution being formed by 0.019 g Potassium Persulphate and 16 g water, continue insulation 2～3 hours, obtain non-ionic water polyurethane-poly acrylate composite emulsion product.
embodiment 8
By the number-average molecular weight after vacuum hydro-extraction, be 1000, hydroxyl value is polycaprolactone dibasic alcohol 4.97 g of 112 mg KOH/g, isophorone diisocyanate 5.37 g, TriMethylolPropane(TMP) poly glycol monomethyl ether 9.55 g, catalyzer dibutyl tin laurate 0.025g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 2 hours at 90 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0194 mol) or when following, system temperature is down to room temperature, add Isooctyl acrylate monomer 6.37 g, acetone 4g, continue to stir 15～30 minutes, under 950 rpm high shear forces, add 27 g deionized waters, emulsification 2min, add again 53 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 0.61 g hydrazine hydrate (massfraction 80%) and 4 g water, react after 1～2 hour, then pass into nitrogen, be warming up to 90 ℃, in 2 hours, drip the mixed solution being formed by 0.019 g Ammonium Persulfate 98.5 and 16 g water, continue insulation 2～3 hours, obtain non-ionic water polyurethane-poly acrylate composite emulsion product.
embodiment 9
M112 4.97 g that are 1000 by the number-average molecular weight after vacuum hydro-extraction, isophorone diisocyanate 5.37 g, TriMethylolPropane(TMP) poly glycol monomethyl ether 9.55g, catalyzer dibutyl tin laurate 0.025 g adds in 250 mL reaction vessels, under mechanical stirring, control temperature reacted after 3.5 hours at 80 ℃, sampling and measuring NCO content, when NCO content reaches preset value (0.0194 mol) or when following, system temperature is down to room temperature, add butyl acrylate 3.37 g, ethyl propenoate 3.00 g, acetone 4 g, continue to stir 15～30 minutes, under 950 rpm high shear forces, add 27 g deionized waters, emulsification 2 min, add again 53 g deionized waters, continue emulsification 13 minutes, reduce stirring velocity, the hydrazine hydrate solution that dropping is comprised of 0.61 g hydrazine hydrate (massfraction 80%) and 4 g water, react after 1～2 hour, then pass into nitrogen, be warming up to 70 ℃, in 2 hours, drip the mixed solution being formed by 0.019 g Sodium Persulfate and 16 g water, continue insulation 2～3 hours, obtain non-ionic water polyurethane-poly acrylate composite emulsion product.
Claims (10)
1. a preparation method for non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish, is characterized in that processing step is as follows:
1) preparation of acrylate-polyurethane seed emulsion
A is by polymer diatomic alcohol vacuum hydro-extraction processing in advance, get 25～42 parts, get again 0.06～0.2 part of 10～20 parts of vulcabond, 23～29 parts of nonionic hydrophilic chain extenders, catalyzer and add in reaction vessel, under mechanical stirring, in 70～100 ℃ of reactions 2～5 hours;
B is cooled to room temperature by the reactant of steps A, adds 19～29 parts of acrylate monomers, 10～15 parts of solvents, stirs 15～30 minutes, makes prepolymer dissolve viscosity reduction;
C, under high shear, adds 240 parts of 10 ℃ of deionized waters below, emulsification 5～20 minutes;
D finally adds containing 10～25 parts of the aqueous solution of 0.12～3 part of small molecules amine chainextender, continues to stir 1～2 hour, obtains acrylate-polyurethane seed emulsion;
2) preparation of polyurethane-polyacrylate composite emulsion
Get seed emulsion prepared by the D step of step 1); pass into protection nitrogen; be warming up to 70～90 ℃; dropping is dissolved in by 0.05～0.15 part of initiator the aqueous solution that 48 parts of water form; and dropwised in 2 hours; continue insulation 2～3 hours, obtain polyurethane-polyacrylate composite emulsion product.
2. the preparation method of non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish according to claim 1, it is characterized in that: the polymer diatomic alcohol described in steps A is one or more in Polyoxypropylene diol, PCDL, polycaprolactone dibasic alcohol, polyester diol, and number-average molecular weight is 1000～4000.
3. the preparation method of non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish according to claim 1, it is characterized in that: the vulcabond described in steps A is isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 4,4-dicyclohexyl methane diisocyanate, cyclohexanedimethyleterephthalate vulcabond, tolylene diisocyanate, diphenylmethanediisocyanate, 1, one or more in 5-naphthalene diisocyanate, xylylene diisocyanate, tetramethyl-benzene dimethyl vulcabond.
4. the preparation method of non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish according to claim 1, it is characterized in that: the nonionic hydrophilic chain extender described in steps A refers to TriMethylolPropane(TMP) poly glycol monomethyl ether, number-average molecular weight is 1000～2000.
5. the preparation method of non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish according to claim 1, is characterized in that: the catalyzer described in steps A is selected from organic tin catalyzer dibutyl tin acetate, dialkyl tin dimaleate, dibutyl tin laurate or stannous octoate.
6. the preparation method of non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish according to claim 1, is characterized in that: the catalyzer described in steps A is selected from the BiCAT organo-bismuth Polyurethane catalyzer that the leading chemical company of the U.S. is produced.
7. the preparation method of non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish according to claim 1, is characterized in that: a kind of in C1～C18 ester that the acrylate monomer described in step B is methacrylic acid, acrylic acid C1～C18 ester, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, ethylene glycol dimethacrylate or glycol diacrylate or its combine arbitrarily.
8. the preparation method of non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish according to claim 1, is characterized in that: the solvent described in step B is acetone or butanone.
9. the preparation method of non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish according to claim 1, is characterized in that: the small molecules amine chainextender described in step D is one or more in hydrazine hydrate, quadrol, butanediamine, hexanediamine, different Fo Er diamines, dimethylene amido benzene, polyether diamine, diethylenetriamine or triethylene tetramine.
10. the preparation method of non-ion aqueous polyurethane-poly acrylate composite emulsion for leather finish according to claim 1, is characterized in that: step 2) described in initiator be Potassium Persulphate, Sodium Persulfate or ammonium persulphate.
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119543A (en) * | 2014-07-16 | 2014-10-29 | 江南大学 | Preparation method of non-ionic UV-cured aqueous polyurethane acrylate |
| CN104356343A (en) * | 2014-11-04 | 2015-02-18 | 佛山市功能高分子材料与精细化学品专业中心 | Epoxy resin and castor oil double-modified polyurethane leather finishing agent and preparation method thereof |
| CN106833361A (en) * | 2017-02-23 | 2017-06-13 | 广州优瑞塑料有限公司 | A kind of antibacterial aqueous polyurethane coating glue of silver ion deodorizing |
| CN107446108A (en) * | 2017-07-27 | 2017-12-08 | 滁州金桥德克新材料有限公司 | A kind of aqueous polyurethane acrylate emulsion and preparation method thereof |
| CN107522839A (en) * | 2017-08-30 | 2017-12-29 | 广东德美精细化工集团股份有限公司 | A kind of solvent-free waterborne polyurethane resin preparation method for possessing anion and nonionic nature |
| CN107938357A (en) * | 2017-12-04 | 2018-04-20 | 上海雅运纺织助剂有限公司 | A kind of Fabric Style finishing agent composition and preparation method thereof |
| CN108129636A (en) * | 2017-12-19 | 2018-06-08 | 传化智联股份有限公司 | A kind of preparation method of amphipathic pectinate texture polysiloxane-polyurethane graft copolymer |
| CN109457493A (en) * | 2018-12-27 | 2019-03-12 | 浙江东进新材料有限公司 | A kind of environment-friendly waterproof bag fabric |
| CN109608605A (en) * | 2017-12-19 | 2019-04-12 | 传化智联股份有限公司 | A kind of ion-non-ion aqueous polyurethane dispersion preparation |
| CN109971254A (en) * | 2019-03-04 | 2019-07-05 | 上海图赢科技发展有限公司 | A kind of aqueous leather digit printing ink-jet writing ink and its preparation method and application |
| CN110354823A (en) * | 2019-07-10 | 2019-10-22 | 丽水学院 | A kind of novel quaternization cyclodextrin polyurethane copolymer material and preparation method thereof |
| CN111019082A (en) * | 2019-12-16 | 2020-04-17 | 东南大学 | Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof |
| CN112194769A (en) * | 2020-09-28 | 2021-01-08 | 广州科苑新型材料有限公司 | Waterborne polyurethane/polyacrylate modified ketone-aldehyde resin composite emulsion and preparation method and application thereof |
| WO2021118124A1 (en) * | 2019-12-13 | 2021-06-17 | 주식회사 아이센스 | Non-mixed amphiphilic thermoplastic polyurethane, method for producing same, and implantable medical device including same |
| CN113195648A (en) * | 2018-12-21 | 2021-07-30 | Dic株式会社 | Aqueous urethane resin dispersion, coating film, laminate, and method for producing aqueous urethane resin dispersion |
| CN113244132A (en) * | 2020-02-13 | 2021-08-13 | 万华化学集团股份有限公司 | Aqueous nail polish based on dopa modified aqueous polyurethane (meth) acrylate dispersion and preparation method thereof |
| CN113874453A (en) * | 2019-06-04 | 2021-12-31 | 陶氏环球技术有限责任公司 | Heat-sensitive aqueous polyurethane dispersion and preparation method thereof |
| CN114057950A (en) * | 2020-07-30 | 2022-02-18 | 湖北远大生命科学与技术有限责任公司 | Spherical polyurethane graft modified polyacrylate macroporous anion resin, preparation method thereof and application thereof in taurine production |
| CN114164679A (en) * | 2021-11-08 | 2022-03-11 | 福建冠兴皮革有限公司 | Stain-resistant and folding-resistant leather product and preparation method thereof |
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| CN102604015A (en) * | 2012-02-28 | 2012-07-25 | 张家界市桐发科技有限公司 | Preparation method of waterborne polyurethane emulsion modified by methyl esterification tung oil and product of waterborne polyurethane emulsion |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119543A (en) * | 2014-07-16 | 2014-10-29 | 江南大学 | Preparation method of non-ionic UV-cured aqueous polyurethane acrylate |
| CN104356343A (en) * | 2014-11-04 | 2015-02-18 | 佛山市功能高分子材料与精细化学品专业中心 | Epoxy resin and castor oil double-modified polyurethane leather finishing agent and preparation method thereof |
| CN104356343B (en) * | 2014-11-04 | 2017-05-17 | 佛山市功能高分子材料与精细化学品专业中心 | Epoxy resin and castor oil double-modified polyurethane leather finishing agent and preparation method thereof |
| CN106833361A (en) * | 2017-02-23 | 2017-06-13 | 广州优瑞塑料有限公司 | A kind of antibacterial aqueous polyurethane coating glue of silver ion deodorizing |
| CN107446108A (en) * | 2017-07-27 | 2017-12-08 | 滁州金桥德克新材料有限公司 | A kind of aqueous polyurethane acrylate emulsion and preparation method thereof |
| CN107522839A (en) * | 2017-08-30 | 2017-12-29 | 广东德美精细化工集团股份有限公司 | A kind of solvent-free waterborne polyurethane resin preparation method for possessing anion and nonionic nature |
| CN107938357B (en) * | 2017-12-04 | 2020-01-10 | 上海雅运新材料有限公司 | Fabric style finishing agent composition and preparation method thereof |
| CN107938357A (en) * | 2017-12-04 | 2018-04-20 | 上海雅运纺织助剂有限公司 | A kind of Fabric Style finishing agent composition and preparation method thereof |
| CN109608605A (en) * | 2017-12-19 | 2019-04-12 | 传化智联股份有限公司 | A kind of ion-non-ion aqueous polyurethane dispersion preparation |
| CN108129636A (en) * | 2017-12-19 | 2018-06-08 | 传化智联股份有限公司 | A kind of preparation method of amphipathic pectinate texture polysiloxane-polyurethane graft copolymer |
| CN108129636B (en) * | 2017-12-19 | 2021-01-01 | 传化智联股份有限公司 | Preparation method of amphiphilic comb-structure organic silicon-polyurethane graft copolymer |
| CN113195648A (en) * | 2018-12-21 | 2021-07-30 | Dic株式会社 | Aqueous urethane resin dispersion, coating film, laminate, and method for producing aqueous urethane resin dispersion |
| CN109457493A (en) * | 2018-12-27 | 2019-03-12 | 浙江东进新材料有限公司 | A kind of environment-friendly waterproof bag fabric |
| CN109457493B (en) * | 2018-12-27 | 2021-04-30 | 浙江东进新材料有限公司 | Environment-friendly waterproof case fabric |
| CN109971254B (en) * | 2019-03-04 | 2021-07-20 | 上海图赢科技发展有限公司 | Water-based ink-jet ink for digital printing of leather and preparation method and application thereof |
| CN109971254A (en) * | 2019-03-04 | 2019-07-05 | 上海图赢科技发展有限公司 | A kind of aqueous leather digit printing ink-jet writing ink and its preparation method and application |
| CN113874453A (en) * | 2019-06-04 | 2021-12-31 | 陶氏环球技术有限责任公司 | Heat-sensitive aqueous polyurethane dispersion and preparation method thereof |
| CN110354823A (en) * | 2019-07-10 | 2019-10-22 | 丽水学院 | A kind of novel quaternization cyclodextrin polyurethane copolymer material and preparation method thereof |
| WO2021118124A1 (en) * | 2019-12-13 | 2021-06-17 | 주식회사 아이센스 | Non-mixed amphiphilic thermoplastic polyurethane, method for producing same, and implantable medical device including same |
| CN111019082A (en) * | 2019-12-16 | 2020-04-17 | 东南大学 | Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof |
| CN113244132A (en) * | 2020-02-13 | 2021-08-13 | 万华化学集团股份有限公司 | Aqueous nail polish based on dopa modified aqueous polyurethane (meth) acrylate dispersion and preparation method thereof |
| CN114057950A (en) * | 2020-07-30 | 2022-02-18 | 湖北远大生命科学与技术有限责任公司 | Spherical polyurethane graft modified polyacrylate macroporous anion resin, preparation method thereof and application thereof in taurine production |
| CN114057950B (en) * | 2020-07-30 | 2024-03-22 | 湖北远大生命科学与技术有限责任公司 | Spherical polyurethane grafted modified polyacrylate macroporous anion resin, preparation method thereof and application thereof in taurine production |
| CN112194769A (en) * | 2020-09-28 | 2021-01-08 | 广州科苑新型材料有限公司 | Waterborne polyurethane/polyacrylate modified ketone-aldehyde resin composite emulsion and preparation method and application thereof |
| CN114164679A (en) * | 2021-11-08 | 2022-03-11 | 福建冠兴皮革有限公司 | Stain-resistant and folding-resistant leather product and preparation method thereof |
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Denomination of invention: Preparation of nonionic waterborne polyurethane polyacrylate composite emulsion for leather finishing Effective date of registration: 20220225 Granted publication date: 20160120 Pledgee: Industrial Bank Limited by Share Ltd. Chengdu branch Pledgor: DOWELL TECHNOLOGY Co.,Ltd. Registration number: Y2022510000047 |
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Denomination of invention: Preparation method of non-ionic waterborne polyurethane polyacrylate composite lotion for leather finishing Effective date of registration: 20231009 Granted publication date: 20160120 Pledgee: Industrial Bank Limited by Share Ltd. Chengdu branch Pledgor: DOWELL TECHNOLOGY Co.,Ltd. Registration number: Y2023980060498 |
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