CN106893041A - 一种无溶剂水性聚氨酯分散液的制造方法 - Google Patents
一种无溶剂水性聚氨酯分散液的制造方法 Download PDFInfo
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- CN106893041A CN106893041A CN201610883599.7A CN201610883599A CN106893041A CN 106893041 A CN106893041 A CN 106893041A CN 201610883599 A CN201610883599 A CN 201610883599A CN 106893041 A CN106893041 A CN 106893041A
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- Prior art keywords
- acrylate
- sodium
- acid
- aqueous polyurethane
- manufacture method
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 229920003009 polyurethane dispersion Polymers 0.000 title 1
- 239000004814 polyurethane Substances 0.000 claims abstract description 78
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229920002635 polyurethane Polymers 0.000 claims abstract description 72
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- -1 acrylic ester Chemical class 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 25
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 22
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 21
- 239000004970 Chain extender Substances 0.000 claims description 20
- 239000000839 emulsion Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 12
- 239000012895 dilution Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- QDPMLKBAQOZXEF-UHFFFAOYSA-N ethanesulfonic acid;sodium Chemical compound [Na].CCS(O)(=O)=O QDPMLKBAQOZXEF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims description 5
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 150000004985 diamines Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- 150000001336 alkenes Chemical class 0.000 claims 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005345 coagulation Methods 0.000 abstract description 2
- 230000015271 coagulation Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 35
- 239000012948 isocyanate Substances 0.000 description 15
- 150000002513 isocyanates Chemical class 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 235000015424 sodium Nutrition 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 8
- 229920000058 polyacrylate Polymers 0.000 description 7
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 description 7
- UEUIKXVPXLWUDU-UHFFFAOYSA-N 4-diazoniobenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C([N+]#N)C=C1 UEUIKXVPXLWUDU-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000002171 ethylene diamines Chemical class 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 210000000481 breast Anatomy 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- CAFAOQIVXSSFSY-UHFFFAOYSA-N 1-ethoxyethanol Chemical class CCOC(C)O CAFAOQIVXSSFSY-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
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- 230000000052 comparative effect Effects 0.000 description 3
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 3
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- 238000012545 processing Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- 241000737241 Cocos Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 2
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- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
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- 238000005354 coacervation Methods 0.000 description 2
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- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
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- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 150000002118 epoxides Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000003916 ethylene diamine group Chemical group 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
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- 125000003010 ionic group Chemical group 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
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- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 description 1
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- ZCKVAJCGPPVONU-UHFFFAOYSA-N 2,3-diethylbutane-1,4-diol Chemical class CCC(CO)C(CC)CO ZCKVAJCGPPVONU-UHFFFAOYSA-N 0.000 description 1
- HXMRREGZBXNQRL-UHFFFAOYSA-N 2,3-diethylpentane-1,5-diol Chemical class CCC(CO)C(CC)CCO HXMRREGZBXNQRL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
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Abstract
一种水性聚氨酯无溶剂制造方法,以丙烯酸酯(acrylate)单体取代丙酮作为稀释聚氨酯预聚物的溶剂,在制程中,不需降温即可添加丙烯酸酯单体,且预聚物经过丙烯酸酯接枝改性后的分散效果佳,不但后续分散于水不发生凝聚现象,且无丙酮残留的问题;尤其所制得的水性聚氨酯,具备优异的机械强度、耐热性与耐水性等特点。
Description
技术领域
本发明涉及一种水性聚氨酯分散液,尤其是无溶剂水性聚氨酯分散液的制造方法。
背景技术
近年来,随着环保意识以及环保法规的加强,全球共同要求降低挥发性有机化合物(VOC)的排放;其中,关于水性聚氨酯或水性压克力的应用,也被要求需降低溶剂的使用量。
水性聚氨酯(PU)的合成方法,目前是使用丙酮法(acetone process),以丙酮为溶剂。此制法,是以聚醚或聚酯多元醇与异氰酸酯反应,合成末端为NCO官能基的高粘度预聚物,反应到NCO含量达到理论值后,加入亲水性扩链剂及与水相容的低沸点溶剂(如丙酮、丁酮或四氢呋喃等),完成后,将预聚物分散于水,以形成通过水成为连续相而均匀分散的水性聚氨酯(下文,简称水性聚氨酯分散液),最后(如丙酮等)溶剂再以蒸馏方法分离回收利用。
所述水性聚氨酯的亲水性扩链剂,选自2,2-二羟甲基丙酸(DMPA)或2,2-二羟甲基丁酸(DMBA),且需搭配中和剂三乙基胺(TEA)使用;但TEA为有毒化合物,且气味刺激,不符合水性聚氨酯产品要求低气味的标准。
所述丙酮法因为在制程中需使用溶剂,如果丙酮回收不当,容易造成环境污染。为解决此问题,又发展出另一种预聚物混合法,为了不使用大量的溶剂,采用NCO端已被中断的聚氨酯(PU)预聚物在水相中进行乳化反应。然而,预聚物的粘度,是这种预聚物混合法的重要限制因素,若粘度太高,则预聚物分散很困难,甚至不能分散。因此,为了降低粘度,通常采用少许溶剂调整粘度,但因为水与异氰酸盐会起反应,故分散阶段不宜太久,需尽快加入扩链剂,避免消耗过多异氰酸盐,或是选择使用反应性较低的异氰酸盐,此结果,造成由这种预聚物混合法制得的水性聚氨酯(PU)的质量,通常较丙酮法来得差。
更具体而言,水性聚氨酯的传统丙酮法制法,溶剂消耗量大,会危害人类健康与环境的污染,还需增设丙酮蒸馏回收设备,但溶剂蒸馏后残留仍多,无法达到真正水性化的要求。
而水性聚氨酯的另一种预聚物混合法,预聚物的分散程度,却受限于预聚物的粘度,因此只能选择反应性较低的异氰酸盐,以至于由此法制得的水性PU的质量通常较差。
发明内容
为解决上述两种制法的问题,尤其是为解决水性聚氨酯的传统丙酮法制法的问题,包括:当预聚物反应时的粘度高,则分散效果差,加入溶剂的时机,需降温后才能加入溶剂以避免造成突沸,以及后续蒸馏回收丙酮不当,易造成环境污染等问题,本发明利用丙烯酸酯接枝改性方法,来改善聚氨酯机械强度低、耐热性与耐水性差等缺点。
本发明提供一种无溶剂水性聚氨酯分散液的制造方法,其技术特征,是使用丙烯酸酯单体取代丙酮稀释聚氨酯预聚物,不需降温即可添加单体,尤其预聚物的分散效果佳,不但有利后续高速分散于水,且不发生凝聚现象,尤其是无丙酮残留的问题。
本发明的无溶剂水性聚氨酯分散液的制造方法,得以组合丙烯酸2羟乙酯(2-Hydroxyethyl Acrylate,2-HEA)、甲基丙烯酸甲酯(Methyl Methacrylate,MMA)及丙烯酸乙酯(Ethyl Acrylate,EA)三种丙烯酸酯单体并用,兼具溶剂的功效,且加入的时机,是在聚醚或聚酯多元醇与二异氰酸酯经过氨酯化反应合成预聚物(下文,简称预聚物反应)的2-3小时后加入,不需降温,并且可发挥溶剂分散的功效,更可在最后丙烯酸酯聚合阶段进行接枝聚合;因为,这三种单体的丙烯酸2羟乙酯(2-HEA)含羟基(-OH),可与异氰酸盐反应,而甲基丙烯酸甲酯(MMA)与丙烯酸乙酯(EA)可提高压克力分子量,弥补聚氨酯的耐热性差、机械强度低等缺点,达到优化聚氨酯物性的作用;尤其是,不需使用大量丙酮,合成反应产量可大幅提高,生产成本有效降低。
本发明的无溶剂水性聚氨酯分散液,在制程中使用的亲水性扩链剂选自乙二胺基乙磺酸钠(AAS)或3,5-二胺基苯磺酸钠(DABS),其亲水性强于传统丙酮法使用的DMPA或DMBA,具有较高离子化强度,可降低亲水性扩链剂的使用量,且AAS或DABS呈电中性,无须加胺类物质中和,即可制得高稳定性的水性聚氨酯。
本发明公开的无溶剂水性聚氨酯分散液,是一种通过丙烯酸酯接枝改性的水性聚氨酯分散液,其特点包括:聚氨酯树脂有丙烯酸酯基团分散其中,以及,聚氨酯树脂的主链,具有由多元异氰酸酯(polyisocyanate)与聚多元醇(polyol)所形成的基团及非离子基团,且其侧链具有含磺酸基的阴离子基团以及非离子基团。
本发明的水性聚氨酯合成方法,使用丙烯酸酯接枝改性,包含以下步骤:
1)预聚物的制备:
基于总反应原料量(包含去离子水,以下皆同),取聚多元醇15~25wt%,真空脱水后,加入装有搅拌器、温度计和冷凝管的反应器中,待油浴温度达到70-80℃时,加入计量的二异氰酸酯5~12wt%,使其合成反应;
2)预聚物的稀释及扩链:
预聚物反应2-3小时后,再加入10~30wt%丙烯酸酯单体稀释降粘,保持温度85-90℃保温反应,直到NCO含量达到理论值(二正丁胺法测定),加入磺酸盐扩链剂1.5~3.0wt%,优选为加入乙二胺基乙磺酸钠(AAS)或3,5-二胺基苯磺酸钠(DABS),继续反应25-40分钟;
3)分散于水:
将2)所得聚合物降温至室温,在转速500rpm高速搅拌下,加入适量去离子水35~55wt%,再加入计量的扩链剂0.1~0.5wt%进行扩链反应约30分钟,制得不含溶剂的磺酸盐型水性聚氨酯分散液;
4)丙烯酸酯聚合:
对前步骤分散液加入乳化剂0.3~1.0wt%混合形成乳化液,升温至50-70℃后滴加起始剂0.01~0.10wt%进行聚合丙烯酸酯,继续升温至75-85℃,且恒温1-3小时,再降温至50-70℃后,加入还原剂0.01~0.08wt%,得到丙烯酸酯接枝改性水性聚氨酯。
聚氨酯(PU)反应的NCO(%)理论值,是指:多元异氰酸酯的异氰酸基(-NCO)与聚多元醇所含的羟基(-OH)完全反应后,剩余的异氰酸基重量占所有参与的反应物重量的百分比。
也就是,NCO%理论值=[(多元异氰酸酯用量/多元异氰酸酯分子量)-(聚多元醇用量/聚多元醇分子量)]*42*2*100%,其NCO%理论值为0.5-10%;相对地,在实施例中,NCO%反应滴定值系在进行反应时,即在制备方法的步骤中加水并进行乳化前,使用二丁基胺(dibutylamine)滴定法所量测得到的NCO%数值。
聚氨酯树脂的NCO%反应滴定值,介于NCO%理论值的50-85%时,可使得聚氨酯树脂在水性聚氨酯分散液中呈现稳定分散状态,避免产生团聚凝胶。
但是,在合成聚氨酯时,如果过度地反应消耗多元异氰酸酯,聚氨酯树脂的NCO%反应滴定值低于NCO%理论值的50%以下,将造成聚氨酯反应过量及导致聚氨酯网状结构交联度太高,进而导致聚氨酯在水相中产生大量团聚凝胶而失败;反之,NCO%反应滴定值如果高于NCO%理论值的85%以上,将造成聚氨酯合成后的网状结构比例不足,导致水性聚氨酯加工形成薄膜后,该薄膜表面产生过高的粘滞性,易造成薄膜间沾粘而报废。
本发明的有益效果,包括:
1、本发明利用丙烯酸酯接枝改性方法,可改善聚氨酯机械强度低、耐热性与耐水性差等缺点;
2、本发明的无溶剂水性聚氨酯分散液的制造方法,使用丙烯酸酯单体取代丙酮稀释聚氨酯预聚物,不需降温即可添加单体,预聚物的分散效果佳,无丙酮残留的问题,且分散于水不发生凝聚现象。
具体实施方式
本发明的水性聚氨酯合成方法,使用具溶剂功效的丙烯酸酯单体取代丙酮稀释制备的聚氨酯预聚物,采用四阶段聚合的制程,有利于合成无溶剂水性聚氨酯,及达到丙烯酸酯接枝改性的效果。经过四阶段聚合后,得到使用丙烯酸酯接枝改性的水性聚氨酯分散液(简称水性聚氨酯丙烯酸酯接枝改性分散液),其合成步骤包括:
1、预聚物的制备:
由聚多元醇与二异氰酸酯经过氨酯化反应合成预聚物;优选为制得预聚物的NCO理论当量比值(NCO/OH)介于1.1~2.3。其中,所述聚多元醇选自聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇或聚酯酰胺多元醇;所述二异氰酸酯选自脂肪族二异氰酸酯或脂环族二异氰酸酯或其改性体,可以单独使用,也可混合二种以上使用。
所述聚酯多元醇是经由低分子二醇及二羧酸缩合制得,其中,二醇选自乙二醇、1,3-丙二醇或1,4-丁二醇;二羧酸选自琥珀酸、戊二酸、己二酸、庚二酸、软木酸(subericacid)、壬二酸(azelaic acid)、癸二酸(sebacic acid)、癸烷二羧酸或环己烷二羧酸。
所述聚酯酰胺多元醇为胺类聚酯酰胺多元醇,选自六亚甲基二胺或异佛尔酮二胺(isophorone diamine)。
上述各多元醇皆可单独使用,也可混合数个使用,也可使用其共聚物。
所述聚醚多元醇选自聚四亚甲基醚二醇(PTMG)、聚丙二醇(PPG)或其主链及侧链为聚乙二醇(PEG)的聚醚多元醇。
所述脂肪族二异氰酸酯选自四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、十亚甲基二异氰酸酯(decamethylene diisocyanate)或赖胺酸二异氰酸酯(lysinediisocyanate);优选为六亚甲基二异氰酸酯。
所述脂环族二异氰酸酯选自异佛尔酮二异氰酸酯(isophorone diisocyanate)、氢化甲苯二异氰酸酯、氢化二甲苯二异氰酸酯、氢化二苯甲烷二异氰酸酯或四甲基二甲苯二异氰酸酯(tetramethylxylene diisocyanate);优选为异佛尔酮二异氰酸酯。
所述脂肪族二异氰酸酯或脂环族二异氰酸酯的氨酯改性体,选自碳二亚胺(carbodiimide)改性体、脲基甲酸酯(allophanate)改性体、尿素改性体、二缩脲(biuret)改性体、异氰酸二元基(uretodion)改性体、脲酮亚胺基(uretonimine)改性体或异氰脲酸酯(isocyanurate)改性体等。
所述二异氰酸酯也可使用芳香族聚异氰酸酯或芳香族二异氰酸酯取代,其中,所述芳香族聚异氰酸酯选自聚苯聚亚甲基聚异氰酸酯(polyphenylene polymethylenepolyisocyanate)或未精制的甲苯二异氰酸酯(crude tolylene diisocyanate)。
所述芳香族二异氰酸酯选自2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、二甲苯-1,4-二异氰酸酯、二甲苯-1,3-二异氰酸酯、4,4’-二苯甲烷二异氰酸酯、2,4’-二苯甲烷二异氰酸酯、4,4’-二苯醚二异氰酸酯、2-硝基二苯基-4,4’-二异氰酸酯、2,2’-二苯丙烷-4,4’-二异氰酸酯、3,3’-二甲基二苯基甲烷-4,4’-二异氰酸酯、4,4’-二苯丙烷二异氰酸酯、间苯二异氰酸酯、对苯二异氰酸酯、萘-1,4-二异氰酸酯、萘-1,5-二异氰酸酯或3,3’-二甲氧基二苯基-4,4’-二异氰酸酯。
本发明得使用低分子多元醇与二异氰酸酯进行氨酯化反应;其中,所述低分子多元醇选自乙二醇、1,3-丙二醇、1,2-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、新戊二醇、1,8-辛二醇、1,9-壬二醇、3,3-二羟甲基庚烷、二乙二醇、1,4-环己烷二醇、1,4-环己烷二甲醇、2-乙基-1,3-丙二醇、2-正丙基-1,3-丙二醇、2-异丙基-1,3-丙二醇、2-正丁基-1,3-丙二醇、2-异丁基-1,3-丙二醇、2-第三丁基-1,3-丙二醇、2-甲基-2-乙基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-乙基-2-正丙基-1,3-丙二醇、2-乙基-2-正丁基-1,3-丙二醇、2-乙基-3-乙基-1,4-丁二醇、2-甲基-3-乙基-1,4-丁二醇、2,3-二乙基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇或2,3,4-三乙基-1,5-戊二醇;或选自三羟甲基丙烷、二羟甲基丙酸、二羟甲基丁酸、二元酸二醇、甘油、季戊四醇或双酚A的烯烃氧化物加成物等。
2、预聚物的稀释及扩链:
丙烯酸酯单体可使用丙烯酸酯系单体,选自丙烯酸甲酯、甲基丙烯酸甲酯(MMA)、丙烯酸乙酯(EA)、丙烯酸异辛酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸乙基己基酯或丙烯酸2羟乙酯(2-HEA)中的一种或以上;也可进一步使用顺丁烯二酸单甲酯、衣康酸单甲酯、反丁烯二酸单甲酯、苯乙烯及其混合物取代丙烯酸酯系单体;
优选为使用丙烯酸2羟乙酯(2-HEA)、甲基丙烯酸甲酯(MMA)及丙烯酸乙酯(EA)三种丙烯酸酯单体并用,其彼此间可达到物性互补相乘的作用,兼具溶剂功效的作用。
其中,所述丙烯酸2羟乙酯(2-HEA)含羟基(-OH),可与异氰酸盐反应;所述甲基丙烯酸甲酯(MMA)与所述丙烯酸乙酯(EA)可提高压克力分子量,弥补聚氨酯的耐热性差、机械强度低等缺点,达到优化聚氨酯物性的作用;尤其是,不需使用大量丙酮,合成反应产量可大幅提高,生产成本有效降低。
基于总丙烯酸酯单体重量,2-HEA、MMA及EA三种丙烯酸酯单体的组合比例如下:
(a)甲基丙烯酸甲酯 85~94wt%;
(b)丙烯酸2羟乙酯 4~9wt%;
(c)丙烯酸乙酯 2~6wt%。
特优选组合为甲基丙烯酸甲酯92wt%,丙烯酸2羟乙酯5wt%及丙烯酸乙酯3%。
为使预聚物扩链,本发明使用磺酸盐扩链剂(chain extender),除了当作聚氨酯亲水剂,还作为高分子乳化剂,其用量为NCO理论当量比值(NCO/OH)的80至90%。所述磺酸盐扩链剂选自乙二胺基乙磺酸钠(AAS)、2,4-二胺基苯磺酸钠、3,5-二胺基苯磺酸钠(DABS)、1,4-丁二醇-2-磺酸钠、1,2-二羟基-3-丙磺酸钠或N,N-二羟乙基胺乙基磺酸钠;优选为使用AAS或DABS。
3、分散于水:
所得聚合物分散于水后,加入计量的水溶性二胺类(diamines)扩链剂(chainextender)进行扩链反应;所述扩链剂选自(数均)分子量未满500的低分子聚胺,包括乙二胺、六亚甲基二胺、二甲苯二胺、异佛尔酮二胺、二乙烯三胺或N-胺基乙基-N-乙醇胺;且该扩链剂用量为(NCO/OH)当量比10%至20%。
4、丙烯酸酯聚合:
对前步骤分散液加入乳化剂0.3~1.0wt%混合形成乳化液,升温至50-70℃后滴加起始剂0.01~0.10wt%进行聚合丙烯酸酯,继续升温至75-85℃,且恒温1-3小时,再降温至50-70℃后,加入还原剂0.01~0.08wt%,得到水性聚氨酯丙烯酸酯接枝改性分散液。
乳化剂是一种表面活性剂,它可以大幅降低表面张力,使互不相溶的油水两相经由搅拌的作用转变为能够稳定存在、不易分层的白色乳液,是乳液聚合必不可少的组成。乳化剂可使用阴离子、非离子或反应型乳化剂的一种或多种的混合。
所述阴离子型乳化剂选自十二烷基硫酸钠(SLS)、十二烷基苯磺酸钠、硬脂酸钾、二辛基磺基琥珀酸钠、十二烷基二苯化氧基二磺酸钠、壬基苯氧乙基多(1)乙氧乙硫酸铵盐、苯乙烯磺酸钠、十二烷基烯丙基磺基琥珀酸钠、亚麻子油脂肪酸、乙氧化壬基酚磷酸酯的钠或铵盐、辛苯昔醇(octoxynol)-3-磺酸钠、椰基肌胺酸钠、1-烷氧基-2-羟丙基磺酸钠、α-烯烃(C14-C16)磺酸钠、羟基烷醇的硫酸盐、N-(1,2-二羧基乙)-N-十八烷基磺基琥珀酰胺酸四钠、N-十八烷基磺基琥珀酰胺酸二钠、烷酰胺基多乙氧基磺基琥珀酸二钠、乙氧化壬酚磺基琥珀酸半酯二钠或乙氧乙基硫酸钠盐。乳化剂的用量,基于丙烯酸酯单体重量为3wt%以下,基于总反应原料量为0.3~1.0wt%。
所述非离子型或反应型乳化剂包括特辛基苯氧乙基多(39)-乙氧基乙醇、十二烷氧多(10)乙氧基乙醇、壬基苯氧乙基-多(40)乙氧基乙醇、聚乙二醇2000单油酸酯、羟乙基化蓖麻油、氟化烷酯与烷氧化物、多氧乙烯(20)花楸糖醇单月桂酸酯、蔗糖单椰酸酯、二(2-丁)苯氧基多(20)乙氧基乙醇或羟乙基纤维素多丙烯酸丁酯接枝共聚物。
所述起始剂优选为水溶性自由基起始剂,选自过氧化氢、特丁基过氧化物或碱金属过硫酸盐;或选自过硫酸钠、过硫酸钾、过硫酸锂或过硫酸铵(APS);起始剂的用量,基于丙烯酸酯单体总量为0.01~3wt%,基于总反应原料量为0.01~0.10wt%。
在乳液聚合后期,为避免升温造成乳液凝聚,可用还原剂在50-70℃条件下进行单体的后消除,降低单体残留率。所述还原剂选自亚硫酸盐如偏亚硫酸碱金属盐、亚硫氢盐及次亚硫酸盐;甲醛合次硫酸氢钠(SFS);叔丁基过氧化氢(TBHP);及还原糖类如抗坏血酸与异抗坏血酸等。其中甲醛合次硫酸氢钠(SFS)适用于甲基丙烯酸甲酯、丙烯酸2羟乙酯等单体后消除,叔丁基过氧化氢(TBHP)适用于丙烯酸乙酯、丙烯酸丁酯等单体后消除。还原剂的用量,基于丙烯酸酯单体总量为0.1~0.3wt%,基于总反应原料量为0.01~0.08wt%。
本发明的水性聚氨酯分散液,使用丙烯酸酯接枝改性,不使用丙酮溶剂,具体合成水性聚氨酯丙烯酸酯接枝改性分散液的实施例,包含以下步骤:
1)预聚物的制备:
基于总反应原料量(包含去离子水),取聚多元醇15~25wt%,真空脱水后,加入装有搅拌器、温度计和冷凝管的反应器中,待油浴温度达到70-80℃时,加入计量的二异氰酸酯5~12wt%,使其合成反应;
2)预聚物的稀释及扩链:
预聚物反应2-3小时后,再加入10~30wt%丙烯酸酯单体稀释降粘,保持温度85-90℃保温反应,直到NCO含量达到理论值(二正丁胺法测定),加入磺酸盐扩链剂1.5~3.0wt%,优选为加入乙二胺基乙磺酸钠(AAS)或3,5-二胺基苯磺酸钠(DABS),继续反应25-40分钟;
3)分散于水:
将2)所得聚合物降温至室温,在转速500rpm高速搅拌下,加入适量去离子水35~55wt%,再加入计量的扩链剂0.1~0.5wt%进行扩链反应约30分钟,制得不含溶剂的磺酸盐型水性聚氨酯分散液;
4)丙烯酸酯合成:
对前步骤分散液加入乳化剂0.3~1.0wt%混合形成乳化液,升温至50-70℃后滴加起始剂0.01~0.10wt%进行聚合丙烯酸酯,续升温至75-85℃,且恒温1-3小时,再降温至50-70℃后,加入还原剂0.01~0.08wt%,得到水性聚氨酯丙烯酸酯接枝改性分散液。
以下以实施例及对比实施例进一步说明本发明以丙烯酸酯接枝改性的无溶剂水性聚氨酯制造方法,但本发明的范畴并不限于此等例子。
实施例1:
本实施例由水性聚氨酯为A树脂与聚丙烯酸乳液为B树脂共混合而成,说明如下。
制备水性聚氨酯(A树脂):
将98.8g PTMG2000(聚醚二元醇,分子量2000)、6.44g 1,4-BG(1,4-丁二醇,分子量90)依次加入反应器中,均速搅拌下,升温至80℃,之后,加入43.5g异佛尔酮二异氰酸酯,升温至85-90℃,在此温度下,反应2-3小时,此时可批次加入147.2g甲基丙烯酸甲酯(MMA)、8g丙烯酸2羟乙酯(2-HEA)、4.8g丙烯酸乙酯(EA)稀释降粘,预聚物加入10.7g乙二胺基乙磺酸钠(AAS),继续反应25-40分钟后,降温至室温,在500rpm搅拌转速下,加入236.3g去离子水,再加入0.95g乙二胺进行扩链反应约30分钟,制得不含溶剂的磺酸盐型水性聚氨酯乳液。
制备聚丙烯酸乳液(B树脂):
在快速搅拌下,将4.8g十二烷基硫酸钠(SLS)加入上述的磺酸盐型水性聚氨酯乳液,升温至50-70℃,之后,滴加过硫酸铵水溶液(APS)0.40g,继续升温至75-85℃,在此温度下,恒温1-3小时,降温至50-70℃后,加入还原剂叔丁基过氧化氢水溶液(TBHP)0.15g及甲醛合次硫酸氢钠(SFS)0.16g,反应30分钟,得到丙烯酸酯接枝改性水性聚氨酯,其成分中的固型份,为A树脂及B树脂,比例为1:1。
实施例2:
如实施例1,本实施例由水性聚氨酯为A树脂与聚丙烯酸乳液为B树脂共混合而成,但将A树脂提高比例,说明如下。
制备水性聚氨酯(A树脂):
将197.6g PTMG2000(聚醚二元醇,分子量2000)、12.9g 1,4-BG(1,4-丁二醇,分子量90)依次加入反应器中,均速搅拌下,升温至80℃,之后,加入87g异佛尔酮二异氰酸酯,升温至85-90℃,在此温度下,反应2-3小时,此时可批次加入147.2g甲基丙烯酸甲酯(MMA)、8g丙烯酸2羟乙酯(2-HEA)、4.8g丙烯酸乙酯(EA)稀释降粘,预聚物加入21.4g乙二胺基乙磺酸钠(AAS),继续反应25-40分钟后,降温至室温,在500rpm搅拌转速下,加入472.6g去离子水,再加入1.9g乙二胺进行扩链反应约30分钟,制得不含溶剂的磺酸盐型水性聚氨酯乳液。
制备聚丙烯酸乳液(B树脂):
在快速搅拌下,将4.8g十二烷基硫酸钠(SLS)加入上述的磺酸盐型水性聚氨酯乳液,升温至50-70℃,之后,滴加过硫酸铵水溶液(APS)0.40g,继续升温至75-85℃,在此温度下,恒温1-3小时,降温至50-70℃后,加入还原剂叔丁基过氧化氢水溶液(TBHP)0.15g及甲醛合次硫酸氢钠(SFS)0.16g,反应30分钟,得到丙烯酸酯接枝改性水性聚氨酯,其成分中的固型份,为A树脂及B树脂,比例为2:1。
实施例3:
如实施例1,本实施例由水性聚氨酯为A树脂与聚丙烯酸乳液为B树脂共混合而成,但将A树脂提高比例,说明如下。
制备水性聚氨酯(A树脂):
将296.4g PTMG2000(聚醚二元醇,分子量2000)、19.3g 1,4-BG(1,4-丁二醇,分子量90)依次加入反应器中,均速搅拌下,升温至80℃,之后,加入130.5g异佛尔酮二异氰酸酯,升温至85-90℃,在此温度下,反应2-3小时,此时可批次加入147.2g甲基丙烯酸甲酯(MMA)、8g丙烯酸2羟乙酯(2-HEA)、4.8g丙烯酸乙酯(EA)稀释降粘,预聚物加入32.1g乙二胺基乙磺酸钠(AAS),继续反应25-40分钟后,降温至室温,在500rpm搅拌转速下,加入708.9g去离子水,再加入2.9g乙二胺进行扩链反应约30分钟,制得不含溶剂的磺酸盐型水性聚氨酯乳液。
制备聚丙烯酸乳液(B树脂):
在快速搅拌下,将4.8g十二烷基硫酸钠(SLS)加入上述的磺酸盐型水性聚氨酯乳液,升温至50-70℃,之后,滴加过硫酸铵水溶液(APS)0.40g,继续升温至75-85℃,在此温度下,恒温1-3小时,降温至50-70℃后,加入还原剂叔丁基过氧化氢水溶液(TBHP)0.15g及甲醛合次硫酸氢钠(SFS)0.16g,反应30分钟,得到丙烯酸酯接枝改性水性聚氨酯,其成分中的固型份,为A树脂及B树脂,比例为3:1。
对比实施例1:
使用水性聚氨酯为A树脂,以习知丙酮法合成,与聚丙烯酸乳液共混,说明如下。
将75g PTMG2000(聚醚二元醇,分子量2000)、7.3g 1,4-BG(1,4-丁二醇,分子量90)依次加入反应器中,均速搅拌下,升温至80℃,之后,加入58.8g异佛尔酮二异氰酸酯,升温至85-90℃,在此温度下,反应2-3小时,随后降温至30-50℃,然后加入160g丙酮稀释降粘,20分钟后加入17.5g乙二胺基乙磺酸钠(AAS),继续反应25-40分钟后,降温至室温,在500rpm转速下加入266.6g去离子水,再加入1.1g乙二胺进行扩链反应约30分钟,之后,蒸馏丙酮,得到不含丙烯酸酯的磺酸盐型水性聚氨酯乳液。
结果:
1、取上述实施例1-3与对比实施例1的水性聚氨酯分散液,分别制成薄膜,经物性测试,结果如表1所示。
表1配方组成及所制备薄膜物性测试结果
2、根据表1的测试结果,本发明的实施例1-3的水性聚氨酯,经过丙烯酸酯接枝改性,其成分中的固型份,随着丙烯酸酯的比例增加,所制得的薄膜制品的拉伸强度随着提高,断裂伸长率随着下降,耐热粘着与耐水解性能随着提升。此结果,代表水性聚氨酯使用丙烯酸酯接枝改性,可以弥补未改性的水性聚氨酯原本的机械强度低、耐热性及耐水解性差等缺点,且无丙酮残留问题,可以达到真正水性化的要求。
Claims (10)
1.一种无溶剂水性聚氨酯分散液的制造方法,使用丙烯酸酯取代丙酮溶剂,制得以丙烯酸酯接枝改性的水性聚氨酯,其特征在于,包括以下步骤:
1)预聚物的制备:
基于包含去离子水的总反应原料量,取聚多元醇15~25wt%,真空脱水后,加入装有搅拌器、温度计和冷凝管的反应器中,待油浴温度达到70-80℃时,加入二异氰酸酯5~12wt%,进行氨酯化反应合成预聚物;且预聚物的NCO理论当量比值(NCO/OH)介于1.1~2.3;
2)预聚物的稀释及扩链:
预聚物反应2-3小时后,再加入丙烯酸酯单体10~30wt%稀释降粘,保持温度85-90℃保温反应,直到NCO含量达到理论值,加入磺酸盐扩链剂1.5~3.0wt%,继续反应25-40分钟;
其中,所述丙烯酸酯单体选自丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸2羟乙酯、丙烯酸异辛酯、丙烯酸丁酯或丙烯酸乙基己基酯中的一种以上;
3)分散于水:
将步骤2)所得聚合物降温至室温,在转速500rpm高速搅拌下,加入适量去离子水35~55wt%,再加入二胺类扩链剂0.1~0.5wt%进行扩链反应约30分钟,得到不含溶剂的磺酸盐型水性聚氨酯分散液;
4)丙烯酸酯聚合:
基于总反应原料量,对步骤3)的分散液加入乳化剂0.3~1.0wt%混合形成乳化液,搅拌均匀后升温至50-70℃,再滴加起始剂0.01~0.10wt%,接着继续升温至75-85℃进行丙烯酸酯聚合约1-3小时后,降温至50-70℃后加入还原剂0.01~0.08wt%,制得水性聚氨酯丙烯酸酯接枝改性分散液。
2.根据权利要求1所述的制造方法,其中,步骤1)使用的聚多元醇选自聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇或其组合物。
3.根据权利要求1或2所述的制造方法,其中,步骤2)使用的丙烯酸酯单体为丙烯酸2羟乙酯(2-HEA)、甲基丙烯酸甲酯(MMA)及丙烯酸乙酯(EA)的混合物。
4.根据权利要求1或2所述的制造方法,其中,基于总丙烯酸酯单体重量,步骤2)使用的丙烯酸酯单体为:
(a)甲基丙烯酸甲酯 85~94wt%;
(b)丙烯酸2羟乙酯 4~9wt%;及
(c)丙烯酸乙酯 2~6wt%。
5.根据权利要求1或2所述的制造方法,其中,基于总丙烯酸酯单体重量,步骤2)使用的丙烯酸酯单体为:甲基丙烯酸甲酯92wt%、丙烯酸2羟乙酯5wt%及丙烯酸乙酯3%。
6.根据权利要求1所述的制造方法,其中,步骤2)使用的磺酸盐扩链剂选自乙二胺基乙磺酸钠、2,4-二胺基苯磺酸钠、3,5-二胺基苯磺酸钠、1,4-丁二醇-2-磺酸钠、1,2-二羟基-3-丙磺酸钠或N,N-二羟乙基胺乙基磺酸钠。
7.根据权利要求1所述的制造方法,其中,步骤2)使用乙二胺基乙磺酸钠(AAS)为扩链剂。
8.根据权利要求1所述的制造方法,其中,步骤3)使用的二胺类扩链剂的(数均)分子量未满500,并选自乙二胺、六亚甲基二胺、二甲苯二胺、异佛尔酮二胺、二乙烯三胺或N-胺基乙基-N-乙醇胺;且该扩链剂用量为(NCO/OH)当量比10%至20%。
9.根据权利要求1所述的制造方法,其中,步骤4)使用的起始剂选自特丁基过氧化物或碱金属过硫酸盐,或者选自由过氧化氢、过硫酸钠、过硫酸钾、过硫酸锂及过硫酸铵所组成的群组中的一种以上。
10.根据权利要求1所述的制造方法,其中,步骤4)使用的还原剂选自甲醛合次硫酸氢钠或叔丁基过氧化氢。
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