CN111971265A - 包含具有一个或两个仲氨基的二羧酸盐的聚氨酯的水分散体 - Google Patents
包含具有一个或两个仲氨基的二羧酸盐的聚氨酯的水分散体 Download PDFInfo
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- CN111971265A CN111971265A CN201980025505.4A CN201980025505A CN111971265A CN 111971265 A CN111971265 A CN 111971265A CN 201980025505 A CN201980025505 A CN 201980025505A CN 111971265 A CN111971265 A CN 111971265A
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- Prior art keywords
- polyurethane
- aqueous dispersion
- compounds
- secondary amino
- group
- Prior art date
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- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 title claims abstract description 27
- 229920003009 polyurethane dispersion Polymers 0.000 title claims description 14
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 title claims 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- 229920002635 polyurethane Polymers 0.000 claims abstract description 47
- 239000004814 polyurethane Substances 0.000 claims abstract description 47
- 150000002009 diols Chemical class 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000012948 isocyanate Substances 0.000 claims abstract description 15
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- -1 alkali metal cations Chemical class 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000001767 cationic compounds Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 150000002892 organic cations Chemical class 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000010985 leather Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 239000004566 building material Substances 0.000 claims description 2
- 239000011111 cardboard Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims 2
- 239000000203 mixture Substances 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 125000005442 diisocyanate group Chemical group 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 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 10
- 239000005056 polyisocyanate Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 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 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
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- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
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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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- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- ODKSRULWLOLNJQ-UHFFFAOYSA-N 1,2-diisocyanatocyclohexane Chemical compound O=C=NC1CCCCC1N=C=O ODKSRULWLOLNJQ-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 1
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- 229940035437 1,3-propanediol Drugs 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- JMFCAIUTSABFDU-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O JMFCAIUTSABFDU-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
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- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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Classifications
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/28—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and containing rings
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- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L75/06—Polyurethanes from polyesters
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Abstract
一种聚氨酯的水分散体,其中所述聚氨酯通过使二‑或多官能异氰酸酯、二醇、具有一个或两个仲氨基的二羧酸盐和任选的其他化合物反应而获得。
Description
本发明涉及一种聚氨酯的水分散体,其中所述聚氨酯通过使二-或多官能异氰酸酯、二醇、具有一个或两个仲氨基的二羧酸盐和任选的其他化合物反应而获得。
聚氨酯水分散体通常使用称为“预聚物混合技术”的方法工业化生产。在该方法中,首先在有机溶剂中制备聚氨酯,随后将所得聚氨酯溶液分散在水中以获得聚氨酯水分散体。需要亲水性基团以使聚氨酯可分散在水中。一种可能性是添加乳化剂或保护性胶体。然而,该类乳化剂和保护性胶体可能对聚氨酯在技术应用中的性能具有负面影响。乳化剂和保护性胶体由于它们没有键合到聚氨酯上而倾向于迁移。
另一种可能性是通过共聚具有异氰酸酯基或与异氰酸酯具有反应性的官能团以及另外的亲水性基团的化合物,将亲水性基团引入到聚氨酯本身中。DE-A 2035732公开了具有氨基和磺酸基的化合物共聚以获得可分散于水中的聚氨酯。从DE-A 2034479已知由于包含具有一个羧基的化合物而可分散于水中的聚氨酯。该类化合物通过不饱和羧酸如丙烯酸与伯二胺反应而获得。不饱和基团加成到伯氨基上,这称为迈克尔加成反应。迈克尔加成反应的产物包括一个羧基、一个仲氨基和一个未反应的伯氨基。
本发明的目的是提供分散的聚氨酯颗粒具有高稳定性的聚氨酯分散体。该制备聚氨酯分散体的方法应易于进行并且应具有高效率。特别地,希望在聚合中使用较少的亲水性共聚单体。当使用较少的亲水性共聚单体时,可使用更多的有助于聚氨酯的机械性能的共聚单体。
因此,已发现了上述聚氨酯分散体和制备该聚氨酯分散体的方法。具有至少一个仲氨基的二羧酸盐
所述聚氨酯通过使二-或多官能异氰酸酯、二醇、具有一个或两个仲氨基的二羧酸盐和任选的其他化合物反应而获得。
所述二羧酸盐包含一个或两个仲氨基。优选地,二羧酸包含两个仲氨基。
优选地,所述二羧酸盐为式I的化合物:
其中R表示键或具有1-20个碳原子的烃基,K+表示无机或有机阳离子。
优选地,R表示具有2-16个,特别是2-10个碳原子的烃基。
优选地,R为非芳族烃基。
更优选地,R表示包含脂环族环体系的脂族烃基。
优选地,K+表示金属阳离子或季铵阳离子。季铵阳离子优选通过叔氨基化合物与二羧酸盐的相应二羧酸反应形成。叔氨基化合物优选为被三个有机基团取代的氨基化合物,所述有机基团选自烷基或羟烷基,特别是C1-C8烷基或C1-C8羟烷基。
更优选地,K+为碱金属的阳离子,特别为钠或钾的阳离子。
在本发明最优选的实施方案中,所述二羧酸盐为式II的化合物:
具有一个或两个仲氨基的二羧酸盐可例如通过如下物质的反应合成:
X)具有双键和羧基或可转变为羧基的基团的化合物,
Y)包含两个伯氨基的化合物。
优选地,X)是具有双键和可转变为羧基的基团的化合物。可转变为羧基的基团优选为腈基。
所得化合物包括X):Y)摩尔比为2:1的X)和Y)。在合成中,X)或Y)可过量使用。优选地,Y)过量使用。产物为迈克尔加合物。
在优选的实施方案中,化合物X)为丙烯腈,通过X)和Y)反应形成的加合物为式III的化合物:
其中R具有与式I中相同的含义。
化合物Y)例如为二氨基乙烷、二氨基丙烷、二氨基丁烷、二氨基己烷、氨基-3-氨基甲基-3,5,5-三甲基环己烷(称为异佛尔酮二胺,简称IPDA)、4,4'-二氨基二环己基甲烷、4,4'-二氨基-3,3'-二甲基二环己基甲烷、1,4-二氨基环己烷、肼,也可以以其水合物的形式使用。
优选的化合物Y)为氨基-3-氨基甲基-3,5,5-三甲基环己烷(异佛尔酮二胺,IPDA)和4,4'-二氨基二环己基甲烷,其中IPDA是最优选的。
通过两个腈基的皂化,式III化合物容易地转变成式I化合物。通过皂化,腈基变成羧基。
优选地,皂化通过使式III化合物与碱,特别是与碱金属氢氧化物反应进行。
聚氨酯
所述聚氨酯通过使二-或多官能异氰酸酯、二醇、具有至少一个仲氨基的二羧酸和任选的其他化合物反应而获得。
具体地,聚氨酯通过如下物质的反应获得:
a)具有4-30个碳原子的二-或多官能异氰酸酯,
b)二醇,其中
b.1)基于二醇(b)的总量,10-100mol%具有500-5000的分子量,和
b.2)基于二醇(b)的总量,0-90mol%具有60-500g/mol的分子量,
c)具有一个或两个仲氨基的二羧酸盐,和
d)任选地,不同于化合物a)、b)和c)的具有至少一个异氰酸酯基或至少一个异氰酸酯反应性基团的化合物。
二官能异氰酸酯是具有两个异氰酸酯基的化合物,也称为二异氰酸酯。
多官能异氰酸酯是具有至少三个异氰酸酯基的化合物,也称为多异氰酸酯。
二-或多官能异氰酸酯可为脂族、芳族和脂环族化合物,其包括具有(环)脂族或芳族基团的组合的化合物。优选地,二-或多官能异氰酸酯不包含除异氰酸酯基和烃基以外的任何其他成分。
通常使用不同的二-或多官能异氰酸酯的混合物。混合物的NCO官能度优选为2-4。
二异氰酸酯优选为具有4-20个碳原子的异氰酸酯。常规二异氰酸酯的实例为脂族二异氰酸酯,例如四亚甲基二异氰酸酯、六亚甲基二异氰酸酯(1,6-二异氰酸酯基己烷)、八亚甲基二异氰酸酯、十亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、十四亚甲基二异氰酸酯、赖氨酸二异氰酸酯、四甲基亚二甲苯基二异氰酸酯、三甲基己烷二异氰酸酯或四甲基己烷二异氰酸酯;脂环族二异氰酸酯,例如1,4-、1,3-或1,2-二异氰酸酯基环己烷,4,4'-或2,4'-二(异氰酸酯基环己基)甲烷的反/反、顺/顺和顺/反异构体,1-异氰酸酯基-3,3,5-三甲基-5-(异氰酸酯基甲基)环己烷(异佛尔酮二异氰酸酯)、2,2-双(4-异氰酸酯基环己基)丙烷、1,3-或1,4-双(异氰酸酯基甲基)环己烷或2,4-或2,6-二异氰酸酯基-1-甲基环己烷;以及芳族二异氰酸酯,例如2,4-或2,6-亚甲苯基二异氰酸酯及其异构体混合物、间-或对-亚二甲苯基二异氰酸酯、2,4'-或4,4'-二异氰酸酯基二苯基甲烷及其异构体混合物、1,3-或1,4-亚苯基二异氰酸酯、1-氯-2,4-亚苯基二异氰酸酯、1,5-亚萘基二异氰酸酯、亚联苯基-4,4’-二异氰酸酯、4,4’-二异氰酸酯基-3,3’-二甲基联苯、3-甲基二苯基甲烷-4,4'-二异氰酸酯、1,4-二异氰酸酯基苯或二苯基醚4,4'-二异氰酸酯。
合适的二异氰酸酯还有上述二异氰酸酯的脲二酮。
也可使用所述二异氰酸酯的混合物。
优选脂族和脂环族二异氰酸酯,特别优选异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、间四甲基亚二甲苯基二异氰酸酯(m-TMXDI)和1,1-亚甲基双[4-异氰酸酯基]环己烷(H12MDI)。
合适的多异氰酸酯包括含有异氰脲酸酯基的多异氰酸酯、含有缩二脲基的多异氰酸酯、含有氨基甲酸酯基或脲基甲酸酯基的多异氰酸酯、含有噁二嗪三酮基的多异氰酸酯、线性或支化C4-C20亚烷基二异氰酸酯的脲酮亚胺改性的多异氰酸酯、总共具有6-20个碳原子的脂环族二异氰酸酯或总共具有8-20个碳原子的芳族二异氰酸酯,或其混合物。
可使用的二异氰酸酯和多异氰酸酯优选具有10-60重量%,更优选15-60重量%,非常优选20-55重量%的异氰酸酯基含量(以NCO计算,分子量=42),基于二异氰酸酯和多异氰酸酯(混合物)。
优选的是脂族和/或脂环族二异氰酸酯和多异氰酸酯,实例是上述脂族和脂环族二异氰酸酯和多异氰酸酯或其混合物。
二醇b.1)具有500-5000g/mol,优选约1000-3000g/mol的分子量。
二醇b.1)特别为聚酯二醇。该聚酯二醇优选通过二元醇与二元羧酸反应获得。代替游离多羧酸,也可使用相应的多羧酸酐或相应的低级醇的多羧酸酯或其混合物来制备聚酯多元醇。多羧酸可以是脂族、脂环族、芳脂族、芳族或杂环的,并且可以是未取代的或被例如卤素原子取代,和/或饱和的或不饱和的。实例为辛二酸、壬二酸、邻苯二甲酸和间苯二甲酸、四氢邻苯二甲酸、六氢邻苯二甲酸、四氯邻苯二甲酸、内亚甲基四氢邻苯二甲酸、戊二酸酐和马来酸酐、马来酸、富马酸和二聚脂肪酸。优选通式HOOC-(CH2)y-COOH的二羧酸,其中y为1-20的数,优选为2-20的偶数,实例为琥珀酸、己二酸、癸二酸和十二烷二羧酸。
合适的二元醇的实例为乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁烯二醇、1,4-丁炔二醇、1,5-戊二醇、新戊二醇、双(羟甲基)环己烷如1,4-双(羟甲基)环己烷、2-甲基-1,3-丙二醇以及二甘醇、三甘醇、四甘醇、聚乙二醇、二丙二醇、聚丙二醇、二丁二醇和聚丁二醇。优选新戊二醇和通式HO-(CH2)x-OH的醇,其中x为1-20的数,优选为2-20的偶数。该类醇的实例为乙二醇、1,4-丁二醇、1,6-己二醇、1,8-辛二醇和1,12-十二烷二醇。
聚碳酸酯二醇、内酯基聚酯二醇也是合适的。
其他合适的二醇b.1)为聚醚二醇。它们尤其可通过环氧乙烷、环氧丙烷、环氧丁烷、四氢呋喃、氧化苯乙烯或表氯醇自身在例如BF3存在下的加成聚合获得,或通过这些化合物单独或以混合物形式或依次加成反应到含有反应性氢的起始剂组分例如醇或胺上获得,所述起始剂组分例如为水、乙二醇、1,2-丙二醇、1,3-丙二醇、2,2-双(4-羟基二苯基)丙烷或苯胺。特别优选分子量为500-5000g/mol,特别为1000-4500g/mol的聚四氢呋喃。
可使用不同二醇b.1)的混合物。
作为二醇b),不仅可使用二醇b.1),而且可使用分子量为约50-500g/mol,优选60-200g/mol的低分子量二醇b.2)。
用作单体(b2)的化合物特别为上文对制备聚酯多元醇所述的短链链烷二醇,优选具有2-12个碳原子和偶数个碳原子的非支化二醇,以及1,5-戊二醇和新戊二醇。
基于二醇(b)的总量,二醇(b1)的比例优选为10-100mol%;基于二醇(b)的总量,二醇(b2)的比例优选为0-90mol%。
化合物c)是具有一个或两个仲氨基的二羧酸盐,优选式I的化合物,最优选式II的化合物。
术语“具有一个或两个仲氨基的二羧酸盐”应包括具有一个或两个仲氨基的二羧酸盐的混合物。在优选的实施方案中,化合物c)仅为一种具有一个或两个仲氨基的特定二羧酸盐。
优选地,聚氨酯以0.01-0.5mol/1kg聚氨酯的量包含具有一个或两个仲氨基的二羧酸盐。
更优选地,聚氨酯以0.05-0.3mol/1kg聚氨酯的量包含具有一个或两个仲氨基的二羧酸盐。
最优选地,聚氨酯以0.08-0.25mol/1kg聚氨酯的量包含具有一个或两个仲氨基的二羧酸盐。
化合物d)是任选的。化合物d)包括具有至少一个异氰酸酯基或至少一个异氰酸酯反应性基团,例如羟基、巯基或伯或仲氨基的任何化合物,但不落入化合物a)、b)和c)的定义内。
该类化合物例如为化合物d.1),其具有至少两个伯氨基或至少两个仲氨基,或具有至少一个伯氨基和至少一个仲氨基,但不具有另外的亲水性基团。化合物d.1)可用作扩链剂或交联剂。
该类化合物例如为化合物d.2),其具有至少三个羟基但不具有另外的亲水性基团。该类化合物可用作交联剂。
该类化合物例如为化合物d.3),其具有至少一个异氰酸酯基或至少一个异氰酸酯反应性基团和另外的至少一个亲水性基团或一个可转变为亲水性基团的潜在亲水性基团。
与化合物c)类似,化合物d.3)具有使聚氨酯可分散在水中的能力。
d.3)的亲水性基团可为非离子的,或优选为离子的,即阳离子或阴离子基团。潜在的亲水性基团是当意欲将聚氨酯分散在水中时可容易地转变为亲水性基团的基团。该类潜在的亲水性基团特别为酸基团,其可通过成盐转变为亲水性基团,或者为叔氨基,其可通过与酸反应或通过与烷基化剂季铵化而转变为离子基团。
在优选的实施方案中,化合物d.3)仅以少量使用,如果有的话。优选地,化合物d.3)的用量小于50重量%,更优选小于20重量%,尤其是小于5重量%,基于化合物c)和d.3)的总量。
在最优选的实施方案中,根本不使用化合物d.3)。
其他化合物d)例如为化合物d.4),其具有一个异氰酸酯基或一个异氰酸酯反应性基团而不具有亲水性基团或潜在的亲水性基团。由于该类化合物仅具有一个反应性基团,因此其可用于通过链终止来限制聚氨酯的分子量。实例为甲醇、乙醇、异丙醇、正丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、乙二醇单甲醚、乙二醇单乙醚、1,3-丙二醇单甲醚、正己醇、正庚醇、正辛醇、正癸醇、正十二烷醇(月桂醇)和2-乙基己醇。
如果使用,化合物d.4)通常以少量使用,例如每100mol化合物b)小于10mol,尤其小于1mol的量。
化合物a)、b)、c)和d)优选以使得A:B为0.5:1至2:1,优选为0.8:1至1.5,更优选为0.9:1至1.2:1的摩尔量反应,其中:
A)为异氰酸酯基的摩尔量,且
B)为羟基和所有其他能在加成反应中与异氰酸酯反应的官能团的摩尔量之和。
非常特别优选地,比值A:B尽可能接近1:1。
化合物a)-d)的反应是公知的加聚反应。所述加聚反应优选在20-80℃,优选50-150℃的温度下在大气压下进行。
所需的反应时间通常从几分钟到几小时。聚氨酯化学领域中已知的是,反应时间如何受到多种参数如温度、单体浓度和单体反应性的影响。
为了加速反应,可使用催化剂。合适的催化剂是公知的。
这些例如为有机胺,特别是脂族、脂环族或芳族叔胺,和/或路易斯酸有机金属化合物。
优选的路易斯酸有机金属化合物为二乙酸二甲基锡、二丁酸二丁基锡、双(2-乙基己酸)二丁基锡、二月桂酸二辛基锡、乙酰丙酮锆和2,2,6,6-四甲基-3,5-庚二酸锆。
也可使用铋、钴或铯基催化剂。
用于加聚反应的合适装置包括搅拌釜,特别是当使用溶剂以确保低粘度和有效除热时。
如果反应在本体中进行,由于通常的高粘度和通常的短反应时间,合适的设备特别包括挤出机,尤其是自清洁多螺杆挤出机。
聚氨酯及其水分散体优选通过如下方法获得,其中:
I)在有机溶剂中使化合物a)、b)、c)和任选的d)反应成聚氨酯,和
II)将聚氨酯分散在水中,
其中具有伯氨基或仲氨基作为异氰酸酯反应性基团的组分d)也可在I)中反应,或者可在步骤II期间或之后部分或全部加入。
步骤I中使用的有机溶剂可以是溶解化合物a)-e)的任何溶剂。优选的溶剂具有与水的高混溶性,特别是与水具有无限混溶性。优选地,所用的有机溶剂具有最高100℃的沸点(常压)。优选的溶剂例如为丙酮。
如果需要,可从水分散体中完全除去有机溶剂。或者,溶剂可全部或部分保留在水分散体中。
在优选的实施方案中,不使用另外的乳化剂或保护性胶体来将聚氨酯分散在水中。因此,根据本发明获得的聚氨酯的优选水分散体不含乳化剂和保护性胶体。
分散体通常具有10-75重量%,优选20-65重量%的固含量和10-500mPas的粘度(在20℃的温度和250s-1的剪切速率下测量)。
根据本发明制备的分散体可另外与通常用于所述应用的其他组分混合,实例为表面活性剂、洗涤剂、染料、颜料、颜色转移抑制剂和荧光增白剂。
如果需要,在其制备之后,可对分散体进行物理除臭。
物理除臭可包括使用蒸汽、含氧气体,优选空气或氮气汽提分散体,例如在搅拌容器中,如DE-B 1248943所述,或在逆流塔中,如DE-A 19621027所述。
本发明的含水聚氨酯配制剂适于涂覆和粘合基材。它们特别适合于涂覆或粘合木材、薄木片、纸、纸板、卡纸板、纺织品、皮革、无纺布、塑料表面、玻璃、陶瓷、矿物建筑材料、未涂覆的金属或涂覆的金属。
它们例如用于生产膜或薄板,用于浸渍纺织品或皮革,用作分散剂,用作颜料研磨剂,用作底漆,用作增粘剂,用作疏水剂,用作洗衣洗涤剂添加剂或用作化妆品制剂的添加剂,或用于生产模制品或制备水凝胶。
在其用作涂料的情况下,所述聚氨酯分散体可特别用作汽车重涂或大型车辆涂饰领域中的底漆、二道底漆、着色的面漆材料和清漆材料。所述涂料特别适用于要求特别高的施涂可靠性、外部耐候稳定性、光学质量、耐溶剂性、耐化学性和耐水性的应用,例如汽车重涂和大型车辆涂饰。
根据本发明获得的聚氨酯的水分散体是均匀的并且具有高稳定性。不需要另外的乳化剂或保护性胶体。由于在化合物c)中存在两个羧酸基团,因此制备聚氨酯需要较少的具有亲水性基团的化合物。所述聚氨酯具有良好的机械性能。
实施例
实施例1
化合物II的制备
在2升搅拌烧瓶中加入469.0g氢氧化钠(20重量%水溶液,2.35mol)。然后加入197.8g 40重量%化合物II的水溶液,以加速起始物质(其是相应的二腈)的所需皂化反应。皂化反应也可在不加入化合物II的情况下进行,但是必须延长加料时间,尤其是在加料开始时。
将所得混合物的温度升至90℃。然后在180分钟内加入310.2gPC136(1.12mol),其中将反应温度保持在90-95℃下。加料操作使用夹套滴液漏斗,将该漏斗加热到55℃以降低化合物I的粘度。在完成腈添加之后,用102.0g去离子水冲洗滴液漏斗,并将反应混合物在95-100℃下再搅拌120分钟,以完成反应并除去皂化期间形成的氨。获得澄清溶液。在冷却至20℃后,加入去离子水以调节干物质含量至43%。
通过NMR(1H-和13C-NMR)表征最终产物。
*
实施例2
用化合物II制备PUD
将600g(0.30mol)由己二酸、新戊二醇和1,6-己二醇(摩尔比1/1)制备的聚酯二醇(OH值56),26.7g(0.014mol)以丁醇为起始的聚环氧乙烷,100g丙酮和0.3g二月桂酸二丁基锡加入到容器中,在83℃下搅拌。然后加入89.8g(0.404mol)IPDI和106.7g(0.404mol)H12MDI,随后将所得混合物在83℃下搅拌60分钟。然后加入27.0g(0.30mol)1,4-丁二醇,反应继续进行另外120分钟。通过加入850g丙酮来稀释混合物。测得所得混合物的NCO含量为0.91重量%(计算值:0.93重量%)。然后加入73.1g(0.10mol化合物II)实施例1的溶液。在10分钟后,在15分钟内加入1300g水。然后加入5.8g(0.0562mol)DETA和2.7g(0.0159mol)IPDA的混合物。最后,通过减压蒸馏除去丙酮。
获得具有小聚氨酯颗粒的均匀聚氨酯分散体。所述聚氨酯分散体的固含量为36.0重量%。
对比实施例
用二氨基单羧酸制备PUD(类似于DE-A 2034479的公开内容)
将600g(0.30mol)由己二酸、新戊二醇和1,6-己二醇(摩尔比1/1)制备的聚酯二醇(OH值56),26.7g(0.014mol)以丁醇为起始的聚环氧乙烷,100g丙酮和0.3g二月桂酸二丁基锡加入到容器中,在83℃下搅拌。然后加入89.8g(0.404mol)IPDI和106.7g(0.404mol)H12MDI,随后将所得混合物在83℃下搅拌60分钟。然后加入27.0g(0.30mol)1,4-丁二醇,反应继续进行另外120分钟。通过加入850g丙酮来稀释混合物。测得所得混合物的NCO含量为0.93重量%(计算值:0.93重量%)。然后加入42.0g(0.10mol)丙烯酸钠与乙二胺的加合物。在10分钟后,在15分钟内加入1300g水。然后加入5.8g(0.0562mol)DETA和2.7g(0.0159mol)IPDA的混合物。最后,通过减压蒸馏除去丙酮。
获得具有小聚氨酯颗粒的均匀聚氨酯分散体。所述聚氨酯分散体的固含量为38.0重量%。
Claims (11)
1.一种聚氨酯的水分散体,其中所述聚氨酯通过使二-或多官能异氰酸酯、二醇、具有一个或两个仲氨基的二羧酸盐和任选的其他化合物反应而获得。
3.根据权利要求2的水分散体,其中R表示包含脂环族环体系的脂族烃基。
4.根据权利要求1-3中任一项的水分散体,其中所述二羧酸盐的阳离子为碱金属阳离子。
6.根据权利要求1-5中任一项的水分散体,其中所述聚氨酯通过如下物质反应而获得:
a)具有4-30个碳原子的二-或多官能异氰酸酯,
b)二醇,其中
b.1)基于二醇(b)的总量,10-100mol%具有500-5000的分子量,和
b.2)基于二醇(b)的总量,0-90mol%具有60-500g/mol的分子量,
c)具有一个或两个仲氨基的二羧酸盐,和
d)任选地,不同于化合物a)、b)和c)的具有至少一个异氰酸酯基或至少一个异氰酸酯反应性基团的化合物。
7.根据权利要求1-6中任一项的水分散体,其中所述聚氨酯以0.01-0.5mol/1kg聚氨酯的量包含具有一个或两个仲氨基的二羧酸盐。
8.制备根据权利要求1-7中任一项的水分散体的方法,其中:
I)在有机溶剂中使化合物a)、b)、c)和任选的d)反应成聚氨酯,和
II)将聚氨酯分散在水中,
其中具有伯氨基或仲氨基作为异氰酸酯反应性基团的组分d)也可在I)中反应,或者可在步骤II期间或之后部分或全部加入。
9.根据权利要求1-8中任一项的聚氨酯分散体用于涂覆或粘合木材、薄木片、纸、纸板、卡纸板、纺织品、皮革、无纺布、塑料表面、玻璃、陶瓷、矿物建筑材料、未涂覆的金属或涂覆的金属的用途。
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Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1248943C2 (de) | 1965-07-20 | 1974-03-07 | Basf Ag | Verfahren und Vorrichtung zur diskontinuierlichen Entfernung von Geruchs-stoffen auswaessrigen Polymerisatdispersionen |
DE2034479A1 (de) | 1970-07-11 | 1972-01-13 | Bayer | Polyurethan Kunststoffe und Verfahren zu ihrer Herstellung |
DE2035732A1 (de) | 1970-07-18 | 1972-01-27 | Farbenfabriken Bayer AG, 5090 Le verkusen | N (Omega Ammo a/kan) Omega ammo a/kan sulfonsaure salze und ihre Verwendung als anio nische Aufbaukomponente bei der Herstellung von emulgatorfreien Polyurethandispersionen |
FR2345503A1 (fr) * | 1976-03-22 | 1977-10-21 | Oxy Metal Industries Corp | Compositions et procede pour l'enlevement d'alliages de nickel deposes par voie electrolytique |
DE19621027A1 (de) | 1996-05-24 | 1997-11-27 | Basf Ag | Verfahren zur Abtrennung flüchtiger organischer Komponenten aus Suspensionen oder Dispersionen |
DE19750186A1 (de) * | 1997-11-13 | 1999-05-20 | Bayer Ag | Hydrophilierungsmittel, ein Verfahren zu dessen Herstellung sowie dessen Verwendung als Dispergator für wäßrige Polyurethan-Dispersionen |
US5968494A (en) * | 1998-02-24 | 1999-10-19 | National Starch And Chemical Investment Holding Corporation | Polyurethanes with carboxylate functionality for hair fixative applications |
US6232406B1 (en) * | 1999-09-30 | 2001-05-15 | Replication Medical Inc. | Hydrogel and method of making |
GB0512751D0 (en) * | 2005-06-22 | 2005-07-27 | Glaxo Group Ltd | New adjuvant |
EP2186841A1 (de) * | 2008-11-14 | 2010-05-19 | Bayer MaterialScience AG | Vernetzbare Polyurethan-Dispersionen |
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