CN102105541B - 含水涂料组合物及其制备方法 - Google Patents
含水涂料组合物及其制备方法 Download PDFInfo
- Publication number
- CN102105541B CN102105541B CN2009801290259A CN200980129025A CN102105541B CN 102105541 B CN102105541 B CN 102105541B CN 2009801290259 A CN2009801290259 A CN 2009801290259A CN 200980129025 A CN200980129025 A CN 200980129025A CN 102105541 B CN102105541 B CN 102105541B
- Authority
- CN
- China
- Prior art keywords
- carbonyl
- hydrazides
- isocyanuric acid
- coating composition
- aqueous
- Prior art date
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- 239000008199 coating composition Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 ether amine Chemical class 0.000 claims abstract description 90
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 68
- 239000006185 dispersion Substances 0.000 claims abstract description 46
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920002396 Polyurea Polymers 0.000 claims abstract description 33
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 33
- 238000004132 cross linking Methods 0.000 claims abstract description 29
- 125000000524 functional group Chemical group 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 56
- 150000002148 esters Chemical class 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000007665 sagging Methods 0.000 claims description 29
- 229920005596 polymer binder Polymers 0.000 claims description 23
- 239000002491 polymer binding agent Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000005829 trimerization reaction Methods 0.000 claims description 8
- 239000002023 wood Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000009472 formulation Methods 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 239000012948 isocyanate Substances 0.000 abstract description 6
- 150000002513 isocyanates Chemical class 0.000 abstract description 6
- 230000009974 thixotropic effect Effects 0.000 abstract description 5
- 239000007983 Tris buffer Substances 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 40
- 239000002253 acid Substances 0.000 description 19
- 239000000839 emulsion Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 239000003643 water by type Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 13
- 238000000576 coating method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000013543 active substance Substances 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000004815 dispersion polymer Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 150000002429 hydrazines Chemical class 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical group OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000007973 cyanuric acids Chemical class 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- KNYKHCLCBHSFCK-UHFFFAOYSA-N 1-methoxypropan-1-amine Chemical class CCC(N)OC KNYKHCLCBHSFCK-UHFFFAOYSA-N 0.000 description 3
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920005692 JONCRYL® Polymers 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000162 poly(ureaurethane) Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000006254 rheological additive Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- AWMNXQXKGOSXDN-GORDUTHDSA-N (e)-ethylideneurea Chemical compound C\C=N\C(N)=O AWMNXQXKGOSXDN-GORDUTHDSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- 229920005789 ACRONAL® acrylic binder Polymers 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 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
- 229920000570 polyether Polymers 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- GZOKAVHTSXSLNB-UHFFFAOYSA-N 1,1-dimethoxypropan-2-amine Chemical compound COC(OC)C(C)N GZOKAVHTSXSLNB-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-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
- IDPURXSQCKYKIJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 0.000 description 1
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- QAFODUGVXFNLBE-UHFFFAOYSA-N 1-methoxybutan-2-amine Chemical compound CCC(N)COC QAFODUGVXFNLBE-UHFFFAOYSA-N 0.000 description 1
- NAZDVUBIEPVUKE-UHFFFAOYSA-N 2,5-dimethoxyaniline Chemical compound COC1=CC=C(OC)C(N)=C1 NAZDVUBIEPVUKE-UHFFFAOYSA-N 0.000 description 1
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- DHEJIZSVHGOKMJ-UHFFFAOYSA-N 2-ethenylbenzaldehyde Chemical compound C=CC1=CC=CC=C1C=O DHEJIZSVHGOKMJ-UHFFFAOYSA-N 0.000 description 1
- BPGIOCZAQDIBPI-UHFFFAOYSA-N 2-ethoxyethanamine Chemical compound CCOCCN BPGIOCZAQDIBPI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 1
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical group COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- DVFGEIYOLIFSRX-UHFFFAOYSA-N 3-(2-ethylhexoxy)propan-1-amine Chemical compound CCCCC(CC)COCCCN DVFGEIYOLIFSRX-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
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical class NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 1
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical class NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 description 1
- LPUBRQWGZPPVBS-UHFFFAOYSA-N 3-butoxypropan-1-amine Chemical compound CCCCOCCCN LPUBRQWGZPPVBS-UHFFFAOYSA-N 0.000 description 1
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 description 1
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- 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
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
-
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Abstract
一种制备触变性含水涂料组合物的方法，该方法包括如下步骤：i)提供包含用于交联的羰基和酰肼官能团的粘合剂体系的水分散体；以及ii)在水分散体中，使醚胺与三(异氰酸酯)异氰脲酸酯反应以形成聚脲流挂控制剂。
Description
相关申请的交叉参考
本申请要求2008年7月24日提交的GB申请第0813548.5号的优先权，在此作为参考引入其公开的全部内容。
发明背景
1.发明领域
本发明涉及制备含水涂料组合物的方法、由该方法制得的含水涂料组合物、油漆配制剂、以及用涂料组合物或油漆配制剂涂布的制品。
2.相关技术的描述
聚合物涂料在保护表面免受例如湿气进入、磨耗和侵蚀以及增强材料的美学和功能性中的用途是已知的。通常使用如滚动、刷涂、喷洒、浇铸和气动喷涂或静电喷涂的技术将这些聚合物涂料以液体涂料组合物形式施用于表面上。
经常将这些涂料组合物调适成表现出流变特性，即它们在高剪切下自由流动而当在低剪切下时抗流动。如此，涂料组合物在静止时具有凝胶状稠度而当搅拌时具有流体稠度。该流变特性被称为触变性。
该触变性质意味着涂料组合物当在与施用于表面的相关的力作用下时易于流动和达到平稳，而当施用于垂直表面时在较低剪切力如重力作用下具有抵抗流动的趋势。这将涂料组合物的易于施用性与在垂直表面上降低的流挂或滴下趋势相结合。
在常规涂料组合物中使用流变改性剂以产生触变分布型(thixotropicprofile)并由此降低流挂缺陷是普遍的。该类流变改性剂通常称为流挂控制剂。
常规的触变性涂料组合物主要基于具有高挥发性有机化合物(VOC)内容物的溶剂型聚合物分散体。例如，溶剂型醇酸和油改性尿烷。存在各种改性剂以赋予该类溶剂型涂料组合物所需的触变特性，实例包括改性的无机粘土和聚酰胺或聚脲改性的醇酸。
由于需要降低VOC向地球大气中的排放，因此需要常规溶剂型醇酸和油改性尿烷的水性替代物。水性热塑性乙烯基聚合物分散体或热塑性水性聚氨酯分散体可用于含水涂料组合物中，但是不具有合适的性能如耐化学性、防水性、抗粘连性和低温挠性。
用于含水涂料组合物中具有良好性能结合的水性聚合物分散体的一个特定组为包含羰基-酰肼官能交联体系的那些。该类组合物的实例描述在专利申请US6730740和EP1125949中。
在US 6730740中，羰基官能聚合物在水性体系中与多官能酰肼交联剂结合以形成具有羰基-酰肼交联体系的涂料组合物。
在该类羰基-酰肼交联体系中，聚合物的交联在干燥时通过形成席夫碱而发生。在空气干燥过程中例如通过蒸发自体系中除去水，促使反应形成如以下实例图解所示的交联产物。
在具有羰基-酰肼交联体系的含水涂料组合物中通常在粘合剂聚合物上具有羰基官能团，在交联剂中具有酰肼官能团。然而，还有可能的是可在交联剂上具有羰基官能团，可在粘合剂聚合物上具有酰肼官能团。可替代地，可在聚合物粘合剂上具有羰基和酰肼官能团，从而允许聚合物粘合剂的分子直接互相连接而无需另外的交联剂组分。
具有羰基-酰肼交联体系的涂料组合物的水分散体提供有用的含水涂料组合物，由于其低的VOC要求和良好的性能因而是合意的。
然而，使用常规可获得的流挂控制剂如纤维素醚、碱性可膨胀丙烯酸聚合物、疏水改性碱性可膨胀增稠剂或非离子缔合性增稠剂在具有羰基-酰肼交联体系的含水涂料组合物中获得所需的触变性是困难的。这些增稠剂在水性涂料中提供假塑性流变，其中粘度随剪切速率的增加而降低(又称为剪切稀化)。引入假塑性，在恒定剪切速率下粘度随时间的下降复杂得多。可用于水性油漆中以获得该类假塑性的触变剂的实例包括热解法二氧化硅和改性粘土。然而，这些物质的加入常常对涂料性能如光泽或薄膜透明度产生不利影响。
因此需要对具有羰基-酰肼交联体系的含水涂料组合物显示良好结果的流挂控制剂。
WO 2008/030445和WO 2008/030437描述了通过使亲水性聚异氰酸酯与具有至少一个羟基官能或醚基团的伯氨基官能化合物反应而获得的聚脲流挂控制剂的含水组合物。直接在水(任选地包含水可混溶有机溶剂)中制备聚脲化合物，然后加入涂料组合物中。可替换地，它们可在粘合剂和交联体系的存在下“原位”制得。这些专利申请中的流挂控制剂并没有被公开与具有羰基-酰肼交联体系的涂料组合物一起使用。
本发明的目的在于提供用于具有羰基-酰肼交联体系的含水涂料配制剂的流挂控制剂，特别地与羰基-酰肼交联体系原位形成流挂控制剂。
发明概述
发明人已经发现三(异氰酸酯)异氰脲酸酯与醚胺的聚脲加合物对于包含羰基和酰肼交联体系的含水涂料组合物起到有效的流挂控制剂的作用。发明人还发现该类聚脲加合物流挂控制剂可有利地与羰基-酰肼交联体系原位(即在其存在下)形成从而获得使薄膜具有不含凝胶颗粒的改进外观的产物。
聚脲加合物流挂控制剂通过一种或多种醚胺与一种或多种三(异氰酸酯)异氰脲酸酯的反应以得到聚脲加合物而与羰基-酰肼交联体系原位形成。
令人惊讶的是可以在具有羰基-酰肼官能团的交联体系的存在下通过反应形成三(异氰酸酯)异氰脲酸酯与醚胺的加合物。这是由于醚胺对于交联体系的羰基官能团是高度反应的，且三(异氰酸酯)异氰脲酸酯的异氰酸酯对于交联体系的酰肼官能团是高度反应的。多异氰酸酯异氰脲酸酯与醚胺以及交联体系的大量反应因而被预期导致差的结果。
根据本发明，提供一种制备触变性含水涂料组合物的方法，该方法包括如下步骤：
i)提供包含聚合物粘合剂和羰基-酰肼交联体系的含水粘合剂体系；和
ii)在含水粘合剂体系中，使醚胺与三(异氰酸酯)异氰脲酸酯反应以形成聚脲流挂控制剂。
根据本发明的一个优选实施方案，提供一种制备触变性含水涂料组合物的方法，该方法包括如下步骤：
i)提供包含具有羰基和/或酰肼官能团的聚合物粘合剂的分散体和具有用于与聚合物粘合剂的官能团反应以发生交联的羰基和/或酰肼官能团的交联剂的含水粘合剂体系；和
ii)在含水粘合剂体系中，使醚胺与三(异氰酸酯)异氰脲酸酯反应以形成聚脲流挂控制剂。
在反应步骤中，醚胺和三(异氰酸酯)异氰脲酸酯反应以形成它们的聚脲加合物。
本文中使用的术语“醚胺”是指具有末端伯氨基的醚化合物。优选的醚胺为醚-一元胺。合适的醚-一元胺的实例为包含聚醚主链和单末端伯胺的聚醚-一元胺。特定的实例包括可获自Huntsman Performance Products，USA的Jeffamine MTM产品。
三(异氰酸酯)异氰脲酸酯为具有二异氰酸酯的三聚衍生物的化学式的化合物。
优选地，三(异氰酸酯)异氰脲酸酯为三(异氰酸酯烷基)异氰脲酸酯，其中优选各异氰酸酯烷基基团独立地包含5-14、更优选8-12、最优选6个碳原子。
优选地，三(异氰酸酯)异氰脲酸酯具有如下通式：
其中R＝(CH2)n，n＝5-14，优选8-12，最优选6。
三(异氰酸酯烷基)异氰脲酸酯可以常规地制备为二异氰酸酯的三聚衍生物。优选的实例包括含有5-14个碳原子的一种或多种二异氰酸酯的三聚衍生物，特别地包含8-12个碳原子的一种或多种二异氰酸酯的三聚衍生物。最优选地，三-异氰酸酯异氰脲酸酯为1，6-己二异氰酸酯的三聚衍生物。
本文中提到的含水涂料组合物是指包含至少聚合物粘合剂的水分散体和任选地交联剂的组合物。含水涂料组合物通常包含以组合物的总重计15-90重量％的水。优选地，其包含15-85重量％，更优选25-80重量％，最优选至少40重量％的水。其通常还包含以涂料组合物的总重计小于15重量％的挥发性有机化合物。优选地，其包含小于10重量％、更优选小于7重量％、最优选小于5重量％的挥发性有机化合物。
触变性的所需程度可以通过使用流挂控制剂获得，所述流挂控制剂的量以涂料组合物的总重计为至少0.01％、更优选至少0.05％、甚至更优选至少0.10％、最优选至少0.15％，和优选至多30％、更优选至多10％、甚至更优选至多3％、最优选至多1.5％。
根据本发明的第二方面，提供一种含水涂料组合物，其包含a)含有用于交联的羰基和酰肼官能团的粘合剂体系；b)聚脲流挂控制剂；以及c)水；其中所述聚脲流挂控制剂为醚胺与三(异氰酸酯)异氰脲酸酯的聚脲加合物。
在本发明的一个优选实施方案中，进一步提供一种含水涂料组合物，其包含具有羰基和/或酰肼官能团的粘合剂，任选地具有与粘合剂的官能团反应以产生交联的羰基和/或酰肼官能团的交联剂；聚脲流挂控制剂；和水；其中所述聚脲流挂控制剂为醚胺与三(异氰酸酯)异氰脲酸酯的聚脲加合物。
根据本发明，更进一步提供一种包含所述涂料组合物和着色剂如颜料的油漆配制剂。
本发明还提供一种用所述涂料组合物或油漆配制剂涂布的制品。
聚合物粘合剂
聚合物粘合剂可以为任何包含羰基官能团、酰肼官能团或羰基官能团和酰肼官能团两者的水可稀释聚合物粘合剂。优选地，聚合物粘合剂具有适合与交联剂上的酰肼基团发生交联反应的羰基官能团。
优选地，粘合剂为通过烯属不饱和单体的聚合而获得的乙烯基聚合物。可以使用的其它粘合剂为尿烷分散体、尿烷-酰基(acylic)分散体、醇酸分散体或醇酸-丙烯酸分散体。
羰基官能乙烯基聚合物的水分散体可经由乳液聚合方法通过烯属不饱和单体的聚合获得。具有至少一个烯属不饱和基团的单体的自由基引发含水乳液聚合的程序在过去经常被描述，是本领域熟练技术人员充分公知的[参照例如Encyclopedia of Polymer Science and Engineering，第8卷，第659页及随后各页(1987)；D.C.Blackley，in High Polymer Latices，第1卷，第35页及随后各页(1966)；H.Warson，The Applications of SyntheticResin Emulsions，第246页及随后各页，第5章(1972)和EmulsionPolymerization，Interscience Publishers，New York(1965)]。
烯属不饱和乳液聚合单体优选地选自如下：单亚乙烯基芳族单体、α-β烯属不饱和羧酸酯单体、乙烯基酯单体和这些单体的各种组合。
因此，优选的单亚乙烯基芳族单体包括苯乙烯、α-甲基苯乙烯、乙烯基甲苯、邻-、间-和对-甲基苯乙烯、邻-、间-和对-乙基苯乙烯及其组合。
优选的α-β烯属不饱和羧酸酯单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯以及这些酯的组合。
优选的乙烯基酯单体包括乙酸乙烯酯、一种有支链的烷烃羧酸的乙烯基酯，例如由Shell Chemicals以商品名VEOVATM 9、10和11)商业化的单体、丙烯腈以及它们的组合。
聚合物中的羰基优选获自具有羰基官能团的烯属不饱和单体的引入。特别优选的单体为酮官能单体如羟烷基丙烯酸酯和甲基丙烯酸酯的乙酰乙酸基酯如乙酰乙酸基甲基丙烯酸乙酯，以及含酮的酰胺如双丙酮丙烯酰胺。可用于共聚以引入这些基团的其它单体包括但不限于(甲基)丙烯醛、甲酰苯乙烯、双丙酮丙烯酸酯、乙腈丙烯酸酯、双丙酮甲基丙烯酸酯、2-羟基丙基丙烯酸酯乙酰乙酸酯、丁二醇-1，4丙烯酸酯乙酰乙酸酯或乙烯基烷基酮例如乙烯基甲基酮、乙烯基乙基酮或乙烯基丁基酮。
此外，聚合物可包含不同于羰基的官能团，例如羧基、硫酸酯或磺酸酯、磷酸酯、羟基、环氧乙烷、仲胺或叔胺、亚乙基脲或硅烷。
这些官能团用于赋予涂料组合物特定的性能如稳定性或者赋予用聚合物分散体配制的涂料特定的性能如粘合性。涂料组合物的稳定性可通过使用具有亲水基团如酸或酰胺官能团的共聚单体如丙烯酰胺和甲基丙烯酰胺加以改进。
其它可被包含以改进由涂料组合物形成的涂料的粘合性的官能单体包括叔胺或亚乙基脲基官能单体如二甲基氨基乙基甲基丙烯酸酯和N-(2-甲基丙烯酰氧基乙基)亚乙基脲。
用于引入羰基官能团的(甲基)丙烯酸单体的实例为丙烯酸、甲基丙烯酸、衣康酸和丙烯酸α-羧基乙酯。可使用具有其它烯属不饱和羧基的单体，例如马来酸酐的半酯。还可使用具有磺酸的单体，例如苯乙烯p-磺酸。具有酸的单体可作为自由酸或盐聚合，例如甲基丙烯酸乙酯-2-磺酸或2-丙烯酰胺基-2-甲基丙烷磺酸的NH4或碱金属盐，或对应的自由酸。
用于引入羟基官能团的单体的实例为具有羟基的丙烯酸酯，例如甲基丙烯酸羟乙酯、丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯。还可使用具有潜在羟基的单体，例如甲基丙烯酸缩水甘油酯。
当通过乳液聚合形成乙烯基聚合物时，单体混合物可以纯的形式或者以在水中的乳液形式加入。单体混合物在反应期间内可以以一或多次加入或连续地，线性或非线性或者其组合的形式加入。
如果需要，单体混合物可以包含任选的链转移剂(或不止一种任选的链转移剂)以及少量具有不止一个烯属不饱和键的单体。
可使用热或氧化还原引发方法开始乳液聚合。在整个反应过程中，反应温度通常保持在低于100℃的温度下。优选的反应温度为30-95℃、更优选50-90℃。
当形成聚合物分散体时，可使用通常以单体总重量计0.01-3.0重量％水平的常规自由基引发剂，例如过氧化氢、过氧化钠、过氧化钾、叔丁基或叔戊基过氧化氢、氢过氧化枯烯、铵和/或碱金属过硫酸盐、过硼酸钠、过磷酸及其盐、高锰酸钾、和过硫酸的铵或碱金属盐。可以使用氧化还原体系，其采用相同的引发剂作氧化剂与合适的还原剂配对，例如甲醛合次硫酸氢钠、抗坏血酸、异抗坏血酸、含硫的酸的碱金属和铵盐如亚硫酸钠、亚硫酸氢盐(bisulphite)、硫代硫酸盐、亚硫酸氢盐(hydrosulphite)、硫化物、氢硫化物或连二亚硫酸盐、甲脒亚磺酸、羟基甲磺酸、2-羟基-2-亚磺酸基乙酸钠、亚硫酸氢丙酮、胺如乙醇胺、乙醇酸、乙醛酸水合物、乳酸、甘油酸、苹果酸、酒石酸和前述酸的盐。可以使用铁、铜、锰或钴的那些的氧化还原反应催化金属盐。
在通过乳液聚合方法制备聚合物分散体时，通常使用表面活化剂。这些表面活化剂或表面活性剂形成胶束，所述胶束用作颗粒成核的场所，并在乳液聚合过程中有助于稳定生长的聚合物颗粒。表面活性剂还在聚合物分散体被合成之后稳定聚合物分散体。可使用常规的表面活性剂，例如阴离子和/或非离子乳化剂如烷基、芳基的碱金属或铵盐，或烷基芳基硫酸盐、磺酸盐或磷酸盐、烷基磺酸、磺基丁二酸盐、脂肪酸和乙氧基化醇或酚。所用表面活性剂的量通常以单体重量计为0.1-6重量％。
然而，在聚合物分散体中存在表面活性剂总是导致在由分散体形成的最终薄膜中的一定程度的水敏感性。因此，有时使用包含烯属不饱和键的表面活性剂，所述烯属不饱和键使得表面活性剂参与乳液聚合过程。这些表面活性剂，有时称为可聚合的表面活性剂，变成聚合物主链的一部分并赋予最终聚合物薄膜较少的水敏感性。使用可聚合表面活性剂制备的聚合物分散体的实例可在WO1999032522Al、EP1125949Al和Aramendia等人的Journal of Polymer Science，Part A：Polymer Chemistry 2004，42，No.17，第4202-4211页中发现。合适的可聚合表面活性剂包括式子为M+.-OOC-CH＝CHCOOR的马来酸酐的半酯，其中R为C(6-22)烷基和M+为Na+、K+、Li+、NH4+或质子化或季胺。具有烯属不饱和键的聚氧乙烯烷基苯基醚以商品名Noigen
RN(ex Montello，Inc.)，例如NOIGENRN-10TM、NOIGEN RN-20、NOIGEN RN-30、NOIGEN RN-40TM和NOIGEN RN-5065TM出售，或者其硫酸盐以商品名Hitenol
BC(exMontello，Inc.)，例如HITENOL BC-10TM、HITENOL BC-1025TM、HITENOL BC-20TM、HITENOL BC-2020TM、HITENOL BC-30TM出售。
还有具有磷酸酯和乙氧基亲水性两者的MAXEMULTM 6106(可获自Uniquema)，具有丙烯酸酯反应基团的标称C18烷基链。其它有代表性的适合该类反应的具有磷酸酯官能团的反应性表面活性剂包括但不限于MAXEMULTM 6112、MAXEMULTM 5011、MAXEMULTM 5010(所有可获自Croda Industrial Specialties)。适合用于本发明的各个实施方案的可替代的反应性表面活性剂包括烯丙氧基羟丙基磺酸钠(可以SIPOMERCOPS-1TM获自Rhodia)、ADEKA REASOAP SR/ER系列，例如ADEKAREASOAP ER-10、ER-20、ER-30和ER-40、Akeda Reasope SR-10、SR-20、SR-30(所有可获自Asahi Denka Co.，Ltd.)和烯丙基磺基琥珀酸酯衍生物(例如TREM LT-40TM(可获自Henkel))。
稳定含水聚合物分散体的另一方法为使用表面活化低聚物或聚合物。通常这些低聚物的特征为具有相对高的酸值(例如200毫克KOH/克)。最常见地，不得不使用另外的低分子量表面活性剂以控制颗粒大小/数目。有用的丙烯酸聚合物可以商品名″JONCRYL″自BASF市购得到。实例为JONCRYL 67、JONCRYL 586、JONCRYL 611、JONCRYL 678、JONCRYL 680、JONCRYL 682、JONCRYL 683、JONCRYL 690和JONCRYL 693，它们为具有98重量％不挥发性有机化合物和2重量％挥发性有机化合物的苯乙烯丙烯酸树脂，并可以透明薄片形式获得。其它可市购得到的聚合物包括获自获自Cook Composites and Polymers的CRAYMUL 8450、CRAYMUL 8460。
最近，例如Buckmann等(Paint&Coatings Ind.(US)2002，第18卷第10期，96(12pp))描述了在乳液聚合过程中用作稳定剂的低酸值低聚物。这些低聚物表面活性剂为数均分子量Mn为约5000、酸值为50-100毫克KOH/克的丙烯酸聚合物。任选地，这些低聚物可具有交联官能团，例如羰基或羟基或包含接枝位(例如来自甲基丙烯酸烯丙酯)。这些低聚物可在乳液聚合中用作唯一的稳定剂(因而不使用另外的常规表面活性剂)。
交联剂
具有羰基或酰肼官能团的聚合物粘合剂与具有羰基或酰肼官能团的交联剂混合以形成具有羰基-酰肼交联体系的含水粘合剂体系。
粘合剂体系可通过将交联剂简单共混至聚合物粘合剂的分散体中而获得。具有羰基-酰肼交联体系的所得粘合剂体系对于交联是官能性的。
交联剂带有与在聚合物粘合剂上具有的交联基团反应的官能团。优选地，聚合物粘合剂具有羰基官能团和交联剂具有酰肼官能团。酰肼官能交联剂为具有式子-NHNH2的羰基反应性官能团以及通过与具有至少两个碳原子的一元酮或一元醛反应衍生自该基团的羰基反应性腙基团的化合物。显然的是该类官能团通常为较大分子的一部分，例如-R-C(＝O)-NH-NH2、-R-C(＝O)-NH-N＝C＜、-R-NH-C(＝O)NH-NH2、-R-NH-C(＝O)-NH-N＝C＜和-R-NH-NH2，其中R为烷基、取代烷基、取代脂环基或取代芳基。
更优选地，酰肼官能交联剂为二酰肼或双腙例如二羧酸二酰肼例如乙二酸二酰肼、丙二酸二酰肼、琥珀酸二酰肼、戊二酸二酰肼、己二酸二酰肼、癸二酸二酰肼、马来酸二酰肼、富马酸二酰肼、衣康酸二酰肼、苯二甲酸二酰肼或对苯二酸二酰肼。环己烷二羧酸双酰肼、壬二酸双酰肼；以及碳酸酰肼、双氨基脲、三酰肼、二肼基酮和芳烃的二肼，例如1，4-二肼基苯和2，3-二肼基萘(2，3-dihydrazinonophthalene)、二肼和本领域已知的其它酰肼。
可替代地，交联剂可以为水溶性脂族二肼、亚乙基-1，2-二肼、亚丙基-1，3-二肼和亚丁基-1，4-二肼、或多胺如异佛尔酮二胺或4，7-二氧杂癸烷-1，10-二胺。
优选地，交联剂为己二酸二酰肼。
具有聚合物粘合剂和羰基-酰肼交联体系的含水粘合剂体系
合适的包含二-或多-酰肼交联剂的羰基官能含水聚合物粘合剂分散体可以商品名Setaqua 6756TM和Setaqua 6778(可获自Nuplex Resins)、NeoCryl XK-98(可获自DSM NeoResins+)、VIACRYL VSC6286w/45WATM和VIA CRYL VSC 6295w/45WATM(可获自Cytec)、AcronalA-603TM和Acronal A-627(可获自BASF)市购得到。
用流挂控制剂改性
上述含水粘合剂体系可根据本发明的方法用聚脲加合物流挂控制剂进行改性。
醚胺与三(异氰酸酯)异氰脲酸酯的反应优选在5-80℃、优选10-60℃、最优选20-40℃的温度下进行。
在该方法中，可向树脂中连续加入醚胺和三(异氰酸酯)异氰脲酸酯，或者先加入任何一个组分；或者将它们同时加入。优选地，在加入三(异氰酸酯)异氰脲酸酯之前加入醚胺。
在用于制备聚脲加成物的醚胺与三(异氰酸酯)异氰脲酸酯的反应中，醚胺或三(异氰酸酯)异氰脲酸酯可相对于化学计量的量过量使用。然而，比例优选为1∶1。
在优选的实施方案中，方法包括如下步骤：
a.提供包含羰基-酰肼官能交联体系的含水涂料组合物；
b.向组合物中加入醚胺，优选在搅拌下；
c.向含水聚合物分散体的混合物中加入三(异氰酸酯)异氰脲酸酯，优选在搅拌下；以及
d.使醚胺与三(异氰酸酯)异氰脲酸酯反应以得到聚脲加合物流挂控制剂。
三(异氰酸酯)异氰脲酸酯
三(异氰酸酯)异氰脲酸酯为具有二异氰酸酯的三聚衍生物的化学式的化合物。
优选地，三(异氰酸酯)异氰脲酸酯为三(异氰酸酯烷基)异氰脲酸酯或三(异氰酸酯环烷基)异氰脲酸酯，其中优选各异氰酸酯烷基基团独立地包含5-14、更优选8-12、最优选6个碳原子。
优选地，三(异氰酸酯)异氰脲酸酯具有如下通式：
其中R＝(CH2)n，n＝5-14、优选8-12、最优选6。
优选地，用于制备流挂控制剂的三(异氰酸酯)异氰脲酸酯形成为包含5-14个碳原子的一个或多个二异氰酸酯的三聚物，特别是包含8-12个碳原子的一个或多个二异氰酸酯的三聚物。最优选地，三(异氰酸酯)异氰脲酸酯由1，6-己二异氰酸酯形成。
合适的二异氰酸酯的非限定性实例为：亚甲基二异氰酸酯、三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、1，6-己二异氰酸酯、环己基-1，4-二异氰酸酯、二环己基甲烷-4，4′-二异氰酸酯、二环己基二甲基甲烷-4，4′-二异氰酸酯、2，4-甲苯二异氰酸酯、2，6-甲苯二异氰酸酯和二苯基甲烷-4，4′-二异氰酸酯、3-异氰酸基甲基-3，5，5-三甲基环己基异氰酸酯(异氟尔酮二异氰酸酯)。
三(异氰酸酯)异氰脲酸酯可以为由三个相同的二异氰酸酯分子形成的三聚物，或者也可由2或3个不同的二异氰酸酯形成。任选地，可使用得自上述提及的不同组的二异氰酸酯的二异氰酸酯混合物。
三(异氰酸酯)异氰脲酸酯可任选地例如通过用至少一个非离子或阴离子亲水基团进行改性而改性为亲水性的。水溶性或水可分散聚异氰酸酯可例如通过用羧化物、磺酸酯和/或聚氧化乙烯基团和/或聚氧化乙烯/聚氧化乙烯基团进行改性而获得。聚异氰酸酯的亲水化是可能的，例如通过与不足量的一羟基、亲水聚醚醇进行反应。在例如EP-A 0 540 985的第3页第55行-第4页第5行中描述了该类亲水化聚异氰酸酯的制备。上述分散在水中的聚异氰酸酯的实例可包括Bayhydur VPLS-2032TM、BayhydurVPLS-2319TM、Bayhydur 3100TM、Bayhydur VPLS-2336TM和VPLS-2150/1(可获自Bayer)、RhodocoatTM WAT、RhodocoatTMWAT-l、RhodocoatTM WT 2102、RhodocoatTM X EZ-DTM 401、RhodocoatTM XEZ-DTM 803、RhodocoatTM X EZ-MTM 501、RhodocoatTM X EZ-MTM 502、RhodocoatTM X WAT-3、RhodocoatTM X WAT-4(可获自Rhodia)。
任选地，可以使用三(异氰酸酯)异氰脲酸酯的混合物。
醚胺
以下为用在本发明中的有代表性的醚胺的实例：(环)烷氧基(环)烷基一元胺、单(环)烷氧基芳烃胺、多(环)烷氧基芳烃胺、芳烃氧(环)烷氧基胺、芳氧基(环)烷基胺、芳烃氧芳烃胺、芳氧基芳基胺。醚胺可任选地包含一个或多个羟基基团。醚胺优选不包含大于55个碳原子，优选仅具有1-24个，更特别地1-12个碳原子。
合适的醚胺的特定实例包括：2-甲氧基乙胺、2-乙氧基乙胺、3-甲氧基-1-丙胺、1-甲氧基甲基丙胺、1，1-二甲氧基-2-丙胺、3-乙氧基-1-丙胺、3-丁氧基-1-丙胺、3-(2-乙基己氧基)-1-丙胺、3-十三烷氧基丙胺、3-硬脂氧基丙胺、对甲氧基苄胺、3，4-二甲氧基苄胺、对甲氧基苯基乙胺、3，4-二甲氧基苯基-乙胺、9-苯氧基-4，7-二氧环己酮基-1-胺、2-甲基-4-甲氧基苯胺、2，5-二甲氧基-苯胺、糠胺、四氢糠胺、2-(4-吗啉基)乙胺、4-(3-氨基丙基)吗啉、2，2′-氨基乙氧基乙醇、4，7-二氧杂癸烷-1，10-二胺、4，9-二氧杂癸烷-1，12-二胺、7-甲基-4，10-二氧杂十三烷-1，13-二胺、4，7，10-三氧杂十三烷-1，13-二胺和分子量为约750的双(3-氨丙基)聚四氢呋喃。
可用于本发明的聚醚胺可以商品名Jeffamine MTM获得(获自Huntsman Performance Products，USA)。Jeffamine M 600TM例如为具有甲氧乙基末端的聚丙二醇一元胺，分子量约为600。其它类型包括JeffamineM-1000TM(MW约1000)、Jeffamine M-2005TM(MW约2000)、JeffamineM-2070TM(MW约2000)。
最优选的醚胺为3-甲氧基-1-丙胺。
还可使用上述提及的醚胺的混合物。
含水涂料组合物的另外的组分
含水涂料组合物可进一步包含另外的流变改性剂、聚结剂、溶剂、抗微生物剂、湿润剂、消泡剂、染料、保湿剂、蜡、表面活性剂、填料或增量剂、着色剂、平光剂、中和剂、缓冲剂、冷冻-解冻添加剂、增塑剂、抗泡剂、增粘剂、受阻胺光稳定剂、UV吸收剂如二苯甲酮、取代的二苯甲酮，和取代的苯乙酮、分散剂、抗氧化剂和颜料。
合适的颜料和增量剂的实例包括二氧化钛如锐钛矿和金红石二氧化钛、氧化锌、氧化锑、氧化铁、硅酸镁、碳酸钙、有机和无机有色颜料、硅铝酸盐、二氧化硅、各种粘土如高岭土和层状瓷土、以及氧化铅。
可向油漆或涂料中加入挥发性有机组分(VOC)以改进薄膜性能或者辅助应用性能。合适的VOC的实例为乙二醇醚、有机酯、芳族化合物、乙二醇和丙二醇，以及脂族烃。
本发明的含水组合物特别适合形成用于保护性和装潢性修整的组合物，例如抗水剂、半透明着色料、透明清漆；或用在木质底物上的单色着色料。这些木质底物包括之前未经保护性组合物处理的风化或未风化的木材，以及其中由于风化导致之前的处理已经退化的经处理的木材。
实施例
实施例1用3％聚脲(以固体计)改性的丙烯酸分散体
将2000克Setaqua 6756TM(可市购得到的包含二酰肼交联剂的羰基-官能丙烯酸聚合物分散体，其中固体含量为40±1％，可获自Nuplex Resins)称重至配备有锚式搅拌器的5升烧瓶中。将内容物加热至35℃，同时以200rpm进行搅拌。加入8.5克甲氧基丙胺，并伴随着将搅拌速率提高至600rpm。继续混合15分钟。在15分钟的时间内逐滴加入18.30克TolonateHDT LVTM(由Rhodia以非挥发性液体形式提供的脂族聚异氰酸酯(1，6-己二异氰酸酯三聚物))。以650rpm继续搅拌另外的30分钟，将反应混合物的温度保持在40℃以下。然后以450rpm将反应混合物冷却至30℃。
在玻璃上刮涂改性聚合物分散体呈现了透明和无点(bit-free)的薄膜。改性聚合物分散体的固体含量为40.8％，pH为8.6。
使用Physica Measuring设备MC 200SN 280754；FW 2.07(锥/板)，测量系统MK22/Ti/442比较改性聚合物分散体的流变性与未改性聚合物分散体Setaqua 6756TM的流变性。
实施例2用3％聚脲改性的丙烯酸聚合物分散体
2.a根据EP1125949Al合成丙烯酸聚合物分散体
向配备有两叶片搅拌器，冷凝器和用于加入单体预制乳液、引发剂的入口，及其它辅助设备的两升双夹套玻璃反应器中装入417克软化水、22.5克马来酸酐的正十二烷基半酯、1.7克碳酸氢钠和0.1克25％氨水溶液。将该混合物在搅拌下加热至70℃。
同时在分开的容器A和B中通过混合如表I中所示的成分而制备两种混合物。
从容器A中获取1.24克混合物1，将其加入反应器中。在混合10分钟后，将0.75克在7克软化水中的过硫酸钠溶液加入反应器中。在放热减退后，使用下述步骤开始单体加入。同时将容器B的内容物按定量加入容器A中，将容器A的内容物泵送至反应器中。控制加入速率以在90分钟后排空两个容器。容器A配备有搅拌器以确保内容物良好混合。
同时，对于单体加入，将1克在114克水中的过硫酸钠溶液定量加入反应器中。在单体加入过程中，使温度升至85℃。在完成加入后，将反应器内容物在85℃下保持另外的30分钟。将批量料冷却至65℃，并将0.9克叔丁基过氧化氢(70％水溶液)在3克软化水中的溶液送料至反应器中。然后将0.4克甲醛合次硫酸氢钠在5克软化水中的溶液在15分钟的时间内定量加入反应器中。在完成加入后，将批量料在65℃下保持另外的30分钟。在搅拌下，将13克己二酸二酰肼溶解在反应器的内容物中。为确保合适的溶液，继续搅拌和加热另外的30分钟。将批量料冷却至30℃，最后向反应器中加入0.3％分散的Proxel AQ(可获自Arch Chemicals)，使内容物过滤经过80微米的Perlon滤袋以除去任何凝块。
所得聚合物分散体具有的颗粒大小为87纳米(Z均平均值，MalvernZetasizer)，固体含量为42％。分散体的pH为8.4，粘度为0.41帕·秒(在23℃下)。
2.b.在实施例2.a中获得的聚合物分散体的聚脲改性
在5升的反应烧瓶中，将获自实施例2.a的1840克的丙烯酸聚合物分散体和184克软化水加热至35℃并以200rpm进行搅拌。将7.82克甲氧基丙胺加入至烧瓶中，并在15分钟内进行混合。搅拌速率提高至650-700rpm。在3分钟的时间内，加入22.49克Desmodur VP LS 2032(基于1，6-己二异氰酸酯的水可分散的聚异氰酸酯，可获自Bayer)。使用9.20克软化水冲洗加料漏斗。继续搅拌30分钟，不允许温度超过40℃。以200rpm的搅拌速率将批量料冷却至30℃。
改性聚合物分散体的固体含量为40％，pH为8.6，颗粒大小为111纳米(Z均平均值，Malvern Zetasizer)。
将改性聚合物分散体的流变性与如上所述获自实施例2.a的未改性聚合物分散体的流变性进行比较。
实施例3用3％聚脲改性的苯乙烯丙烯酸分散体
3.a合成苯乙烯-丙烯酸聚合物分散体
向配备有两叶片搅拌器，冷凝器和用于加入单体预制乳液、引发剂的入口及其它辅助设备的两升双夹套玻璃反应器中装入833克软化水、12克Dextrol OC 7525TM(可获自Dexter Chemicals)和1克氨(25％水溶液)。在氮气流下将反应器的内容物加热至72℃。同时制备两个预制乳液。通过混合263克软化水、4克Dextrol OC 7525、2克氨(25％水溶液)和693克单体混合物A(参见表2)来制备单体预制乳液A。
通过混合239克软化水、4克Dextrol OC 7525、1克氨(25％水溶液)和679克单体混合物B(参见表2)来制备单体预制乳液B。
向反应器中加入49克预制乳液A以及由在14克水中的1克过硫酸铵组成的引发剂溶液。使反应混合物的温度升高至79℃。在放热减退后，将由2克过硫酸铵和227克软化水组成的引发剂溶液和预制乳液A在150分钟的时间内定量加入反应器中。在相同时间内将预制乳液B定量加入包含预制乳液A的容器中。在定量加入后，使用80克软化水冲洗包含预制乳液的容器。将批量料冷却至65℃。在10分钟的时间内加入13克氨(25％水溶液)在20克软化水中的溶液，然后加入2克叔丁基过氧化氢(70％水溶液)在6克水中的溶液。将温度在65℃下保持30分钟。然后将1克甲醛合次硫酸氢钠在11克软化水中的溶液在15分钟的时间内定量加入反应器中。将温度在65℃下保持另外的30分钟。将25.9克己二酸二酰肼加入反应混合物中，并将温度在65℃下保持30分钟。然后将批量料冷却至40℃以下的温度。加入溶解在12克软化水中的5克氨(25％水溶液)，接着加入5克Proxel AQTM(可获自Arch Chemicals)。将反应器的内容物过滤经过100微米GAF滤袋，并存储在合适的容器中。
表2：单体组合物
所得苯乙烯丙烯酸分散体具有的固体含量为44％，pH为8.5，颗粒大小为100纳米(Z均平均值，Malvern Zetasizer)。
3.b获自实施例3.a的苯乙烯-丙烯酸聚合物分散体的聚脲改性
在5升烧瓶中，将获自实施例3.a的1840克聚合物分散体和184克软化水加热至35℃并以200rpm进行搅拌。
加入7.82克甲氧基丙胺，并在15分钟的过程中以650-700rpm进行混合。在3分钟的时间内，加入22.49克Desmodur VPLS 2032(基于1，6-己二异氰酸酯的水可分散的聚异氰酸酯，可获自Bayer)。使用9.20克软化水冲洗装异氰酸酯的漏斗。继续混合30分钟。温度不允许超过40℃。将反应混合物冷却至30℃，并倒入存储容器中。所得产物具有的固体含量为41.4％，pH为8.6，颗粒大小为110纳米(Z均平均值，Malvern Zetasizer)。
将改性聚合物分散体的流变性与如上所述获自实施例3.a的未改性聚合物分散体的流变性进行比较。
测量体系：MK24/Ti/102
实施例4用如欧洲专利申请1 048 681中所述的聚脲氨酯(poly ureaurethane)改性的丙烯酸分散体(对比)
在环境温度下利用高速搅拌机(1000rpm)在搅拌下，向147.7克可市购得到的包含二酰肼交联剂的羰基官能丙烯酸聚合物分散体SetaquaTM 6756中加入13.8克软化水和3.46克如EP 1 048 681中所述的可以Byk 420(在N-甲基吡咯烷酮中的52％溶液，ex Byk Chemie)市购得到的聚脲氨酯。在加入后，继续搅拌5分钟。
对改性分散体进行刮涂(150微米湿膜厚度)。薄膜为混浊的且包含很多凝胶颗粒。
实施例5水性木材着色料
使用表3中所列的成分制备预混合物。在室温下使用Dispermat
或螺旋桨式搅拌器进行混合。
表3：预混合物
| 成分 | 重量份 | |
| 水 | 320.00 | |
| Mergal 710(ex Troy Corporation) | 8.00 | 抗微生物剂 |
| 丙二醇 | 15.00 | 助溶剂 |
| BYK 345(ex Byk Chemie) | 2.00 | 湿润剂 |
| Tego Foamex 810(ex Tego) | 2.00 | 消泡剂 |
| 2-氨基-2-甲基-1-丙醇(90％水溶液) | 3.00 | 中和胺 |
| 一缩二丙二醇正丁醚 | 20.00 | 助溶剂 |
将31.5克获自实施例1、2和3的聚脲改性丙烯酸分散体用软化水稀释至固体含量为36.4％，并使用Dispermat
将其与18.5克预混合物进行混合；在加入后以1000rpm混合5分钟。以类似方式制备基于Setaqua 6756TM的木材着色料。粘度数据如下所列：
测量体系：MK 22/TI/442
使用制膜器将木材着色料施用至玻璃片。湿膜厚度为150微米。基于SetaquaTM 6756和实施例1的分散体的着色料呈现透明薄膜。基于实施例4的木材着色料为混浊的且包含凝胶颗粒。使用多切口涂板器根据ASTMD4400-99(2007)测定木材着色料的抗流挂性。结果如下所示。
| 木材着色料，基于 | Setaqua 6756 | 实施例1 | 实施例4(对比) |
| 抗流挂性(微米) | ＜75 | 175 | 75 |
这些结果表明当使用根据本发明的聚脲改性时，具有优越的抗流挂性能。
因此，已经参照上述特定实施方案描述了本发明。应该认识到可对这些实施方案进行本领域熟练技术人员公知的各种改变和替代形式。
除了上述的那些外，在不背离本发明的实质和范围的情况下可对本文中描述的技术进行进一步的改变。因此，尽管已经描述了具体的实施方案，但是这些仅是实施例而不限制本发明的范围。
Claims (13)
1.一种制备触变性含水涂料组合物的方法，包括如下步骤：
i)提供包含聚合物粘合剂的分散体和羰基-酰肼交联体系的含水粘合剂体系；和
ii)在含水粘合剂体系中，使醚胺与三(异氰酸酯)异氰脲酸酯反应以形成聚脲流挂控制剂，
其中所述醚胺为(环)烷氧基(环)烷基一元胺，和所述三(异氰酸酯)异氰脲酸酯具有包含5-14个碳原子的一个或多个二异氰酸酯的三聚衍生物的化学式。
2.根据权利要求1所述的方法，其中所述聚合物粘合剂包含羰基和/或酰肼官能团，和任选地所述含水粘合剂体系包含具有用于与聚合物粘合剂的官能团反应以产生交联的羰基和/或酰肼官能团的交联剂。
3.根据权利要求1所述的方法，其中所述三(异氰酸酯)异氰脲酸酯具有如下通式：
其中R为取代或未取代的烷基。
4.根据权利要求1所述的方法，其中所述三(异氰酸酯)异氰脲酸酯包含亲水基团。
5.根据权利要求1所述的方法，其中所述醚胺与三(异氰酸酯)异氰脲酸酯的反应在5-80℃下进行。
6.根据权利要求1所述的方法，其中所述含水粘合剂体系包含具有羰基官能团的聚合物粘合剂和具有酰肼官能团的交联剂。
7.根据权利要求1所述的方法，其中所述聚合物粘合剂具有500-250000的数均分子量。
8.一种含水涂料组合物，其包含：
a)含有聚合物粘合剂的分散体以及羰基和酰肼交联体系的含水粘合剂体系；
b)聚脲流挂控制剂；以及
c)水；
其特征在于所述聚脲流挂控制剂为醚胺与三(异氰酸酯)异氰脲酸酯的聚脲加合物，其中所述醚胺为(环)烷氧基(环)烷基一元胺，和所述三(异氰酸酯)异氰脲酸酯具有包含5-14个碳原子的一个或多个二异氰酸酯的三聚衍生物的化学式。
9.根据权利要求8所述的含水涂料组合物，其包含：
i)10-90重量％的聚合物粘合剂固体，其包含至少一种酰肼和羰基交联基团；
ii)0-70重量％的交联剂固体，其包含至少一种可与聚合物粘合剂上的交联基团反应的酰肼和羰基交联基团；
iii)0.01-30重量％的聚脲流挂控制剂固体；和
iv)15-90重量％的水；
其中i)至iv)的重量％合计达涂料组合物的100％。
10.根据权利要求8或9所述的含水涂料组合物，其包含0.01-30重量％的聚脲流挂控制剂。
11.一种包含根据权利要求8、9或10所述的涂料组合物和任选地涂料添加剂和/或有机溶剂的油漆配制剂。
12.一种包含根据权利要求8、9或10所述的涂料组合物的木材着色料配制剂。
13.一种用权利要求8、9或10所述的涂料组合物、权利要求11所述的油漆配制剂或权利要求12所述的木材着色料涂布的制品。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0813548A GB2462105A (en) | 2008-07-24 | 2008-07-24 | Thixotropic aqueous coating composition |
| GB0813548.5 | 2008-07-24 | ||
| PCT/EP2009/059554 WO2010010171A1 (en) | 2008-07-24 | 2009-07-24 | Aqueous coating composition and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102105541A CN102105541A (zh) | 2011-06-22 |
| CN102105541B true CN102105541B (zh) | 2013-09-25 |
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| CN2009801290259A Active CN102105541B (zh) | 2008-07-24 | 2009-07-24 | 含水涂料组合物及其制备方法 |
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| US (1) | US9023942B2 (zh) |
| EP (1) | EP2326689B1 (zh) |
| JP (1) | JP5647605B2 (zh) |
| CN (1) | CN102105541B (zh) |
| AU (1) | AU2009273214A1 (zh) |
| GB (1) | GB2462105A (zh) |
| MY (1) | MY150534A (zh) |
| WO (1) | WO2010010171A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2842949A1 (en) * | 2011-08-08 | 2013-02-14 | Momentive Specialty Chemicals Inc. | Compositions and processes for dust suppression |
| EP2945994B1 (en) | 2013-01-18 | 2018-07-11 | Basf Se | Acrylic dispersion-based coating compositions |
| CN109777177B (zh) | 2013-03-15 | 2022-03-15 | 宣伟投资管理有限公司 | 耐沾污性的水基组合物 |
| US10196537B2 (en) | 2013-03-15 | 2019-02-05 | The Sherwin-Williams Company | Dirt pick-up resistant composition |
| BR112016004952B1 (pt) | 2013-09-13 | 2021-07-20 | Dow Global Technologies Llc | Dispersão tixotrópica, método para fazer a dispersão tixotrópica e composição de resina curável |
| JP6216890B2 (ja) * | 2013-09-30 | 2017-10-18 | サートゥンティード コーポレーション | 防汚およびｖｏｃ除去塗料ならびにその使用 |
| ES2763773T3 (es) * | 2015-10-20 | 2020-06-01 | Basf Se | Composiciones de revestimiento para revestir placas de fibrocemento |
| AR107710A1 (es) * | 2016-02-23 | 2018-05-23 | Ecolab Usa Inc | Emulsiones de polímero entrecruzado de hidrazida para usar en recuperación de petróleo crudo |
| CN107603440B (zh) * | 2017-08-22 | 2021-07-09 | 山西省建筑科学研究院 | 聚脲型建筑用反射隔热涂料的制备方法 |
| MX2020012514A (es) | 2018-05-29 | 2021-02-16 | Swimc Llc | Composiciones a base de agua con retencion de brillo a largo plazo. |
| JP7198615B2 (ja) * | 2018-07-10 | 2023-01-04 | ダイセル・オルネクス株式会社 | 硬化性樹脂組成物及びその硬化物 |
| CA3129878C (en) * | 2019-02-15 | 2023-08-29 | Kansai Paint Co., Ltd. | Paint composition comprising a binder component, a first rheology control agent and a second rheology control agent |
| CN110105799B (zh) | 2019-05-07 | 2021-10-01 | 广东华润涂料有限公司 | 木器用涂料组合物以及由其制成的木制品 |
| KR102386765B1 (ko) * | 2020-07-20 | 2022-04-18 | 에코리아 주식회사 | 철강제품 표면 코팅용 보수재 및 이를 이용한 보수방법 |
| CN114621387B (zh) * | 2020-12-10 | 2023-08-11 | 万华化学集团股份有限公司 | 用于柔性防水材料的脲基改性的聚丙烯酸酯水性分散体 |
| WO2022258507A1 (en) * | 2021-06-07 | 2022-12-15 | Basf Coatings Gmbh | Water-borne coating composition, its preparation method and application thereof |
| KR102442868B1 (ko) * | 2022-04-12 | 2022-09-14 | 맥스지오 주식회사 | 고분자 초속경 폴리우레아 도료 및 이를 이용한 도장 및 방수 공법 |
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| US4540734A (en) * | 1984-07-30 | 1985-09-10 | General Motors Corporation | Sag control of high solid polyurethane clearcoats by urea thixotrope/acrylic microgel systems |
| NL8500475A (nl) * | 1985-02-20 | 1986-09-16 | Akzo Nv | Thixotrope bekledingssamenstelling. |
| NL8500476A (nl) * | 1985-02-20 | 1986-09-16 | Akzo Nv | Thixotrope bekledingssamenstelling. |
| GB2237277A (en) * | 1989-10-26 | 1991-05-01 | Ici Plc | Thixotropic binder system |
| JP3394588B2 (ja) * | 1994-03-10 | 2003-04-07 | 三菱レイヨン株式会社 | 水性被覆材組成物 |
| GB9726890D0 (en) | 1997-12-20 | 1998-02-18 | Ici Plc | Polymerisation method |
| CA2283373A1 (en) * | 1998-09-25 | 2000-03-25 | Akzo Nobel Nv | Aqueous cross-linkable polymer composition for use in coatings |
| DE19919482C2 (de) * | 1999-04-29 | 2001-04-26 | Byk Chemie Gmbh | Verfahren zur Herstellung eines Thixotropie-Mittels und dessen Verwendung |
| EP1125949B1 (en) * | 2000-02-16 | 2006-05-03 | Nuplex Resins B.V. | Aqueous dispersions of particles of polymers with a glass transition temperature gradient |
| US8742052B2 (en) * | 2005-01-11 | 2014-06-03 | Nuplex Resins B.V. | Polyurea compound |
| EP1838747B1 (en) * | 2005-01-11 | 2018-04-18 | Allnex Netherlands B.V. | Comixtures for use in rheology modification |
| KR101317545B1 (ko) * | 2005-06-28 | 2013-10-15 | 누플렉스 레진스 비브이 | 요변성 레올로지 개량제로서의 폴리우레아 생성물 |
| JP4866140B2 (ja) * | 2006-04-28 | 2012-02-01 | 関西ペイント株式会社 | 硬化型樹脂組成物 |
| CN101443377A (zh) * | 2006-05-12 | 2009-05-27 | 树脂核动力工业有限公司 | 自氧化干燥聚氨酯水分散体 |
| WO2008030445A1 (en) | 2006-09-05 | 2008-03-13 | E. I. Du Pont De Nemours And Company | Sagging control agents |
| CN101511897A (zh) * | 2006-09-05 | 2009-08-19 | 纳幕尔杜邦公司 | 流挂控制剂的含水组合物 |
-
2008
- 2008-07-24 GB GB0813548A patent/GB2462105A/en not_active Withdrawn
-
2009
- 2009-07-24 WO PCT/EP2009/059554 patent/WO2010010171A1/en active Application Filing
- 2009-07-24 EP EP09781030.3A patent/EP2326689B1/en active Active
- 2009-07-24 MY MYPI20110311 patent/MY150534A/en unknown
- 2009-07-24 CN CN2009801290259A patent/CN102105541B/zh active Active
- 2009-07-24 JP JP2011519182A patent/JP5647605B2/ja active Active
- 2009-07-24 AU AU2009273214A patent/AU2009273214A1/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| GB0813548D0 (en) | 2008-09-03 |
| US20110124795A1 (en) | 2011-05-26 |
| EP2326689B1 (en) | 2013-06-26 |
| MY150534A (en) | 2014-01-30 |
| GB2462105A (en) | 2010-01-27 |
| JP5647605B2 (ja) | 2015-01-07 |
| WO2010010171A1 (en) | 2010-01-28 |
| CN102105541A (zh) | 2011-06-22 |
| AU2009273214A1 (en) | 2010-01-28 |
| EP2326689A1 (en) | 2011-06-01 |
| JP2011528747A (ja) | 2011-11-24 |
| US9023942B2 (en) | 2015-05-05 |
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