CN110945038A - 水性聚合物分散体 - Google Patents
水性聚合物分散体 Download PDFInfo
- Publication number
- CN110945038A CN110945038A CN201780093482.1A CN201780093482A CN110945038A CN 110945038 A CN110945038 A CN 110945038A CN 201780093482 A CN201780093482 A CN 201780093482A CN 110945038 A CN110945038 A CN 110945038A
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- polymer
- polymer dispersion
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- aqueous
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- 239000006185 dispersion Substances 0.000 title abstract description 16
- 239000008199 coating composition Substances 0.000 claims abstract description 51
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- 239000004815 dispersion polymer Substances 0.000 claims description 60
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 57
- 239000004094 surface-active agent Substances 0.000 claims description 44
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 28
- 125000000524 functional group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 3
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
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- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 claims 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 70
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- 230000000052 comparative effect Effects 0.000 description 57
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- 238000000034 method Methods 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 21
- 239000000839 emulsion Substances 0.000 description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 20
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 19
- -1 hydroxyalkyl acrylates Chemical class 0.000 description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 17
- 229910000077 silane Inorganic materials 0.000 description 17
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
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- 238000002360 preparation method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
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- 239000002562 thickening agent Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
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- 239000000758 substrate Substances 0.000 description 9
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000013530 defoamer Substances 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 6
- 239000000080 wetting agent Substances 0.000 description 6
- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical compound C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 5
- 239000004606 Fillers/Extenders Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000003906 humectant Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 230000003472 neutralizing effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000006254 rheological additive Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 2
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
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- XDIAMRVROCPPBK-UHFFFAOYSA-N 2,2-dimethylpropan-1-amine Chemical compound CC(C)(C)CN XDIAMRVROCPPBK-UHFFFAOYSA-N 0.000 description 1
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- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- MRVQOBZDYPXTGD-UHFFFAOYSA-N prop-2-enoyloxymethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCOC(=O)C=C MRVQOBZDYPXTGD-UHFFFAOYSA-N 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- VSVCAMGKPRPGQR-UHFFFAOYSA-N propan-2-one;sulfurous acid Chemical compound CC(C)=O.OS(O)=O VSVCAMGKPRPGQR-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
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- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
提供了水性聚合物分散体和包含这种水性聚合物分散体的水性涂料组合物,并提供了具有改进的早期耐水泡性以及令人满意的耐水纹性和良好耐久性的涂料。
Description
技术领域
本发明涉及水性聚合物分散体和包含其的水性涂料组合物。
前言
水性或水基涂料组合物由于较少的环境问题变得比溶剂基涂料组合物越来越重要。对于将涂料日常地暴露于户外的外部涂料应用,水性涂料组合物需要快速发展出耐水性和耐水纹性,以及提供具有良好耐久性以抵抗紫外线(UV)暴露的涂料。
通过掺入疏水性单体可以改善耐水纹性和早期耐水泡性。US6630533B2涉及一种外部整理组合物,以改善耐污垢性、耐湿磨性、耐洗出性和耐水泛白性。所述组合物包含:a)基于所述组合物的重量为3至65重量%的一种聚合物,所述聚合物包含疏水性单体作为聚合单元(即所述聚合物的20至100重量份的至少一种C12至C40(甲基)丙烯酸的烷基酯)和流变改性剂。该聚合物是在不可聚合的阴离子表面活性剂如十二烷基硫酸钠的存在下通过乳液法制备的。仍然需要进一步改善早期耐水疱性,并最小化昂贵的疏水性单体的使用。
因此,期望提供一种具有成本效益的解决方案,其对于外部应用具有良好的早期耐水泡性和令人满意的耐水纹性,同时保持良好耐久性。
发明内容
本发明提供了由单体混合物获得的聚合物的新型水性分散体,该单体混合物包括特定的可聚合表面活性剂、带有至少一个烷氧基硅烷官能团的烯键式不饱和单体和苯乙烯单体的新型组合。包含这种水性聚合物分散体的水性涂料组合物使涂料具有出乎意料的良好的早期耐水起泡性和令人满意的耐水纹性,同时保持良好的耐久性。
在第一方面,本发明是水性聚合物分散体,其包括一种聚合物,其中按聚合物的重量计,所述聚合物包含,
(a)0.55重量%至5重量%的具有式(I)结构的可聚合表面活性剂的结构单元,
其中R1是苯基或苯基取代的烷基;m1是1、2、3或4;R2是烷基或取代的烷基;m2是0或1;R3是氢或C1-C20烷基;R4是氢或C1-C20烷基;A表示具有2至4个碳原子的亚烷基或取代的亚烷基;n是1至100范围内的整数;并且X表示氢或选自-(CH2)a-SO3M、-(CH2)b-COOM、-PO3M2、-P(Z)O2M或-CO-CH2-CH(SO3M)-COOM的阴离子亲水基团,其中a和b各自独立地是0至4的整数,Z表示通过从通式(I)中除去X得到的残基,并且每个M表示氢、碱金属原子、碱土金属原子、铵残基或链烷醇胺残基;
(b)0.15重量%至2重量%的带有至少一个烷氧基硅烷官能团的烯键式不饱和单体的结构单元;和
(c)5重量%至40重量%的苯乙烯单体的结构单元。
在第二方面,本发明是水性涂料组合物,其包含第一方面的水性聚合物分散体。
具体实施方式
如本文所用,“丙烯酸”包括(甲基)丙烯酸、丙烯酸(甲基)烷基酯、(甲基)丙烯酰胺、(甲基)丙烯腈以及其经改性的形式,如丙烯酸(甲基)羟烷基酯。在整篇文件中,词片“(甲基)丙烯酰基”是指“甲基丙烯酰基”和“丙烯酰基”。例如,(甲基)丙烯酸是指甲基丙烯酸和丙烯酸两者,并且(甲基)烯丙酸酯是指甲基丙烯酸酯和丙烯酸甲酯两者。
本发明中的“玻璃转化温度”或“Tg”可以通过各种技术测量,包含例如差示扫描量热法(“DSC”)或通过使用Fox方程式进行计算。本文所报告的Tg的特定值是使用Fox方程式计算的那些值(T.G.Fox,《美国物理学会公报(Bull.Am.Physics Soc.)》,第1卷,第3期,第123页(1956)。例如,用于计算单体M1和M2的共聚物的Tg,
其中Tg(经计算的)是共聚物的所计算的玻璃转化温度,w(M1)是共聚物中的单体M1的重量分数,w(M2)是共聚物中的单体M2的重量分数,Tg(M1)是单体M1的均聚物的玻璃转化温度并且Tg(M2)是单体M2的均聚物的玻璃转化温度,所有温度均为K。均聚物的玻璃转化温度可以在例如由J.Brandrup和E.H.Immergut所编辑的“《聚合物手册(Polymer Handbook)》”,国际科学出版社(Interscience Publishers)中找到。
也称为“聚合单元”的“结构单元”是指聚合之后单体的残余物,即聚合的单体或聚合形式的单体。例如,甲基丙烯酸甲酯的结构单元如下示出:
其中虚线表示结构单元与聚合物主链的连接点。
本发明的水性聚合物分散体包含一种聚合物。可用于本发明的聚合物包括一种或多种可聚合表面活性剂的结构单元。可聚合表面活性剂可具有式(I)的结构,
其中R1是苯基或苯基取代的烷基;
m1为1、2、3或4,优选为1至3;
R2是烷基或取代的烷基,优选C1-C4烷基或取代的C1-C4烷基;
m2为0或1,优选为0;
R3是氢或C1-C20或C1-C4烷基,如甲基;
R4是氢或C1-C20或C1-C4烷基,如甲基;
A表示具有2到4个碳原子的亚烷基或经取代的亚烷基,例如亚乙基、亚丙基和亚丁基;优选地,亚乙基;
n表示环氧烷的平均加成摩尔数。n为1或以上、2或以上、3或以上、4或以上、甚至5或以上并且同时100或以下、60或以下、50或以下、40或以下、甚至20或以下的整数;优选地,5至20;和
X表示氢或选自-(CH2)a-SO3M、-(CH2)b-COOM、-PO3M2、-P(Z)O2M或-CO-CH2-CH(SO3M)-COOM的阴离子亲水基团,其中a和b各自独立地为0至4的整数,Z表示通过从通式(I)中除去X获得的残基,并且M各自表示氢、碱金属原子、碱土金属原子、铵残基或烷醇胺残基。优选地,X表示-SO3M。
在一些实施方案中,A为亚乙基,n为5至20的整数。
在一个优选的实施方案中,可聚合表面活性剂具有式(II)的结构,
其中R1、m1和n如上式(I)中所定义,并且M是抗衡离子,例如NH4 +、Li+、Na+或K+。
在式(I)或(II)中,优选R1为具有结构的苯基取代的烷基,其中R是具有一至四个碳原子,优选两个至三个碳原子的亚烷基,例如,-CH2-、优选的m1是3。更优选地,在式(II)中,m1为3;n在5至20的范围内;并且R1是
基于聚合物的重量,可用于本发明的聚合物可包含按重量计0.55%或以上、0.6%或以上、0.65%或以上、0.7%或以上、0.75%或以上、0.8%或以上、0.85%或以上、0.9%或以上、0.95%或以上、1.0%或以上、1.05%或以上、或甚至1.1%或以上并且同时5%或以下、4.5%或以下、4%或以下、3.5%或以下、3%或以下、2.5%或以下、2%或以下、1.5%或以下、或甚至1.3%或以下的聚合表面活性剂的结构单元。本发明中的“聚合物的重量”指聚合物的干或固体重量。
可用于本发明的聚合物可进一步包含一种或多种带有至少一个烷氧基硅烷官能团的烯键式不饱和单体的结构单元(以下称为“烷氧基硅烷官能团单体”),优选可水解的烷氧基硅烷官能团。合适的烷氧基硅烷官能单体包括,例如,乙烯基三烷氧基硅烷,例如乙烯基三甲氧基硅烷;和烷基乙烯基二烷氧基硅烷;(甲基)丙烯酰氧基烷基三烷氧基硅烷,例如(甲基)丙烯酰氧基乙基三甲氧基硅烷和(甲基)丙烯酰氧基丙基三甲氧基硅烷;其衍生物,及其组合。基于聚合物的重量,按重量计,聚合物可包含0.15%或以上、0.2%或以上、0.3%或以上、0.4%或以上、或甚至0.5%或以上并且同时2%或以下、1.5%或以下、1.3%或以下、1.0%或以下、0.8%或以下、0.7%或以下、或甚至0.6%或以下的烷氧基硅烷官能单体的结构单元。
用于本发明的聚合物可进一步包含一种或多种苯乙烯单体的结构单元。苯乙烯单体可包括苯乙烯、取代的苯乙烯或它们的混合物。取代的苯乙烯可包括,例如,丙烯酸苄酯、丙烯酸2-苯氧基乙酯、丁基苯乙烯、甲基苯乙烯、对甲氧基苯乙烯或其混合物。优选的苯乙烯单体是苯乙烯。基于聚合物的重量,按重量计,所述聚合物可包含5%或以上、10%或以上、15%或以上、17%或以上、19%或以上、或甚至21%或以上并且同时40%或以下、35%或以下、30%或以下、28%或以下、或甚至26%或以下的苯乙烯单体的结构单元。
在本发明中有用的聚合物可以进一步包含带有至少一种官能团的一种或多种另外的烯键式不饱和单体的结构单元(以下称为“另外的包含官能团的烯键式不饱和单体”),其不同于上述烷氧基硅烷官能单体。所述官能团可以选自羰基、乙酰乙酸、脲基、酰胺、酰亚胺、氨基、羧基、羟基或磷基团。另外的包含官能团的烯键式不饱和单体的实例可以包括含带酸单体的α,β-烯键式不饱和羧酸,如甲基丙烯酸、丙烯酸、衣康酸、顺丁烯二酸或反丁烯二酸;或含酸形成基团的单体,其产生或随后可转化为这种酸基团如酸酐、(甲基)丙烯酸酐或马来酸酐;乙酰基乙酰氧基甲基丙烯酸酯(AAEM);乙烯基膦酸、烯丙基膦酸、(甲基)丙烯酸磷酸烷基酯如(甲基)丙烯酸磷酸酯、(甲基)丙烯酸磷酸酯、(甲基)丙烯酸磷酸酯、或其盐;2-丙烯酰胺基-2-甲基-1-丙磺酸;2-丙烯酰胺基-2-甲基-1-丙磺酸的钠盐;2-丙烯酰胺基-2-甲基-1-丙磺酸的铵盐;苯乙烯磺酸钠;乙烯基磺酸钠;烯丙基醚磺酸的钠盐;等;双丙酮丙烯酰胺(DAAM)、芳基酰胺、甲基丙烯酰胺、单基取代的(甲基)丙烯酰胺、N-甲基丙烯酰胺、N-乙基丙烯酰胺、N-异丙基丙烯酰胺、N-丁基丙烯酰胺、N-叔丁基丙烯酰胺、N-2-乙基己基丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、甲基丙烯酰胺基乙基亚乙基脲、羟基官能的(甲基)丙烯酸烷基酯例如甲基丙烯酸羟乙酯和甲基丙烯酸羟丙酯、或其混合物。优选的含官能团的烯键式不饱和单体选自丙烯酸、甲基丙烯酸、丙烯酰胺、对苯乙烯磺酸钠或其混合物。基于聚合物的重量,聚合物可以包括0.1重量%到20重量%、0.3重量%到10重量%、0.5重量%到5重量%或1重量%到3重量%的所述另外的含官能团烯键式不饱和单体的结构单元。
可用于本发明的聚合物还可包含一种或多种烯键式不饱和非离子单体的结构单元,其不同于含官能团的烯键式不饱和单体和烷氧基硅烷官能单体。如本文所用,术语“非离子单体”是指在pH=1-14之间不带有离子电荷的单体。合适的烯键式不饱和非离子单体可包括,例如,单烯键式不饱和非离子单体包括(甲基)丙烯酸的烷基酯,如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸癸酯、丙烯酸月桂酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸异癸酯、甲基丙烯酸月桂酯、(甲基)丙烯腈或它们的混合物。优选地,烯键式不饱和非离子单体选自甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯和丙烯酸2-乙基己酯。基于聚合物的重量,聚合物可包含35重量%至94.35重量%或40重量%至80重量%的烯键式不饱和非离子单体的结构单元。
在一些实施方案中,基于聚合物的重量,聚合物包括,
0.5重量%至3重量%的可聚合表面活性剂的结构单元,
0.2重量%至1.0重量%的带有至少一个烷氧基硅烷官能团的烯键式不饱和单体的结构单元;
15重量%至30重量%的苯乙烯的结构单元;和
其余为所述另外的含官能团的烯键式不饱和单体和/或烯键式不饱和非离子单体。
可用于本发明的聚合物可通过自由基聚合,优选乳液聚合包含可聚合表面活性剂、带有至少一个烷氧基硅烷官能团的烯键式不饱和单体、苯乙烯单体和任选的上述其他单体的单体混合物进行制备。用于制备聚合物的单体的总重量浓度等于100%。单体混合物可以纯或于水中的乳液形式添加;或在制备聚合物的反应时间段内以一次或多次添加或连续、线性或非线性地添加。适用于乳液聚合反应过程的温度可以低于100℃、在30℃至95℃的范围、或在50℃至90℃的范围。
在制备聚合物的聚合方法中,可使用自由基引发剂。聚合方法可为热引发的或氧化还原引发的乳液聚合。合适的自由基引发剂的实例包括过氧化氢、叔丁基过氧化氢、过氧化氢异丙苯、过硫酸铵和/或碱金属过硫酸盐、过硼酸钠、过磷酸和其盐;高锰酸钾,和过二硫酸的铵或碱金属盐。以单体的总重量计,自由基引发剂通常可以0.01重量%到3.0重量%的含量使用。可在聚合方法中使用包含上述引发剂外加合适的还原剂的氧化还原体系。适合的还原剂的实例包括甲醛次硫酸钠、抗坏血酸、异抗坏血酸、含硫的酸的碱金属盐和铵盐(如亚硫酸钠、亚硫酸氢盐、硫代硫酸盐、次硫酸盐、硫化物、硫氢化物或连二亚硫酸盐)、甲脒亚磺酸、羟甲基磺酸、丙酮亚硫酸氢盐、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。铁、铜、锰、银、铂、钒、镍、铬、钯或钴的金属盐可用于催化氧化还原反应。可任选地使用金属的螯合剂。
在制备聚合物的聚合方法中,可以使用一种或多种另外的表面活性剂。另外的表面活性剂不同于具有上述式(I)的结构的可聚合表面活性剂。所述另外的表面活性剂可在单体聚合之前或单体聚合期间或其组合添加。一部分该另外的表面活性剂也可在聚合之后添加。这些另外的表面活性剂可包括阴离子和/或非离子乳化剂。合适的另外的表面活性剂的例子包括RHODAFAC RS-610烷基乙氧基化磷酸盐,可得自Solvay S.A.;DISPONIL FES 32脂肪醇醚硫酸盐,可得自BASF;TERGITOLTM 15-S-40仲醇乙氧基化物,可得自陶氏化学公司(Dow Chemical Company)(TERGITOL是陶氏化学公司的商标),或其混合物。基于用于制备聚合物的单体混合物的总重量,所述另外的表面活性剂可以以0重量%到3重量%、0.5重量%到2.5重量%、或0.7重量%到1.5重量%的量使用。
在制备聚合物的聚合方法中,可使用链转移剂。合适的链转移剂的实例包括3-巯基丙酸、正十二烷基硫醇、3-巯基丙酸甲酯、3-巯基丙酸丁酯、苯硫酚、壬二酸烷基硫醇或其混合物。链转移剂可以以有效量被用于控制聚合物的分子量。基于用于制备聚合物的单体混合物的总重量,链转移剂可以以0重量%到1重量%、0.1重量%到0.5重量%、或0.15重量%到0.4重量%的量使用。
在完成聚合物的聚合之后,获得的聚合物可通过一种或多种碱作为中和剂中和到pH值例如至少6、6到10或7到9。碱可导致聚合物的离子或潜在离子基团的部分或完整中和。合适的碱的实例包括氨水;碱金属或碱土金属化合物,如氢氧化钠、氢氧化钾、氢氧化钙、氧化锌、氧化镁、碳酸钠;伯胺、仲胺和叔胺,如三乙胺、乙胺、丙胺、单异丙胺、单丁胺、己胺、乙醇胺、二乙胺、二甲胺、三丁胺、三乙醇胺、二甲氧基乙胺、2-乙氧基乙胺、3-乙氧基丙胺、二甲基乙醇胺、二异丙醇胺、吗啉、乙二胺、2-二乙氨基乙胺、2,3-二氨基丙烷、1,2-丙二胺、新戊二胺、二甲基氨基丙胺、己二胺、4,9-二氧杂十二烷-1,12-二胺、聚乙烯亚胺或聚乙烯胺;氢氧化铝;或其混合物。
在本发明中有用的聚合物可以具有50纳米(nm)至500纳米、80纳米至200纳米或90纳米至150纳米的平均粒径,如通过Brookhaven BI-90或90Plus粒度分析仪测量的。
本发明的水性聚合物分散体可进一步包括水。基于水性聚合物分散体的总重量,水的浓度可为30重量%至90重量%、40重量%至80重量%或45重量%至70重量%。
本发明的水性涂料组合物包含所述水性聚合物分散体。水性涂料组合物还可包含一种或多种颜料和/或增量剂。如本文所用,术语“颜料”是指能够实质上有助于涂料的不透明性或遮盖能力的颗粒状无机材料。这类材料通常具有大于1.8的折射率,并且包括无机颜料和有机颜料。合适的无机颜料的实例包括二氧化钛(TiO2)、氧化锌、硫化锌、氧化铁、硫酸钡、碳酸钡或其混合物。用于本发明的优选颜料是TiO2。TiO2还可以浓缩的分散体形式获得。术语“增量剂”是指具有小于或等于1.8且大于1.3的折射率的颗粒状无机材料。合适的增量剂的实例包括碳酸钙、氧化铝(Al2O3)、粘土、硫酸钙、铝硅酸盐、硅酸盐、沸石、云母、硅藻土、实心或中空玻璃、瓷珠和不透明聚合物,如可购自陶氏化学公司(The Dow ChemicalCompany)的ROPAQUETM Ultra E(ROPAQUE为陶氏化学公司的商标),或其混合物。水性涂料组合物的颜料体积浓度(PVC)可为15%到65%、30%到60%或40%到55%。涂料组合物的PVC可根据下式确定:
本发明的水性涂料组合物可进一步包含一种或多种消泡剂。本文中的“消泡剂”是指减少泡沫并且阻止泡沫形成的化学添加剂。消泡剂可为基于聚硅氧的消泡剂、基于矿物油的消泡剂、基于环氧乙烷/环氧丙烷的消泡剂、或其混合物。合适的可商购的消泡剂包括例如购自迪高公司(TEGO)的TEGO Airex 902W和TEGO Foamex 1488聚醚硅氧烷共聚物乳液、可购自毕克公司(BYK)的BYK-024硅酮消泡剂或其混合物。基于水性涂料组合物的总重量,消泡剂可以通常以0至0.5重量%、0.05重量%至0.4重量%、或0.1重量%至0.3重量%的量存在。
本发明的水性涂料组合物可进一步包含一种或多种增稠剂,也称为“流变改性剂”。增稠剂可包括聚乙烯醇(PVA)、粘土材料、酸衍生物、酸共聚物、氨基甲酸酯相关增稠剂(UAT)、聚醚脲聚氨基甲酸酯(PEUPU)、聚醚聚氨基甲酸酯(PEPU)或其混合物。合适的增稠剂的实例包括碱溶胀性乳液(ASE),如经钠或铵中和的丙烯酸聚合物;疏水改性的碱溶胀性乳液(HASE),如疏水改性的丙烯酸共聚物;相关增稠剂,如疏水改性的乙氧基化氨基甲酸酯(HEUR);和纤维素增稠剂,如甲基纤维素醚、羟甲基纤维素(HMC)、羟乙基纤维素(HEC)、疏水性改质的羟乙基纤维素(HMHEC)、羧甲基纤维素钠(SCMC)、羧甲基2-羟乙基纤维素钠、2-羟丙基甲基纤维素、2-羟乙基甲基纤维素、2-羟丁基甲基纤维素、2-羟乙基乙基纤维素和2-羟丙基纤维素。优选地,增稠剂是HMHEC、HEUR或其组合。基于水性涂料组合物的总重量,增稠剂的含量通常为0至1.0重量%,0.1至0.8重量%,或0.2至0.6重量%。
本发明的水性涂料组合物可进一步包含一种或多种润湿剂。本文中的“润湿剂”是指降低涂料组合物的表面张力,引起涂料组合物更容易扩散通过或渗透基材表面的化学添加剂。润湿剂可是多羧酸盐,阴离子、两性离子或非离子的。合适的市售湿润剂包括例如可得自陶氏化学公司的TRITONTM CF-10非离子湿润剂(TRITON是陶氏化学公司的商标)、可得自空气产品(Air Products)的基于乙炔二醇的SURFYNOL 10非离子湿润剂、可得自毕克公司的BYK-346和BYK-349聚醚改性的硅氧烷、或其混合物。基于水性涂料组合物的总重量,润湿剂可以以0至1.0重量%、0.1重量%至0.8重量%或0.2重量%至0.6重量%的量存在。
本发明的水性涂料组合物可进一步包含一种或多种聚结剂。本文中的“聚结剂”是指在环境条件下使聚合物颗粒融合成连续膜的缓慢蒸发溶剂。合适的聚结剂的实例包括2-正丁氧基乙醇、二丙二醇正丁醚、丙二醇正丁醚、二丙二醇甲醚、丙二醇甲醚、丙二醇正丙醚、二乙二醇单丁醚、乙二醇单丁醚、乙二醇单己醚、三乙二醇单丁醚、二丙二醇正丙醚、正丁醚或其混合物。优选的聚结剂包括二丙二醇正丁醚、乙二醇单丁醚、二乙二醇单丁醚、正丁醚或其混合物。基于水性涂料组合物的总重量,聚结剂可以以0至3.0重量%、0.1重量%至2.0重量%或0.2重量%至1.5重量%的量存在。
本发明的涂料组合物可进一步包含一种或多种分散剂。分散剂包括非离子、阴离子和阳离子分散剂,如具有适合的分子量的多元酸、2-氨基-2-甲基-1-丙醇(AMP)、二甲基氨基乙醇(DMAE)、三聚磷酸钾(KTPP)、多磷酸三钠(TSPP)、柠檬酸和其它羧酸。所用的多元酸可包括基于多元羧酸的均聚物和共聚物,包括已经疏水或亲水改性的那些,例如聚丙烯酸或聚甲基丙烯酸或马来酸酐与各种单体如苯乙烯、丙烯酸酯或甲基丙烯酸酯,二异丁烯和其他亲水或疏水共聚单体;其盐;或其混合物。通过凝胶渗透色谱法(GPC)(柱:One PLgelGUARD柱(10μm,50x7.5mm)和One Mixed B柱(7.8x300mm)串联;和校准:分子量范围为2329000至580g/mol的PL聚苯乙烯窄标准品,使用多项式3拟合)测量,这些多元酸的分子量可以在1,000至50,000、1,200至40,000、1,500至20,000、2,000至15,000或2,500至10,000的范围内。基于水性涂料组合物的总重量,分散剂可以以0至1.0重量%、0.1至0.8重量%或0.2至0.6重量%的量存在。
除上文所描述的组分以外,本发明的水性涂料组合物可进一步包含以下添加剂中的任一种或组合:缓冲剂、中和剂、保湿剂、防霉剂、杀生物剂、防结皮剂、着色剂、流动剂、交联剂、抗氧化剂、塑化剂、调平剂、触变剂、助粘剂以及研磨媒剂。当存在时,基于水性涂料组合物的总重量,这些添加剂可以以0重量%至1重量%或0.1重量%至0.8重量%的组合量存在。
本发明的水性涂料组合物可进一步包含水。基于涂料组合物的总重量,水的浓度可为30重量%至90重量%、40重量%至80重量%或45重量%至70重量%。
本发明的水性涂料组合物可以通过混合水性聚合物分散体、以及任选的颜料和如上所述其他成分进行制备。在水性涂料组合物中的组分可以任何顺序混合以提供本发明的水性涂料组合物。任一种上述任选的组分也可在混合期间或之前添加到组合物中以形成水性涂料组合物。颜料和/或增量剂优选与分散剂混合以形成颜料和/或增量剂的浆料。
由可聚合表面活性剂、具有至少一个烷氧基硅烷官能团的烯键式不饱和单体和苯乙烯单体的组合制得的本发明的水性聚合物分散体中的聚合物可对改善由其制得的涂料的早期耐水起泡性具有协同作用,同时仍为涂料提供令人满意的水纹和良好的耐久性。干燥或使其干燥后,水性涂料组合物可以提供由其获得的涂层,其具有出乎意料的改善的早期耐水起泡性,等级为8或更高或甚至为10,耐水纹等级为6或更高表明的令人满意的耐水纹性,以及QUV测试等级为6或更高表明的良好的耐久性。可以根据以下实施例部分中描述的测试方法测量早期耐水起泡性、水纹和耐久性能。
本发明也涉及形成涂层的方法,其包括形成水性涂料组合物,将水性涂料组合物涂覆到基材,并且干燥或允许干燥水性涂料组合物以形成涂层。在将本发明的水性涂料组合物施加到基材上后,可以在室温(20-25℃)下或在高温,例如35℃至60℃下干燥所述水性涂料组合物或使其干燥以形成膜(也就是涂层)。水性涂料组合物可以单独使用或与其它涂料组合使用以形成多层涂层。本发明的水性涂料组合物可用作各种基材上的涂料,其中涂料的早期耐水起泡性很重要,例如那些通常暴露在户外的表面。水性涂料组合物可涂覆于并粘附于各种基材。合适的基材的实例包括木材、金属、塑料、泡沫、石头、弹性基材、玻璃、墙纸、织品、中密度纸板(MDF)、颗粒板、石膏板、混凝土或水泥基材。本发明的水性涂料组合物可通过包括刷涂、浸涂、辊涂以及喷涂的现有方式施用到基材。水性涂料组合物优选通过喷涂施加。可使用标准喷涂技术和喷涂设备,如空气雾化喷涂、空气喷涂、无空气喷涂、高体积低压喷涂和静电喷涂(如静电钟罩施用)和人工或自动方法。
水性涂料组合物适合于各种应用,如海洋和防护涂料、汽车涂料、交通漆、外墙保温装饰系统(EIFS)、屋面胶泥、木材涂料、卷材涂料、塑料涂料、罐头涂料、建筑涂料和土木工程涂料。水性涂料组合物特别有用于建筑涂料。
实施例
现在将在以下实施例中描述本发明的一些实施方案,除非另外说明,否则其中所有份数和百分比均以重量计。
苯乙烯(ST)、丙烯酸丁酯(BA)和甲基丙烯酸甲酯(MMA)均可从Langyuan ChemicalCo.,Ltd.获得。
对苯乙烯磺酸钠(SSS)、丙烯酰胺(AM)、丙烯酸(AA)、Na2CO3、NH4OH、氢过氧化叔丁基(t-BHP)、过硫酸氨(APS)、亚硫酸氢钠(SBS)、抗坏血酸(IAA)、FeSO4.7H2O和乙二胺四乙酸(EDTA)均可从Sinopharm Chemical Reagent Co.,Ltd.获得。
SILQUEST A-171(“A-171”)乙烯基三甲氧基硅烷、SILQUEST A-187(“A-187”)3-环氧丙氧基丙基三甲氧基硅烷和SILQUEST A-1120(“A-1120”)氨基乙基氨基丙基三甲氧基硅烷全部可从Momentive Chemical获得。
可得自Rhodia的RHODAFAC RS-610(“RS-610”)非反应性表面活性剂是基于支链醇乙氧基化物的磷酸盐。
可得自Rhodia的SOPROPHOR WA1802(“WA 1802”)非反应性表面活性剂是氨烷氧基化的三苯乙烯基苯酚磺酸盐。
可得自BASF公司的DISPONIL A-19(“A-19”)表面活性剂是十二烷基(直链)苯磺酸盐表面活性剂。
可得自Kao Corporation的LATEMUL PD-104(“PD-104”)表面活性剂是具有氧化乙烯和氧化丁烯单元的可聚合磺酸盐表面活性剂。
可得自Dai-ichi kogyo seiyaku Co.,Ltd.的HITENOL AR-1025(“AR-1025”)表面活性剂是可聚合烷氧基化三苯乙烯基苯酚磺酸盐表面活性剂。
PRIMALTM DC-420粘结剂可得自陶氏化学公司。
TRITON CF-10(“CF-10”)湿润剂可得自陶氏化学公司。
NATROSOL 250 HBR羟乙基纤维素(HEC)增稠剂可从Hercules Incorporated获得。
Ti-Pure R-902和Ti-Pure R-706二氧化钛均可从杜邦公司获得。
FOAMASTER NXZ(“NXZ”)消泡剂可得自BASF。
DISPERLAIR CF-246消泡剂可从Blackburn Chemicals获得。
CC-700和Talc 800增量剂可从光复建材集团(Guangfu Building MaterialsGroup)购买。
AMP-95中和剂可从ANGUS Chemical Company获得。
可得自Eastman Chemical Company的TEXANOL酯醇用作聚结剂。
可得自陶氏化学公司的丙二醇用作防冻融剂。
OROTANTM CA-2500(“CA-2500”)分散剂、OROTAN 731A(“731A”)分散剂、ROCIMATM363和KATHONTM LXE杀生物剂、ROPAQUE Ultra E不透明聚合物、ACRYSOLTM RM-2020 NPR(“RM-2020”)疏水改性的环氧乙烷氨基甲酸酯(HEUR)流变改性剂、ACRYSOL RM-8W(“RM-8W”)非离子氨基甲酸酯流变改性剂和CELLOSIZETM QP-15000H(“QP-15000H”)羟乙基纤维素(HEC)增稠剂都可以从陶氏化学公司获得。
OROTAN、ROCIMA、KATHON、ACRYSOL、PRIMAL和CELLOSIZE是陶氏化学公司的商标。
实施例中使用以下标准分析设备、测试方法和合成方法。
粒度测量(BI-90)
水性聚合物分散体的聚合物的粒度通过使用Brookhaven BI-90或90Plus粒度仪来测量,所述粒度仪采用光子相关光谱法的技术(样品颗粒的光散射)。此方法涉及在20ml的0.01M的NaCl溶液中稀释2滴的待测试聚合物分散体,并进一步在样品试管中稀释所得混合物以实现所需的计数率(K)(例如,对于在10-300nm范围内的直径,K范围为250至500计数/秒,而对于在300-500nm范围内的直径,K范围为100至250计数/秒)。然后测量水性聚合物分散体的粒度并报告为强度的平均直径。
水纹测试
根据ASTM D7190-10方法(评估胶乳漆膜中水溶性材料的浸出的标准实践)评估耐水纹性。
测试漆制剂100克(g)与4g酞蓝着色剂一起加入,搅拌均匀和平衡过夜。然后,将所得的着色白色漆涂画在黑白色乙烯基图表上以形成100μm的湿膜,并在室温(RT)下干燥4小时。将3mL去离子(DI)水滴放在漆膜上面,让水滴静置3分钟。然后将面板提升到垂直位置,使水滴顺着漆膜流下。然后在浸出之前使板在RT下干燥。按照如下相对等级1-10对漆膜评级,
10:在漆表面上没有明显可见的水纹;
9-8:油表面的发光边缘小于10%;
7-6:10%≤发光边缘≤30%;
5-4:30%<发光边缘≤60%,并且可见光泽下降;
3-2:60%<发光边缘≤100%,并且可见颜色变化;
1:将水滴放在漆膜上后出现严重水泡。
6及以上的等级表示令人满意的耐水纹性。等级越高,耐水纹性越好。否则,如果等级小于6,则表示耐水纹性不可接受。
早期耐水泡性测试
早期耐水泡性测试根据ASTM D714-87方法(用于评价涂料的起泡程度的标准测试方法)进行。
使用100μm开口的刮涂棒将底漆(基于底漆总重量,按重量计,其包括16%DI水、1.5%丙二醇、0.2%QP-15000H、0.11%氨水、0.8%731A、0.2%CF-10、0.2%KATHON LXE、0.15%DISPERLAIR CF-246、5%Ti-Pure R-706、15%CC-700、10%Talc 800、40%PRIMALDC-420、4%TEXANOL和0.15%DISPERLAIR CF-246、0.6%ACRYSOL RM-8W和6.1%DI水)涂覆到水泥面板上。在室温下干燥2小时后,使用具有120μm开口的刮涂棒进一步用测试涂料制剂涂覆面板。在室温下进一步干燥2小时后,将得到的面板放入雾箱室中,每半小时观察表面变化并记录至4小时。根据水泡的大小和面积,按照如下1-10的相对标尺对漆表面进行评级,
10:没有可见的水泡;
8-9:小水泡,漆表面的≤20%;
6-7:小水泡,漆表面的>20%至≤40%;
4-5:小或中水泡,漆表面的>40%至≤60%;和
1-2:中水泡,漆表面的>60%至≤100%。
等级8或更高表明良好的早期耐水泡性。否则,如果等级小于8,则表明早期耐水泡性差。等级越高,早期耐水泡性越好。
加速风化测试(OUV)
使用涂布机将测试涂料制剂涂布到铝板上,以形成150μm的湿膜。然后将测试板在恒温室(CTR,23±2℃;(45-65%)±10%相对湿度)中干燥一周,然后切成3″*9″的尺寸以适合QUV机架。使用黑色标记在背面识标识每个测试板,并且通过光谱引导机(BYK公司)获得每个面板的初始L0 *、a0 *和b0 *值。同时,记录开始时间。将测试板放入QUV设备(Q-LabCorporation的QUV/Se QUV Accelerated Weathering Tester,340nm光源UVA,和0.77w/m2辐照强度)中,测试区域面向内。一个循环QUV由在60℃下进行8小时紫外线照射,然后在50℃下进行4小时喷水组成。在QUV设备中多次循环200小时后,将所有面板从QUV设备中取出。将这些板在室温下干燥,并测试最终的L1 *、a1 *和b1 *值。
ΔE的计算如下式:
根据ΔE值对膜评级,相对标度是1-10,10为最佳。E≤1的评级为10,1<E≤1.5的评级为8-9,1.5<E≤2的评级为6-7,E>2的评级为1-5。QUV测试等级为6或更高表明耐久性好。否则,如果QUV测试等级小于6,则表明耐久性差。
实施例(Ex)1聚合物分散体
通过混合789g BA、289g MMA、482gST、8g AM、32.5g AA、5.8g SSS、4.8g A-171、57.56g AR-1025(25%活性物)和460g DI水,制备单体乳液(ME),然后在搅拌下乳化。然后,将640g DI水和12.8g AR-1025(25%活性物)装入装有机械搅拌的5升多颈烧瓶中。在氮气氛围下将烧瓶的内含物加热到91℃。向搅拌的烧瓶中,向烧瓶中加入在27g DI水中的2.4gNa2CO3,在40g漂洗DI水中的59g ME,在10g DI水中的0.02g FeSO4.7H2O和0.07g EDTA和在30g DI水中的5.77g APS。在120分钟内逐渐加入剩余的单体乳液,在90克DI水中的2.47克APS和在90克DI水中的2.66克SBS。反应器温度保持在88℃。然后,使用40g去离子水冲洗烧瓶的乳液进料管线。然后,将15克去离子水中的1.48克t-BHP(70%活性物)和15克去离子水中的0.67克IAA注入烧瓶中。然后,在搅拌下在30分钟内将3.36g在27g DI水中的t-BHP(70%活性物)和1.76g在30g DI水中的IAA进料到烧瓶中。将烧瓶中的内容物冷却至室温。在10分钟内添加30克去离子水中的24克NH4OH(25%活性物)作为中和剂。
实施例2聚合物分散体
根据与上述制备实施例1聚合物分散体相同的步骤制备实施例2的聚合物分散体,不同的是ME中ST和MMA的含量不同。通过将789g BA、550g MMA、241g ST、8g AM、32.5g AA、5.8g SSS、4.8g A-171、57.56g AR-1025(25%活性物)和460克去离子水的混合物乳化制备实施例2中使用的单体乳液。
实施例3聚合物分散体
根据与上述制备实施例1聚合物分散体相同的步骤制备实施例3的聚合物分散体,不同之处在于ME中硅烷的含量不同。通过将789g BA、289g MMA、482g ST、8g AM、32.5g AA、5.8g SSS、3.2g A-171、57.56g AR-1025(25%活性物)和460克去离子水的混合物乳化制备实施例3中使用的单体乳液。
比较(Comp)实施例A聚合物分散体
按照与上述制备实施例1聚合物分散体相同的步骤制备比较实施例A的聚合物分散体,不同的是ME中的表面活性剂和直接加入烧瓶中的表面活性剂不同。通过将789g BA、289g MMA、482g ST、8g AM、32.5g AA、5.8g SSS、4.8g A-171、75.74g A-19(19%活性物)和450克去离子水的混合物乳化制备比较实施例A中使用的单体乳液。然后,将635g去离子水和16.84g A-19(19%活性)装入装有机械搅拌的5升多颈烧瓶中。
比较实施例B聚合物分散体
按照与上述制备实施例1聚合物分散体相同的步骤制备比较实施例B的聚合物分散体,不同的是ME中的表面活性剂和直接加入烧瓶中的表面活性剂不同。通过将789g BA、289g MMA、482g ST、8g AM、32.5g AA、5.8g SSS、4.8g A-171、57.56g RS-610(25%活性物)和460克去离子水的混合物乳化制备比较实施例B中使用的单体乳液。然后,将640g去离子水和12.8g RS-610(25%活性)装入装有机械搅拌的5升多颈烧瓶中。
比较实施例C聚合物分散体
按照与上述制备实施例1聚合物分散体相同的步骤制备比较实施例C的聚合物分散体,不同的是ME中的表面活性剂和直接加入烧瓶中的表面活性剂不同。通过将789g BA、289g MMA、482g ST、8g AM、32.5g AA、5.8g SSS、4.8g A-171、49.97g WA 1802(30%活性物)和460克去离子水的混合物乳化制备比较实施例C中使用的单体乳液。然后,将640g去离子水和10.67g RS-610(30%活性)装入装有机械搅拌的5升多颈烧瓶中。
比较实施例D聚合物分散体
按照与上述制备实施例1聚合物分散体相同的步骤制备比较实施例D的聚合物分散体,不同的是ME中使用的和直接加入烧瓶中的表面活性剂不同。通过将789g BA、289gMMA、482g ST、8g AM、32.5g AA、5.8g SSS、4.8g A-171、74.96g PD-104(20%活性物)和460克去离子水的混合物乳化制备比较实施例D中使用的单体乳液。然后,将640g去离子水和16.01g PD-104(20%活性)装入装有机械搅拌的5升多颈烧瓶中。
比较实施例E聚合物分散体
除了除去ME中的A-171硅烷以外,根据与上述制备实施例1聚合物分散体相同的步骤制备比较实施例E的聚合物分散体。通过将789g BA、289gMMA、482g ST、8g AM、32.5g AA、5.8g SSS、57.56g AR-1025(25%活性物)和460克去离子水的混合物乳化制备比较实施例E中使用的单体乳液。
比较实施例F聚合物分散体
根据与上述制备实施例1聚合物分散体相同的步骤制备比较实施例F的聚合物分散体,不同的是ME中ST和MMA的含量不同。通过将789g BA、791g MMA、8g AM、32.5g AA、5.8gSSS、4.8g A-171、57.56g AR-1025(25%活性物)和460克去离子水的混合物乳化制备比较实施例F中使用的单体乳液。
比较实施例G聚合物分散体
根据与上述制备实施例1聚合物分散体相同的步骤制备比较实施例G的聚合物分散体,不同的是ME中ST和MMA的含量不同。通过将789g BA、791g ST、8g AM、32.5g AA、5.8gSSS、4.8g A-171、57.56g AR-1025(25%活性物)和460克去离子水的混合物乳化制备比较实施例G中使用的单体乳液。
比较实施例H聚合物分散体
根据与上述制备实施例1聚合物分散体相同的步骤制备聚合物分散体,不同之处在于ME中A-171硅烷的含量不同。通过将789g BA、289g MMA、482g ST、8g AM、32.5g AA、5.8g SSS、1.6g A-171、57.56g AR-1025(25%活性物)和460克去离子水的混合物乳化制备比较实施例H中使用的单体乳液。
比较实施例I聚合物分散体
根据与上述制备实施例1聚合物分散体相同的步骤制备聚合物分散体,不同之处在于ME中A-171硅烷的含量不同。通过将789g BA、289g MMA、482g ST、8g AM、32.5g AA、5.8g SSS、0.8g A-171、57.56g AR-1025(25%活性物)和460克去离子水的混合物乳化制备比较实施例I中使用的单体乳液。
比较实施例J聚合物分散体
根据与上述实施例1聚合物分散体相同的步骤制备聚合物分散体,不同的是表面活性剂类型和在ME中的量不同。通过将789g BA、289g MMA、482g ST、8g AM、32.5g AA、5.8gSSS、0.8g A-171、19.16g AR-1025(25%活性物)、50.4g A-19(19%活性物)和435克去离子水的混合物乳化制备比较实施例J中使用的单体乳液。
比较实施例K聚合物分散体
按照与上述制备实施例1聚合物分散体相同的步骤制备比较实施例K的聚合物分散体,不同的是除去ME中的A-171硅烷,并在聚合后将A-187硅烷后加入到粘合剂中。通过将789g BA、289g MMA、482g ST、8g AM、32.5g AA、5.8g SSS、57.56g AR-1025(25%活性物)和460克去离子水的混合物乳化制备比较实施例K中使用的单体乳液。在10分钟内加入NH4OH作为中和剂后,向烧瓶中加入4.8g A-187,并搅拌10分钟,然后过滤。
比较实施例L聚合物分散体
按照与上述制备实施例1聚合物分散体相同的步骤制备比较实施例L的聚合物分散体,不同的是除去ME中的A-171硅烷,并在聚合后将A-1120硅烷后加入到粘合剂中。通过将789g BA、289g MMA、482g ST、8g AM、32.5g AA、5.8g SSS、57.56g AR-1025(25%活性物)和460克去离子水的混合物乳化制备比较实施例L中使用的单体乳液。在10分钟内加入NH4OH作为中和剂后,向烧瓶中加入4.8g A-1120,并搅拌10分钟,然后过滤。
上述所得聚合物分散体的性质列于表1中。这些聚合物分散体在以下制备的涂料制剂中用作粘合剂。
表1.聚合物分散体的性质
聚合物分散体 | 粒度 | pH | 固体含量 |
实施例1 | 109nm | 8.51 | 47.85% |
实施例2 | 122nm | 8.72 | 47.9% |
实施例3 | 130nm | 8.42 | 50.2% |
比较实施例A | 138nm | 8.85 | 49.5% |
比较实施例B | 146nm | 8.75 | 49.5% |
比较实施例C | 116nm | 8.58 | 48.38% |
比较实施例D | 133nm | 8.65 | 47.27% |
比较实施例E | 120nm | 8.71 | 49.7% |
比较实施例F | 122nm | 8.79 | 47.9% |
比较实施例G | 134nm | 8.82 | 48.5% |
比较实施例H | 120nm | 8.54 | 47.6% |
比较实施例I | 119nm | 8.44 | 47.7% |
对比实施例J | 123nm | 8.35 | 50.3% |
对比实施例K | 130nm | 8.44 | 49.9% |
比较实施例L | 130nm | 8.44 | 49.9% |
漆制剂
基于表2中列出的配方制备漆制剂(即涂料组合物)。使用高速Cowles分散机以800rpm将用于制备研磨物的成分混合30分钟以形成研磨物。然后,使用常规的实验室混合器将调漆中的成分添加到研磨物中,以获得每种漆制剂。表3给出了每种涂料制剂中使用的粘合剂。
表2.漆制剂
根据上述测试方法评估以上获得的漆制剂的水纹、早期耐水泡性和耐久性能,结果列于表3。
如表3所示,由AR-1025表面活性剂和A-171硅烷(实施例1-3)的特定组合制成的粘合剂为漆膜提供了令人惊讶地改善的早期耐水起泡性,等级为8或更高,甚至高达10同时,实施例1-3的漆膜还显示出令人满意的耐水纹性和良好的耐久性。
值得一提的是,观察到AR-1025反应性烷氧基化三苯乙烯基苯酚表面活性剂与A-171硅烷在提高早期耐水泡性方面的协同作用。在存在AR-1025但无A-171硅烷(比较实施例E)下合成的粘合剂提供漆膜差的早期耐水泡性,评级低至1。此外,由0.3%的A-171硅烷与其他表面活性剂(例如非反应性烷氧基化三苯乙烯基苯酚表面活性剂WA 1802(比较实施例C)或无三苯乙烯基苯酚基团的反应性表面活性剂PD 104(比较实施例D))组合合成的粘合剂均提供了较差的早期耐水泡性的漆膜,分别低至3和1。
此外,由A-171硅烷与常规A-19(比较实施例A)和RS-610表面活性剂(比较实施例B)组合制成的粘合剂使涂料的耐水纹性差(等级:2)。在存在0.5%AR-1025表面活性剂和0.6%A-19表面活性剂的情况下制备的比较实施例J的粘合剂也导致漆膜的耐水纹性差。当不含ST或与48%ST组合的AR-1025和A-171硅烷制成粘合剂时,由此制得的漆膜显示出差的耐水纹性(等级:3,比较实施例F)和差的耐久性(QUV测试等级:3,比较实施例G)。当粘合剂由0.1%的A-171硅烷(比较实施例H)或0.05%的A-171硅烷(比较实施例I)制成时,所得漆膜还表现出较差的早期耐水泡性。当使用量为0.3%的不可聚合的A-187硅烷(比较实施例K)或A-1120硅烷(比较实施例L)制备粘合剂时,所得漆膜还显示出差的早期耐水泡性。
表3.漆膜性能
*基于单体总重量按重量计。
Claims (11)
1.一种水性聚合物分散体,其包括一种聚合物,其中按所述聚合物的重量计,所述聚合物包含,
(a)0.55重量%至5重量%的具有式(I)结构的可聚合表面活性剂的结构单元,
其中R1是苯基或苯基取代的烷基;m1是1、2、3或4;R2是烷基或取代的烷基;m2是0或1;R3是氢或C1-C20烷基;R4是氢或C1-C20烷基;A表示具有2至4个碳原子的亚烷基或取代的亚烷基;n是1至100范围内的整数;并且X表示氢或选自-(CH2)a-SO3M、-(CH2)b-COOM、-PO3M2、-P(Z)O2M或-CO-CH2-CH(SO3M)-COOM的阴离子亲水基团,其中a和b各自独立地是0至4的整数,Z表示通过从通式(I)中除去X得到的残基,并且每个M表示氢、碱金属原子、碱土金属原子、铵残基或链烷醇胺残基;
(b)0.15重量%至2重量%的带有至少一个烷氧基硅烷官能团的烯键式不饱和单体的结构单元;和
(c)5重量%至40重量%的苯乙烯单体的结构单元。
3.根据权利要求1所述的水性聚合物分散体,其中A表示亚乙基,n是在5-20范围的整数。
4.根据权利要求1所述的水性聚合物分散体,其中按所述聚合物的重量计,所述聚合物包含0.6重量%至3重量%的所述可聚合表面活性剂的结构单元。
5.根据权利要求1所述的水性聚合物分散体,其中按所述聚合物的重量计,所述聚合物包含0.2重量%至0.5重量%的所述带有至少一个烷氧基硅烷官能团的烯键式不饱和单体的结构单元。
6.根据权利要求1所述的水性聚合物分散体,其中所述带有至少一个烷氧基硅烷官能团的烯键式不饱和单体选自(甲基)丙烯酰氧基乙基三甲氧基硅烷、(甲基)丙烯酰氧基丙基三甲氧基硅烷、乙烯基三甲氧基硅烷和乙烯基三乙氧基硅烷。
7.根据权利要求1所述的水性聚合物分散体,其中所述聚合物的玻璃化转变温度为0℃至50℃。
8.根据权利要求1所述的水性聚合物分散体,其中基于所述聚合物的重量,所述聚合物包含15重量%至30重量%的所述苯乙烯单体的结构单元。
9.根据权利要求1所述的水性聚合物分散体,其中所述苯乙烯单体是苯乙烯。
10.一种水性涂料组合物,其包含根据权利要求1至9中任一项所述的水性聚合物分散体。
11.根据权利要求10所述的水性涂料组合物,其颜料体积浓度为15%到65%。
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CN110945038B (zh) | 2023-05-23 |
US11976145B2 (en) | 2024-05-07 |
KR102351529B1 (ko) | 2022-01-14 |
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BR112020001280A2 (pt) | 2020-07-28 |
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