US20050131176A1 - Process for production of polymer dispersions containing an acetoacetate moiety - Google Patents
Process for production of polymer dispersions containing an acetoacetate moiety Download PDFInfo
- Publication number
- US20050131176A1 US20050131176A1 US10/733,895 US73389503A US2005131176A1 US 20050131176 A1 US20050131176 A1 US 20050131176A1 US 73389503 A US73389503 A US 73389503A US 2005131176 A1 US2005131176 A1 US 2005131176A1
- Authority
- US
- United States
- Prior art keywords
- base
- meth
- monomer
- acrylate
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical group CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 title claims abstract 6
- 229920000642 polymer Polymers 0.000 title claims description 41
- 230000008569 process Effects 0.000 title description 20
- 239000006185 dispersion Substances 0.000 title description 17
- 239000000178 monomer Substances 0.000 claims abstract description 166
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 117
- 239000002585 base Substances 0.000 claims description 70
- -1 alkali metal bicarbonate Chemical class 0.000 claims description 61
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 60
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 6
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- ZEYMDLYHRCTNEE-UHFFFAOYSA-N ethenyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC=C ZEYMDLYHRCTNEE-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 3
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 claims description 2
- JZYAVTAENNQGJB-UHFFFAOYSA-N 3-tripropoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C(C)=C JZYAVTAENNQGJB-UHFFFAOYSA-N 0.000 claims description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- CHCFOMQHQIQBLZ-UHFFFAOYSA-N azane;phthalic acid Chemical compound N.N.OC(=O)C1=CC=CC=C1C(O)=O CHCFOMQHQIQBLZ-UHFFFAOYSA-N 0.000 claims description 2
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 230000003139 buffering effect Effects 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- LNULXRCZXBXWIL-UHFFFAOYSA-N octaazanium oxalate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LNULXRCZXBXWIL-UHFFFAOYSA-N 0.000 claims description 2
- AXLMPTNTPOWPLT-UHFFFAOYSA-N prop-2-enyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCC=C AXLMPTNTPOWPLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- DOGQRRGVLIGIEG-UHFFFAOYSA-N 1-(prop-2-enoylamino)butane-2-sulfonic acid Chemical compound CCC(S(O)(=O)=O)CNC(=O)C=C DOGQRRGVLIGIEG-UHFFFAOYSA-N 0.000 claims 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims 2
- CHPNMYQJQQGAJS-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C(C)=C CHPNMYQJQQGAJS-UHFFFAOYSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 claims 1
- 229940095064 tartrate Drugs 0.000 claims 1
- 239000004815 dispersion polymer Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 7
- 239000000839 emulsion Substances 0.000 description 75
- 238000006116 polymerization reaction Methods 0.000 description 52
- 239000003995 emulsifying agent Substances 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 31
- 239000007864 aqueous solution Substances 0.000 description 30
- 239000004816 latex Substances 0.000 description 25
- 229920000126 latex Polymers 0.000 description 25
- 238000007720 emulsion polymerization reaction Methods 0.000 description 23
- 239000003973 paint Substances 0.000 description 23
- 239000000126 substance Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 16
- 239000003139 biocide Substances 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 15
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical group CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 14
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000000049 pigment Substances 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 230000003115 biocidal effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical class O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UDMBCSSLTHHNCD-KQYNXXCUSA-N adenosine 5'-monophosphate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H]1O UDMBCSSLTHHNCD-KQYNXXCUSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000003847 radiation curing Methods 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 239000013008 thixotropic agent Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229920002266 Pluriol® Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000001012 protector Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KANZWHBYRHQMKZ-UHFFFAOYSA-N 2-ethenylpyrazine Chemical compound C=CC1=CN=CC=N1 KANZWHBYRHQMKZ-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
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- 150000002398 hexadecan-1-ols Chemical class 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical class OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
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- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- KPAMAVPLAHLEQE-UHFFFAOYSA-N methyl benzenesulfonate;potassium Chemical compound [K].COS(=O)(=O)C1=CC=CC=C1 KPAMAVPLAHLEQE-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- UKIKQWUFUHMMML-UHFFFAOYSA-N n,n-dimethyl-2-propan-2-ylidenehexanamide Chemical compound CCCCC(=C(C)C)C(=O)N(C)C UKIKQWUFUHMMML-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- CXSANWNPQKKNJO-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]prop-2-enamide Chemical compound CCN(CC)CCNC(=O)C=C CXSANWNPQKKNJO-UHFFFAOYSA-N 0.000 description 1
- WDQKICIMIPUDBL-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]prop-2-enamide Chemical compound CN(C)CCNC(=O)C=C WDQKICIMIPUDBL-UHFFFAOYSA-N 0.000 description 1
- ADTJPOBHAXXXFS-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- RBRNEJRTELJNAD-UHFFFAOYSA-N n-ethenyl-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC=C RBRNEJRTELJNAD-UHFFFAOYSA-N 0.000 description 1
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002943 palmitic acids Chemical class 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- JXSPBGQJJXVUSB-UHFFFAOYSA-M potassium;2-ethylhexyl sulfate Chemical compound [K+].CCCCC(CC)COS([O-])(=O)=O JXSPBGQJJXVUSB-UHFFFAOYSA-M 0.000 description 1
- GHKGUEZUGFJUEJ-UHFFFAOYSA-M potassium;4-methylbenzenesulfonate Chemical compound [K+].CC1=CC=C(S([O-])(=O)=O)C=C1 GHKGUEZUGFJUEJ-UHFFFAOYSA-M 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- ZQMAPKVSTSACQB-UHFFFAOYSA-N prop-2-enyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC=C ZQMAPKVSTSACQB-UHFFFAOYSA-N 0.000 description 1
- PPOUXMSMABGDRJ-UHFFFAOYSA-N prop-2-enyl n-[2-(2-oxoimidazolidin-1-yl)ethyl]carbamate Chemical compound C=CCOC(=O)NCCN1CCNC1=O PPOUXMSMABGDRJ-UHFFFAOYSA-N 0.000 description 1
- HPCIWDZYMSZAEZ-UHFFFAOYSA-N prop-2-enyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC=C HPCIWDZYMSZAEZ-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical class C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- AQAAVCJTEANSGJ-UHFFFAOYSA-N propane-2-sulfinic acid Chemical compound CC(C)S(O)=O AQAAVCJTEANSGJ-UHFFFAOYSA-N 0.000 description 1
- 125000006308 propyl amino group Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- FTWCSAMTIKSPAT-UHFFFAOYSA-M sodium;nonyl sulfate Chemical compound [Na+].CCCCCCCCCOS([O-])(=O)=O FTWCSAMTIKSPAT-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
Definitions
- Acetoacetate moieties in polymers have been used to make crosslinkable polymers. These polymers are useful in coatings. Generally, the polymers are prepared from monomer mixtures that contain a monomer with an acetoacetate moiety. After the polymer is formed, the polymer is neutralized with a base.
- These polymers are often associated with a high viscosity. Higher viscosities increase the difficulty of manufacture and transportation of the polymers. Lower viscosities are generally desirable for reasons of heat transfer and energy consumption during manufacturing. Also, lower viscosities allow for easier pumping and handling. Decreased viscosities also allow for increased solids contents, which is desirable in transportation in that less water has to be shipped.
- the present invention relates to a method of making a composition
- a method of making a composition comprising reacting, in a reactor, a non-halogenated acetoacetate group containing monomer, at least one additional monomer, and a base, wherein at least a portion of the base is fed to the reactor during reaction.
- the present invention also relates to a composition
- a composition comprising an aqueous polymer dispersion that is a product of a method comprising reacting a non-halogenated acetoacetate moiety containing monomer, at least one additional monomer, and a base, wherein the base is fed to the reaction during reaction, wherein the composition has a lower viscosity than a second composition, wherein the second composition is prepared from the same materials as the composition, and the second composition is made by a method wherein the base is added to the second composition after a reaction to form the second composition, and wherein the at least one additional monomer is not butadiene.
- ranges are used as a shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range.
- a composition is prepared by reacting a non-halogenated acetoacetate moiety containing monomer, at least one additional monomer, and a base, wherein the base is fed to the reaction.
- the composition of the present invention is prepared as an aqueous polymer dispersion.
- the composition has a lower viscosity than a second composition prepared from the same materials as the composition, wherein the second composition is made by a method wherein the base is added to the second composition after a reaction to form the second composition. By changing the point at which a base is added, a different composition is formed. The difference can be seen in the viscosity of the compositions.
- the composition of the present invention will have a lower viscosity than the second composition. Also, when the composition is included in a coating composition and tested for scrub resistance according to ASTM D-2486, the composition will have a higher scrub resistance as compared to the second composition.
- the base is fed to the reaction while the monomers are reacting.
- a portion of the total base can be provided in the reactor prior to the start of reaction.
- the base can be present with the monomers as the monomers are fed to the reactor, or the base can be fed from a separate feed, or a combination of both. In a preferred embodiment, the base is fed with the monomers.
- the bases that are suitable for use in the present invention include those substances by the following three definitions: (1) a compound that dissociates on solution in water to produce one or more hydroxyl ions; (2) any compound which can accept a proton by a more general definition according to the Brönsted concept and (3) anything which has an un-shared pair of electrons according to a still more general concept of G. N. Lewis.
- a buffer is a solution of a compound that has the capability of minimizing changes in proton (hydrogen ion) concentration.
- the base include, but are not limited to, alkali metal hydroxides, alkaline earth metal hydroxides, hydroxides of elements from Groups 7 through 13 in the periodic table (IUPAC Nomenclature), ammonia, ammonium hydroxide, amines including primary amines, secondary amines, and tertiary amines such as, but not limited to, alkylamines, arylamines, and heterocyclic amines.
- Preferred bases include, but not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, ammonia, ammonium hydroxide, alkylamines such as methylamines, ethylamines, propylamines, dimethylamines, diethylamines, trimethylamines, and triethylamines, 2-amino-2-methyl-1-propanol, triethanolamine, compounds with buffering capabilities such as carbonates and bicarbonates of alkali metals (preferably lithium, sodium, or potassium), ammonium carbonate, ammonium bicarbonate, mono- and dibasic phosphates of alkali metals, ammonium mono- and dibasic phosphates, tetroxalates and tartrates of alkali metals, ammonium tetroxalate, ammonium tartrate, phthalates of alkali metals, and ammonium phthalate.
- alkylamines such as
- the amount of base is selected so that undesired results are minimized or avoided.
- esters of (meth)acrylic acid are used, too much base can lead to excessive hydrolysis of the monomers.
- too much base can drive monomers with acid groups to the aqueous phase and reduce the amount of the acid groups attached covalently to the particles, which can decrease the stability of the polymer particles.
- the base is added during the reacting step in an amount to provide a pH that is at least 0.2 units higher than would be obtained if the base were not used. In another preferred embodiment, the base is added during the reacting step in an amount such that the pH is not higher than 7. In another preferred embodiment, the base is added during the reacting step in an amount to provide a pH that is at least 0.2 units higher than would be obtained if the base were not used, and the base is added during the reacting step in an amount such that the pH is not higher than 7. In another preferred embodiment, the base is used in an amount of from about 0.01 to about 2 weight % based on a total weight of the polymer.
- a non-halogenated acetoacetate moiety has the following general structure: —R 1 —C(O)—CH 2 —X, where R 1 is a divalent organic radical at least three atoms in length, X is organoacyl [—C(O)—R 2 ] or cyano [—CN], wherein R 2 is a methyl group [—CH 3 ] or a monovalent organic radical, and there is no halogen atom on the carbon atom between the two carbonyl carbon atoms.
- Examples of acetoacetate moiety containing monomers can be found in U.S. Pat. No. 3,459,790, which is incorporated herein by reference.
- Preferred ethylenically-unsaturated acetoacetate moiety containing monomers include, but are not limited to, 2-acetoacetoxyethyl (meth)acrylate, 3-acetoacetoxypropyl (meth)acrylate, 4-acetoacetoxybutyl (meth)acrylate, 2-cyanoacetoxyethyl (meth)acrylate, 3-cyanoacetoxypropyl (meth)acrylate, 4-cyanoacetoxybutyl (meth)acrylate, N-(2-acetoacetoxyethyl) (meth)acrylamide, allyl acetoacetate, 2,3-di(acetoacetoxy)propyl (meth)acrylate, vinyl acetoacetate, and combinations thereof.
- the non-halogenated acetoacetate moiety containing monomer is present in an amount from about 0.1 to about 25 weight % based on a total weight of the polymer.
- the at least one additional monomer makes up that balance of the monomers.
- the at least one additional monomer is present in an amount from about 70 to about 99.9 weight % based on a total weight of the polymer.
- the at least one additional monomer suitable for the reaction products of the present invention include all monomers that can be reacted with an acetoacetate moiety containing monomer to form an aqueous dispersion polymer.
- Such monomers can be any ethylenically unsaturated monomer that can be polymerized by a free-radical mechanism. Examples of these monomers can be found in U.S. Patent Application Publication No. 2003/0195297, which is incorporated herein by reference.
- Suitable examples of the at least one additional monomer include, but are not limited to, (meth)acrylates, hydroxyl containing (meth)acrylates, vinyl aromatics, vinyl halides, vinylidene halides, esters of vinyl alcohol and C 1 -C 18 monocarboxylic acids, esters of allyl alcohol and C 1 -C 18 monocarboxylic acids, ethylenically unsaturated monomers containing at least one carboxylic acid group, salts of ethylenically unsaturated monomers containing at least one carboxylic acid group, anhydrides of ethylenically unsaturated dicarboxylic acids, nitriles of ethylenically unsaturated carboxylic acids, ethylenically unsaturated monomers containing at least one sulfonic acid group, salts of ethylenically unsaturated monomers containing at least one sulfonic acid group, ethylenically unsaturated monomers containing at
- the (meth)acrylates are reaction products of ethylenically unsaturated carboxylic acids and C 1 -C 18 alcohols.
- Examples of (meth)acrylates include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)
- hydroxyl containing (meth)acrylates include, but are not limited to, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylates, and hydroxybutyl (meth)acrylates.
- Examples of ethylenically unsaturated monomers containing at least one carboxylic acid group include, but are not limited to, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, ethacrylic acid, crotonic acid, citraconic acid, cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, trimellitic acid, pyromellitic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, succinic acid, 2,6-naphthalenedicarboxylic acid, glutaric acid, sebacic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarbocylic acid.
- anhydrides of ethylenically unsaturated dicarboxylic acids include, but are not limited to, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride.
- esters of ethylenically unsaturated monomers containing at least one carboxylic acid group include, but are not limited to, methyl hydrogen fumarate, benzyl hydrogen maleate, butyl hydrogen maleate, octyl hydrogen itaconate, dodecyl hydrogen citraconate, butyl fumarate, octyl fumarate, octyl maleate, dibutyl maleate, and dioctyl maleate.
- esters of vinyl alcohol and C 2 -C 18 monocarboxylic acids include, but are not limited to, vinyl acetate, vinyl acetoacetate, vinyl propionate, vinyl n-butyrate, vinyl heptanoate, vinyl perlogonate, vinyl 3,6-dioxaheptanoate, vinyl 3,6,9-trioxanundecanote, vinyl laurate, and vinyl stearate.
- esters of allyl alcohol and C 1 -C 18 monocarboxylic acids include, but are not limited to, allyl acetate, allyl propionate, allyl (meth)acrylate, allyl n-butyrate, allyl laurate, allyl stearate, diallyl maleate, and diallyl fumarate.
- nitriles of ethylenically unsaturated carboxylic acids include, but are not limited to, acrylonitrile and methacrylonitrile.
- vinyl aromatics include, but are not limited to, styrene, ⁇ -methyl styrene, o-chlorostyrene, chloromethyl styrene, ⁇ -phenyl styrene, styrene sulfonic acid, salts of styrene sulfonic acid, para-acetoxystyrene, divinylbenzene, diallyl phthalate, vinyl toluene, and vinyl naphthalene.
- dienes include, but are not limited to, butadiene, isoprene, and chloroprene.
- unsaturated monomers containing at least one sulfonic acid group include, but are not limited to, vinyl sulfonic acid, arylsulfonic acid, sulfopropyl acrylate, (Meth)acryloyloxynaphthalenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and acryloyloxybenzenesulfonic acid.
- Examples of unsaturated monomers containing at least one amide group include, but are not limited to, (meth)acrylamide, dimethyl (meth)acrylamide, N-alkyl (meth)acrylamide, N-butylacrylamide, tetramethylbutylacrylamide, N-alkylol (meth)acrylamide, N-methylol (meth)acrylamide, N-octyl acrylamide, methylene bis acrylamide, diacetoneacrylamide, ethyl imidazolidon (meth)acrylate, and N,N-dimethylaminopropylmethacrylamide.
- nitrogen-containing adhesion monomers are free-radically polymerizable monomers that have at least one of an amino group, a ureido group, a urea group, a thiourea group, and a N-heterocyclic group.
- nitrogen-containing adhesion monomers include, but are not limited to, ureido (meth)acrylates, (meth)acrylates with at least one of urea and thiourea in the side chains, acrylic allophanes, aminoethyl acrylate and methacrylate, dimethylaminoethyl acrylate and methacrylate, diethylaminoethyl acrylate and methacrylate, dimethylaminopropyl acrylate and methacrylate, 3-dimethylamino-2,2-dimethylpropyl acrylate and methacrylate, 2-N-morpholinoethyl acrylate and methacrylate, 2-N-piperidinoethyl acrylate and methacrylate, N-(3-dimethylaminopropyl)acrylamide and -methacrylamide, N-dimethylaminoethylacrylamide and -methacrylamide, N-diethylaminoethylacrylamide and
- carbonyl-containing monomers examples include, but are not limited to, acrolein and methacrolein.
- Examples of the monomers containing hydrolyzable Si-organic bonds include, but are not limited to, vinyl silanes, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, methacryloyloxypropyltripropxysilane, methacryloyloxypropyltriisopropxysilane, vinyltrimethoxysilane, vinyl tris (2-methoxyethoxy silane), and vinyl triisopropoxysilane.
- phosphate (meth)acrylates examples include, but are not limited to, sodium phosphate (meth)acrylate, alkylester phosphate (meth)acrylate, and ethoxylated alkylester phosphate (meth)acrylate.
- vinyl monomers include, but are not limited to, 1,4-butanediol bisacrylate, vinyl acetoacetamide, vinyl 1,3-diketone, vinyl pyrrolidone, vinyl pyridine, vinyl pyrazine, vinyl piperadiene, vinyl piperidone, vinyl pyrimidine, vinyl pyrrole, vinyl imidazole, vinyl caprolactam, vinyl oxazole, vinyl thiazole, vinyl morpholine, triallyl cyanurate, glycidyl (meth)acrylate, 3-isopropenyl- ⁇ - ⁇ -dimethylbenzyl isocyanate, ethylene, and propylene.
- the majority of the at least one additional monomer is not a functional monomer.
- a functional monomer is a monomer that has a functional group in addition to a carbon-carbon double bond or has at least two sites of ethylenic unsaturation.
- Functional groups include, but are not limited to, acids, hydroxyls, amides, nitrogen containing groups (such as those in the nitrogen-containing adhesion monomers listed above), silanes.
- the functional monomers in this embodiment are present in an amount from about 0.05 to about 5% by weight based on a total weight of the polymer.
- Preferred functional monomers include, but are not limited to, mono-ethylenically unsaturated acids and diacids, such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid; nitrogen-containing monomers such as acrylamide, methacrylamide, ureido (meth)acrylate, and ureido (meth)acrylamide; AMPS (acrylamidomethypropylsufonic acid or its salts); silane monomers such as methacryloxypropyl trimethoxysilane, methacryloxypropyl triethoxysilane, methacryloxypropyl tripropoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane; crosslinkers with two or more sites of ethylenic unsaturation, such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butylene
- the reference to the acid also includes a reference to its salts.
- the salts of theses acids include alkali metal salts, alkaline earth metal salts, and ammonium salts.
- the polymers of the present invention can be made in a seedless semi-batch polymerization, an in-situ seeded semi-batch polymerization, a seeded semi-batch polymerization, or a continuous polymerization.
- the polymers of the present invention can be made as a single stage polymer, a gradient or power-feed polymer, or they can be made as a multiple stage polymer.
- the reaction to form the polymers of the present invention can be an emulsion polymerization reaction in which the monomers are emulsified in water with a surface active agent or stabilized by a protective colloid and reacted using emulsion polymerization techniques known in the art.
- the resulting product of the emulsion polymerization is an aqueous polymer dispersion, also known as a latex.
- the reaction can be started with any initiator.
- additional materials that are used in emulsion polymerizations can be included.
- additional materials include, but are not limited to, electrolytes, chelating agents, dispersing agents, chain transfer agents, and additional seed polymer particles.
- a redox system which includes an oxidizing agent and a reducing agent, is added to the reaction product to drive the reaction to further completion to reduce the amount of residual monomers.
- any system that reduces residual monomer content can be used. Examples include, but are not limited to, stripping with steam, vacuum, use of adsorbent materials, and combinations thereof.
- reaction temperature any temperature that allows the monomers to react to form a polymer can be used as a reaction temperature.
- emulsion polymerization reactions have a reaction temperature that ranges from about 3° C. to about 130° C.
- surfactants examples include anionic, cationic, nonionic, amphoteric surfactants, and mixtures thereof.
- anionic surfactants include, but are not limited to, organosulfates and sulfonates, e.g., sodium and potassium alkyl, aryl, and arylalkyl sulfates and sulfonates, such as sodium 2-ethylhexyl sulfate, potassium 2-ethylhexyl sulfate, sodium nonyl sulfate, sodium lauryl sulfate, potassium methylbenzene sulfonate, sodium dodecylbenzene sulfonate, potassium toluene sulfonate, and sodium xylene sulfonate; higher fatty alcohols, e.g., stearyl, lauryl, etc., which have been ethoxylated and sulfonated; dialkyl esters of alkali metal sulfosuccinic acid salts, such as sodium diamyl sulfosuccinate,
- cationic surfactants include, but are not limited to, alkylamine salts such as laurylamine acetate, quaternary ammonium salts such as lauryl trimethyl ammonium chloride and alkyl benzyl dimethylammonium chlorides, and polyoxyethylenealkylamines.
- amphoteric surfactants include, but are not limited to, alkylbetaines such as lauryl-betaine.
- nonionic surfactants include, but are not limited to, polyethers, e.g., ethylene oxide and propylene oxide condensates that include straight and branched chain alkyl and alkylaryl polyethylene glycol and polypropylene glycol ethers and thioethers; alkylphenoxypoly (ethyleneoxy) ethanols having alkyl groups containing from about 7 to about 18 carbon atoms and having from about 4 to about 240 ethyleneoxy units, such as heptylphenoxypoly (ethyleneoxy) ethanols, nonylphenoxypoly (ethyleneoxy) ethanols; the polyoxyalkylene derivatives of hexitol including sorbitans, sorbides, mannitans and mannides; partial long-chain fatty acids esters, such as the polyoxyalkylene derivatives of sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate and sorb
- Nonionic surfactant is an organosilanol derivative of tung oil, or linseed oil, or high erucic acid rapeseed oil. These surfactant compositions particularly feature high surface activity in forming stable emulsions of organic/water of various difficult to emulsify materials as compared with conventional emulsifying agents. These silanol-based surfactant compositions are described in U.S. Pat. No. 5,807,922.
- surfactants that can be used are those that are copolymerizable with the monomers described above.
- the amount of surfactants in the emulsion polymerization reaction range from about 0.01 to about 10 weight percent, preferably about 0.2 to about 5 weight percent based on the total weight of monomers and water.
- Oxidizers that can be used alone or in the redox system include, but are not limited to, peroxides such as t-butyl hydroperoxide, hydrogen peroxide, pinane hydroperoxide, dibenzoyl peroxide, cumol hydroperoxide, persulfates such as peroxodisulfuric acid, salts of peroxodisulfuric acid, azo compounds such as azobisisobutyronitrile, agents that donate oxygen with free radical formation, alkali metal chlorates, alkali metal perchlorates, transition metal oxide compounds, potassium permaganate, manganese dioxide, lead oxide, lead tetraacetate, iodobenzene.
- peroxides such as t-butyl hydroperoxide, hydrogen peroxide, pinane hydroperoxide, dibenzoyl peroxide, cumol hydroperoxide, persulfates such as peroxodisulfuric acid, salts of peroxodisulfuric
- Reducing agents that can be included in the redox system include, but are not limited to, sodium formaldehyde sulfoxylate, erythorbic acid, bisulfites, sodium metabisulfite, sodium bisulfite, adducts of a 3 to 8 carbon ketone with the bisulfite ion, adducts of a 3 to 8 carbon ketone with sulfurous acid, reducing sugars, ascorbic acid, sulfinic acids, hydroxymethane-sulfinic acid, alkane sulfinic acids, isopropane sulfinic acid. Additional redox systems are described in U.S. Pat. No. 5,994,457, which is incorporated herein by reference.
- Additional polymers that can be blended with the polymer compositions of the present invention include, but are not limited to, (meth)acrylates, styrenics, styrene-butadienes, polyurethanes, polyethers, polyesters, melamine-formaldehyde polymers, vinyl halides, vinylidene halides, poly(ethyleneimines), and poly(vinyl amines).
- the reaction products (the aqueous polymer dispersions) of the present invention generally have a total solids content of from about 30% to about 70% and a pH from about 2 to about 7.
- the pH of the reaction products can be adjusted to above 7 if required using a pH adjusting agent as described below.
- the particle size can generally range from about 30 nm to about 1000 nm.
- the particle size distribution can be uni- or multi-modal.
- compositions of the present invention may further contain additional additives.
- the additives can be any additive that may be generally included with an emulsion polymerization reaction product or any additive that may be used to make a specific composition.
- Further additives include, but are not limited to, surfactants, wetting agents, protective colloids, fillers, coloring agents, antiseptics, biocides, dispersing agents, thickening agents, thixotropic agents, antifreezing agents, pH adjusting agents, corrosion inhibitors, ultraviolet light stabilizers, crosslinking promoters, and antioxidants.
- surfactants and wetting agents include, but are not limited to, the surfactants listed above, sulfosuccinates, fluorinated surfactants, and silicone surfactants.
- protective colloids are partially and fully hydrolyzed polyvinyl alcohol, hydroxyethyl cellulose, hydroxymethyl cellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose, ethoxylated starch derivatives, polyacrylic acid, alkali metal polyacrylates, polyacrylamide, poly (methyl vinyl ether/maleic anhydride), polyvinylpyrrolidone, water soluble starch, glue, gelatin, water soluble alginates, guar, gum arabic, and gum tragacanth.
- the amount of protective colloids used in the composition varies depending upon the intended application and generally ranges from about 0.1 weight percent to about 2 weight percent based on the total weight of the composition.
- fillers examples include talc, calcium carbonate, diatomaceous earth, mica, kaolin, barium sulfate, magnesium carbonate, fumed silica, vermiculite, graphite, alumina, silica, and rubber powder. Coloring agents such as titanium dioxide and carbon black can also be used as the fillers.
- the amount of the filler generally ranges from about 5 weight percent to about 50 weight percent based on the total weight of the composition of the present invention.
- organic pigments and inorganic pigments may be broadly used as the coloring agents, but non-toxic anticorrosive pigments are preferred.
- non-toxic anticorrosive pigments are preferred.
- examples of such pigments are phosphate-type anticorrosive pigments such as zinc phosphate, calcium phosphate, aluminum phosphate, titanium phosphate, silicon phosphate, and ortho- and fused phosphates of these; molybdate-type anticorrosive pigments such as zinc molybdate, calcium molybdate, calcium zinc molybdate, potassium zinc molybdate, potassium zinc phosphomolybdate and potassium calcium phosphomolybdate; and borate-type anticorrosive pigments such as calcium borate, zinc borate, barium borate, barium meta-borate and calcium meta-borate.
- any color pigment, effect pigment, or color and effect pigment may be used.
- the amount of the coloring agent used may also be properly selected based on the end-use application of the compositions of the present invention.
- antiseptics examples include pyrrole compounds, imidazole compounds, thiazole compounds, pyridine compounds and organic halogen compounds.
- the amount of the antiseptic can be suitably selected, and is, for example, up to about 4 percent by weight based on the total weight (as solids content) of the composition.
- biocides which are used either as wet-state protectors or as film protectors of a coating composition, are a wide variety of bactericides, fungicides or algicides, and include, but are not limited to, zinc oxide, cuprous oxide, organotin pigments, copolymers of organotin esters of methacrylic acid with acrylates, tributyl tin oxide, and mixtures thereof.
- Other examples of biocides particularly useful as wet-state protectors are oxazoladines, organosulfurs, and benzisothiazolins. Any general toxic agent may be suitable as a biocide.
- the dispersing agents include, but are not limited to, sodium salts of polycarboxylic acids, sodium or ammonium salts of fused naphthalene sulfonate, polyoxyalkylene alkyl ethers of phenol ether, sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene styrene phenol, sodium tripolyphosphate and sodium hexametaphosphate.
- organosilanol derivatives of tung oil, or linseed oil, or high erucic acid rapeseed oil that are useful as surfactants are also suitable as dispersing agents.
- the amount of the dispersing agent generally ranges up to about 10 weight percent based on the total weight of the composition.
- the thickening and thixotropic agents may be one and the same or different and may be the same as the protective colloids referred to above.
- thickening or thixotropic agents are polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose salt, polyether compounds, urethane modified polyether compounds, polycarboxylic acid compounds, sodium salts of polycarboxylic compounds, polyvinylpyrrolidone, polyoxyethylene derivatives such as polyethylene glycol ether and polyethylene glycol distearate, sodium alginate and inorganic materials such as sodium silicate and bentonite.
- the amounts of the thickening or the thixotropic agents can be properly chosen depending upon the type of end-application of the composition of the present invention.
- pH adjusting agents examples include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, ammonium hydroxide, ammonia, amines, triethanolamine, and 3-dimethylaminoethanol.
- the amount of the pH adjusting agent is selected such that the composition has a desired pH.
- crosslinking promoters examples include, but are not limited to, carbodiimides.
- compositions of the present invention include, but are not limited to, coatings, including original equipment manufacture (OEM) automotive coatings, refinish automotive coatings, architectural coatings, paper coatings, textile coatings, industrial coatings, furniture coatings, powder coatings, graphic arts, inks, adhesives, binders, nonwovens, paper saturation, medical applications (such as dentifrice, sutures, and bandages), and construction chemicals.
- OEM original equipment manufacture
- refinish automotive coatings architectural coatings
- paper coatings textile coatings
- industrial coatings industrial coatings
- furniture coatings powder coatings
- graphic arts such as inks
- adhesives such as dentifrice, sutures, and bandages
- construction chemicals such as dentifrice, sutures, and bandages
- One or more crosslinking agents or crosslinkers can be added to the polymer composition of the present invention when it is used alone, in a coatings formulation or in a blend with other polymer compositions.
- Polymer crosslinking provides chemical and stain resistance in coatings as well improved processability, toughness, and service life in other applications. All the chemical compounds known to crosslink with the acetoacetate moiety can be used to effect the crosslinking reaction.
- the crosslinking agents include, but not limited to, melamines, isocyanates, electron-deficient olefins, diamines, polyaldehydes.
- an actinic radiation curing agent can be included.
- actinic radiation curing agents include, but are not limited to, benzophenone, 4-methylbenzophenone, benzoyl benzoates, phenylacetophenones, 2,2-dimethoxy-2-phenylacetophenone, and amine modified diacrylates.
- the amount of actinic radiation curing agents that can be included in the compositions can be any amount that promotes or accelerates curing or hardening of the polymers. Generally, the amount of actinic radiation curing agents ranges from about 0% to about 1% based on the weight of the composition, and preferably from about 0% to about 0.5%.
- the viscosities of the polymer dispersions were measured throughout using a Brookfield Viscometer (Model RVDV-II+) with either spindle #2 at a speed of 50 rpm for viscosities below about 800 cps or spindle #3 at a speed of 50 rpm for viscosities higher than about 800 cps.
- the preferred emulsion polymerization process is a semi-continuous one in which all or the bulk of the monomers are added over a period of time into the reactor during polymerization.
- a semi-continuous process may include semi-batch with starved or non-starved monomer feeding, gradient feeding, power feeding, one-stage, multi-stage, swelling polymerization etc.
- a seed can be used for better control of particle size and/or particle size distribution.
- An amount of a 5% solution of ammonium persulfate initiator was prepared fresh and placed in a feeding vessel. Initiator was added to the polymerization reactor via a feed tube having a valve to control the feed rate.
- pre-emulsion vessel To a stirred pre-emulsion vessel were added specified amounts of deionized (DI) water, seed, surfactants, etc. This mixture was agitated to create an emulsion. Additional monomer emulsions or monomer mixtures were optionally prepared in separate vessels and transferred to the pre-emulsion vessel as outlined in the accompanying description.
- DI deionized
- the pre-emulsion vessel was connected to the polymerization reaction via a feeding line with a valve to control the rate of feed.
- Feeding rates of monomer emulsion and initiator were computer-controlled so that exact amounts were delivered into the polymerization reactor.
- the temperature of the reactor was controlled by a thermostated water bath.
- Reactor contents were agitated at a sufficient speed so as to provide adequate mixing of reaction components. All reaction conditions are given in the tables below.
- the reactor was maintained at 75° C. for 30 more minutes and then cooled down to room temperature. 20.36 g of a 28% strength by weight aqueous ammonia and 6.67 g of a 1.5% strength by weight aqueous solution of a biocide were added.
- the polymer dispersion was essentially free of coagulum, had a pH of 9.34, solids content of 49.96% by weight and a Brookfield viscosity of 2540 cps.
- the pH values during emulsion polymerizations were recorded. Table 1 summarizes pH values measured, final latex viscosity, and paint scrub resistance.
- compositions of the monomer emulsions were as follows: Monomer Emulsion I 250.38 g water 33.33 g emulsifier 1 1 15.63 g emulsifier 2 2 13.16 g emulsifier 3 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 0.00 g 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 275.00 g MMA
- Monomer Emulsion II 111.67 g of water 33.33 g of emulsifier 1 1 1.00 g of tert-dodecyl mercaptan 99.00 g of MMA
- the polymerization recipe and process is similar to that of CE1, except NaOH was added into the Monomer Emulsion I.
- the compositions of Emulsion I and II are given below.
- the polymer dispersion has been cooled down to room temperature, 17.32 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE1 were added.
- the product was essentially free of coagulum, had a pH of 9.2, solids content of 50.10% by weight and a Brookfield viscosity of 690 cps.
- the pH values during emulsion polymerizations were recorded. Table 1 summarizes pH values measured, final latex viscosity, and paint scrub resistance.
- compositions of the monomer emulsions were as follows: Monomer Emulsion I 242.73 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g a 50% strength by weight aqueous solution of acrylamide 8.50 g a 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 270.00 g MMA
- the polymerization recipe and process is similar to that of CE1, except NaOH was added into the Monomer Emulsion I.
- the compositions of Emulsion I and II are given below.
- the polymer dispersion was cooled down to room temperature, 14.29 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE1 were added.
- the product was essentially free of coagulum, had a pH of 9.29, solids content of 49.48% by weight and a Brookfield viscosity of 320 cps.
- the pH values during emulsion polymerizations were recorded. Table 1 summarizes pH values measured, final latex viscosity, and paint scrub resistance.
- compositions of the monomer emulsions were as follows: Monomer Emulsion I 235.08 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 17.00 g 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 275.00 g MMA
- the low-shear viscosities of the paints ranged from 100 to 117 K.U. (Krebs Units), whereas the high-shear viscosities ranged from 1.5 to 1.7 poises (measured according to ASTM D4287 and D562-81, respectively).
- the scrub resistance of the paints was tested according to ASTM D-2486 using a “Gardner” scrub machine and the standardized scrub medium SC-2.
- the paints were applied with the help of a film applicator to the Leneta scrub panels with a wet thickness of about 175 ⁇ m.
- the draw-down films were dried in a climate-controlled room (50% Relative Humidity and 23° C.) for 7 days before the scrub test. TABLE 1 pH during Polymerization at different times* Final Latex Scrub Neutralizing 0 15 30 60 120 Viscosity Resistance Agent min. min. min. min. min. min.
- Examples E1 and E2 had higher pH values after the start of the monomer emulsion feeds (at time >0 minute) due to the use of NaOH during polymerization.
- the use of the base sodium hydroxide in monomer emulsion during emulsion polymerization resulted in significantly lower latex viscosity (CE1 vs. E1 and E2). Reduced latex viscosity is desirable for ease of manufacturing and transportation.
- the use of the base sodium hydroxide in monomer emulsion during emulsion polymerization resulted in significantly higher scrub resistance (CE1 vs. E1 and E2). High scrub resistance is a desirable property of latex paint.
- the reactor was maintained at 75° C. for 30 more minutes and then cooled down to room temperature. 20.36 g of a 28% strength by weight aqueous ammonia and 6.67 g of a 1.5% strength by weight aqueous solution of a biocide were added.
- the polymer dispersion was essentially free of coagulum, had a pH of 9.40, solids content of 49.78% by weight, and a Brookfield viscosity of 3030 cps.
- compositions of the monomer emulsions were as follows: Monomer Emulsion I 250.38 g water 33.33 g emulsifier 1 1 15.63 g emulsifier 2 2 13.16 g emulsifier 3 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 0.00 g 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 270.00 g MMA
- Monomer Emulsion II 111.67 g of water 33.33 g of emulsifier 1 1 1.00 g of tert-dodecyl mercaptan 99.00 g of MMA
- the polymerization recipe and process is similar to that of CE2, except NaOH was added into the Monomer Emulsion I.
- the compositions of Emulsion I and II are given below.
- the polymer dispersion was cooled down to room temperature, 17.32 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE2 were added.
- the product was essentially free of coagulum, had a pH of 9.33, solids content of 49.56% by weight, and a Brookfield viscosity of 980 cps.
- compositions of the monomer emulsions were as follows: Monomer Emulsion I 242.73 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 8.50 g 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 270.00 g MMA
- the polymerization recipe and process is similar to that of E3, except no NaOH was added into the Monomer Emulsion I. Instead, the 8.50 g of a 10% aqueous solution of sodium hydroxide was added into the latex after the chemical stripping and cooling down steps. The final product was essentially free of coagulum, had a pH of 9.05, solids content of 49.53% by weight, and a Brookfield viscosity of 2420 cps.
- the polymerization recipe and process is similar to that of CE2, except NaOH was added into the Monomer Emulsion I.
- the compositions of Emulsion I and II are given below.
- the polymer dispersion was cooled down to room temperature, 14.29 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE2 were added.
- the product was essentially free of coagulum, had a pH of 9.20, solids content of 49.70% by weight, and a Brookfield viscosity of 390 cps.
- compositions of the monomer emulsions were as follows: Monomer Emulsion I 235.08 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 17.00 g 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 270.00 g MMA
- the polymerization recipe and process is similar to that of E4, except no NaOH was added into the Monomer Emulsion I. Instead, the 17.0 g of a 10% aqueous solution of sodium hydroxide was added into the latex after the chemical stripping and cooling down steps. The final product was essentially free of coagulum, had a pH of 8.97, solids content of 49.63% by weight, and a Brookfield viscosity of 2188 cps.
- Comparative Examples CE2 through CE4, and Examples E3 and E4 were all formulated into semi-gloss paints using the same formulation as shown above.
- the low-shear viscosities of the paints ranged from 95 to 117 K.U. (Krebs Units), whereas the high-shear viscosities ranged from 1.35 to 1.68 poises (measured according to ASTM D 4287 and D 562-81, respectively).
- the draw-down films were prepared as described above and scrub test was performed according to ASTM D-2486.
- the results in Table 2 indicate that the use of the base sodium hydroxide in monomer emulsion results in significantly lower latex viscosity than the case where no NaOH is used during emulsion polymerization (CE2 vs. E3 and E4).
- the viscosity of the latex is significantly lower when the base sodium hydroxide is used in emulsion feed during polymerization than when it is used after the polymerization (E3 vs. CE3, and E4 vs. CE4).
- the use of the base sodium hydroxide in monomer emulsion during emulsion polymerization results in significantly higher scrub resistance (CE2 vs. E3 and E4).
- the polymerization recipe and process is similar to that of CE1, except ammonium hydroxide was added into the Monomer Emulsion I.
- the compositions of Emulsion I and II are given below.
- the polymer dispersion was cooled down to room temperature, 14.29 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE1 were added.
- the product was essentially free of coagulum, had a pH of 9.24, solids content of 49.89% by weight, and a Brookfield viscosity of 160 cps.
- Table 3 summarizes some properties of the wet latex the the semi-gloss paint based on this latex.
- compositions of the monomer emulsions were as follows: Monomer Emulsion I 246.01 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 6.07 g 28% strength by weight aqueous solution of ammonium hydroxide 40.00 g AAEMA 540.00 g BA 270.00 g MMA
- MMA/BA/AAEMA Copolymer Dispersion Prepared by Using Amp (2-Amino-2-Methyl-1-Propanol) During Polymerization
- the polymerization recipe and process is similar to that of CE1, except 2-amino-2-methyl-1-propanol was added into the Monomer Emulsion I.
- the compositions of Emulsion I and II are given below.
- the polymer dispersion was cooled down to room temperature, 14.29 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE1 were added.
- the product was essentially free of coagulum, had a pH of 8.94, solids content of 50.35% by weight, and a Brookfield viscosity of 930 cps.
- Table 3 summarizes some properties of the wet latex the the semi-gloss paint based on this latex.
- compositions of the monomer emulsions were as follows: Monomer Emulsion I 250.29 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 1.79 g 95% strength by weight aqueous solution of 2-amino-2- methyl-1-propanol 40.00 g AAEMA 540.00 g BA 275.00 g MMA
- the polymerization recipe and process is similar to that of CE1, except KOH was added into the Monomer Emulsion I.
- the compositions of Emulsion I and II are given below.
- the polymer dispersion was cooled down to room temperature, 14.29 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE1 were added.
- the product was essentially free of coagulum, had a pH of 8.93, solids content of 50.23% by weight, and a Brookfield viscosity of 1550 cps.
- Table 3 summarizes some properties of the wet latex the the semi-gloss paint based on this latex.
- compositions of the monomer emulsions were as follows: Monomer Emulsion I 235.08 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 17.00 g 10% strength by weight aqueous solution of potassium hydroxide 40.00 g AAEMA 540.00 g BA 275.00 g MMA
- Comparative Examples CE1 and Examples E5 and E7 were all formulated into semi-gloss paints using the same formulation as shown above.
- the low-shear viscosities of the paints ranged from 93 to 121 K.U. (Krebs Units), whereas the high-shear viscosities ranged from 1.2 to 1.7 poises (measured according to ASTM D 4287 and D 562-81, respectively).
- the draw-down films were prepared as described above and scrub test was performed according to ASTM D-2486.
Abstract
A method of making a composition comprising reacting, in a reactor, a non-halogenated acetoacetate group containing monomer, at least one additional monomer, and a base, wherein at least a portion of the base is fed to the reactor during reaction. Also, a composition comprising an aqueous polymer dispersion that is a product of a method comprising reacting a non-halogenated acetoacetate moiety containing monomer, at least one additional monomer, and a base, wherein the base is fed to the reaction during reaction, wherein the composition has a lower viscosity than a second composition, wherein the second composition is prepared from the same materials as the composition, and the second composition is made by a method wherein the base is added to the second composition after a reaction to form the second composition.
Description
- Acetoacetate moieties in polymers have been used to make crosslinkable polymers. These polymers are useful in coatings. Generally, the polymers are prepared from monomer mixtures that contain a monomer with an acetoacetate moiety. After the polymer is formed, the polymer is neutralized with a base.
- These polymers are often associated with a high viscosity. Higher viscosities increase the difficulty of manufacture and transportation of the polymers. Lower viscosities are generally desirable for reasons of heat transfer and energy consumption during manufacturing. Also, lower viscosities allow for easier pumping and handling. Decreased viscosities also allow for increased solids contents, which is desirable in transportation in that less water has to be shipped.
- It would be desirable to make an acetoacetate moiety containing polymer with a lower viscosity.
- The present invention relates to a method of making a composition comprising reacting, in a reactor, a non-halogenated acetoacetate group containing monomer, at least one additional monomer, and a base, wherein at least a portion of the base is fed to the reactor during reaction.
- The present invention also relates to a composition comprising an aqueous polymer dispersion that is a product of a method comprising reacting a non-halogenated acetoacetate moiety containing monomer, at least one additional monomer, and a base, wherein the base is fed to the reaction during reaction, wherein the composition has a lower viscosity than a second composition, wherein the second composition is prepared from the same materials as the composition, and the second composition is made by a method wherein the base is added to the second composition after a reaction to form the second composition, and wherein the at least one additional monomer is not butadiene.
- As used throughout, ranges are used as a shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range.
- A composition is prepared by reacting a non-halogenated acetoacetate moiety containing monomer, at least one additional monomer, and a base, wherein the base is fed to the reaction. The composition of the present invention is prepared as an aqueous polymer dispersion. The composition has a lower viscosity than a second composition prepared from the same materials as the composition, wherein the second composition is made by a method wherein the base is added to the second composition after a reaction to form the second composition. By changing the point at which a base is added, a different composition is formed. The difference can be seen in the viscosity of the compositions. The composition of the present invention will have a lower viscosity than the second composition. Also, when the composition is included in a coating composition and tested for scrub resistance according to ASTM D-2486, the composition will have a higher scrub resistance as compared to the second composition.
- The base is fed to the reaction while the monomers are reacting. A portion of the total base can be provided in the reactor prior to the start of reaction. Preferably, less than 50% of the total amount of base is present in the reactor at the start of the reaction. More preferably, none of the base is present in the reactor at the start of reaction. The base can be present with the monomers as the monomers are fed to the reactor, or the base can be fed from a separate feed, or a combination of both. In a preferred embodiment, the base is fed with the monomers.
- The bases that are suitable for use in the present invention include those substances by the following three definitions: (1) a compound that dissociates on solution in water to produce one or more hydroxyl ions; (2) any compound which can accept a proton by a more general definition according to the Brönsted concept and (3) anything which has an un-shared pair of electrons according to a still more general concept of G. N. Lewis. Within the scope of the three definitions, the class of compounds that are commonly used in preparing buffers are also included and can be used. A buffer is a solution of a compound that has the capability of minimizing changes in proton (hydrogen ion) concentration.
- General examples of the base include, but are not limited to, alkali metal hydroxides, alkaline earth metal hydroxides, hydroxides of elements from Groups 7 through 13 in the periodic table (IUPAC Nomenclature), ammonia, ammonium hydroxide, amines including primary amines, secondary amines, and tertiary amines such as, but not limited to, alkylamines, arylamines, and heterocyclic amines.
- Preferred bases include, but not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, ammonia, ammonium hydroxide, alkylamines such as methylamines, ethylamines, propylamines, dimethylamines, diethylamines, trimethylamines, and triethylamines, 2-amino-2-methyl-1-propanol, triethanolamine, compounds with buffering capabilities such as carbonates and bicarbonates of alkali metals (preferably lithium, sodium, or potassium), ammonium carbonate, ammonium bicarbonate, mono- and dibasic phosphates of alkali metals, ammonium mono- and dibasic phosphates, tetroxalates and tartrates of alkali metals, ammonium tetroxalate, ammonium tartrate, phthalates of alkali metals, and ammonium phthalate.
- Depending upon the types and amounts of monomers, the amount of base is selected so that undesired results are minimized or avoided. For example, if esters of (meth)acrylic acid are used, too much base can lead to excessive hydrolysis of the monomers. Also, too much base can drive monomers with acid groups to the aqueous phase and reduce the amount of the acid groups attached covalently to the particles, which can decrease the stability of the polymer particles.
- In a preferred embodiment, the base is added during the reacting step in an amount to provide a pH that is at least 0.2 units higher than would be obtained if the base were not used. In another preferred embodiment, the base is added during the reacting step in an amount such that the pH is not higher than 7. In another preferred embodiment, the base is added during the reacting step in an amount to provide a pH that is at least 0.2 units higher than would be obtained if the base were not used, and the base is added during the reacting step in an amount such that the pH is not higher than 7. In another preferred embodiment, the base is used in an amount of from about 0.01 to about 2 weight % based on a total weight of the polymer.
- A non-halogenated acetoacetate moiety has the following general structure: —R1—C(O)—CH2—X, where R1 is a divalent organic radical at least three atoms in length, X is organoacyl [—C(O)—R2] or cyano [—CN], wherein R2 is a methyl group [—CH3] or a monovalent organic radical, and there is no halogen atom on the carbon atom between the two carbonyl carbon atoms. Examples of acetoacetate moiety containing monomers can be found in U.S. Pat. No. 3,459,790, which is incorporated herein by reference. Preferred ethylenically-unsaturated acetoacetate moiety containing monomers include, but are not limited to, 2-acetoacetoxyethyl (meth)acrylate, 3-acetoacetoxypropyl (meth)acrylate, 4-acetoacetoxybutyl (meth)acrylate, 2-cyanoacetoxyethyl (meth)acrylate, 3-cyanoacetoxypropyl (meth)acrylate, 4-cyanoacetoxybutyl (meth)acrylate, N-(2-acetoacetoxyethyl) (meth)acrylamide, allyl acetoacetate, 2,3-di(acetoacetoxy)propyl (meth)acrylate, vinyl acetoacetate, and combinations thereof.
- In a preferred embodiment, the non-halogenated acetoacetate moiety containing monomer is present in an amount from about 0.1 to about 25 weight % based on a total weight of the polymer.
- The at least one additional monomer makes up that balance of the monomers. In a preferred embodiment, the at least one additional monomer is present in an amount from about 70 to about 99.9 weight % based on a total weight of the polymer.
- The at least one additional monomer suitable for the reaction products of the present invention include all monomers that can be reacted with an acetoacetate moiety containing monomer to form an aqueous dispersion polymer. Such monomers can be any ethylenically unsaturated monomer that can be polymerized by a free-radical mechanism. Examples of these monomers can be found in U.S. Patent Application Publication No. 2003/0195297, which is incorporated herein by reference. Suitable examples of the at least one additional monomer include, but are not limited to, (meth)acrylates, hydroxyl containing (meth)acrylates, vinyl aromatics, vinyl halides, vinylidene halides, esters of vinyl alcohol and C1-C18 monocarboxylic acids, esters of allyl alcohol and C1-C18 monocarboxylic acids, ethylenically unsaturated monomers containing at least one carboxylic acid group, salts of ethylenically unsaturated monomers containing at least one carboxylic acid group, anhydrides of ethylenically unsaturated dicarboxylic acids, nitriles of ethylenically unsaturated carboxylic acids, ethylenically unsaturated monomers containing at least one sulfonic acid group, salts of ethylenically unsaturated monomers containing at least one sulfonic acid group, ethylenically unsaturated monomers containing at least one amide group, dienes, alkyds, nitrogen-containing adhesion monomers, glycidyl esters of ethylenically unsaturated monomers, vinyl esters of the formula CH2═CH—O—(CO)—C—(R100)3 wherein R100 is an alkyl (sold under the trade name VEOVA™ by Shell), alkylaminoalkyl group-containing (meth)acrylic monomers, alkyl esters of (meth)acrylic acid containing an ether bond in the alkyl, urethane esters of (meth)acrylic acid, urea esters of (meth)acrylic acid, vinyl monomers, isocyanate esters of (meth)acrylic acid, carbonyl containing monomers, monomers containing hydrolyzable Si-organic bonds, vinyl esters of neo acids (such as those sold under the trade name EXXAR™ NEO 10 and NEO 12 from Exxon), enamines, alkyl crotonates, phosphate (meth)acrylates, and (meth)acryloxy benzophenones.
- The (meth)acrylates are reaction products of ethylenically unsaturated carboxylic acids and C1-C18 alcohols. Examples of (meth)acrylates include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, 4-tertbutylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, dimethyl maleate, n-butyl maleate, alkylene glycol di(meth)acrylates, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, propylene glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, cyclopentadienyl (meth)acrylate, carbodiimide (meth)acrylate, t-butylaminoethyl (meth)acrylate, 2-t-butylaminoethyl (meth)acrylate, and N,N-dimethylaminoethyl (meth)acrylate. The pendant group may contain one or more hetero atoms, aromatic groups, or ethylenic unsaturation.
- Examples of hydroxyl containing (meth)acrylates include, but are not limited to, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylates, and hydroxybutyl (meth)acrylates.
- Examples of ethylenically unsaturated monomers containing at least one carboxylic acid group include, but are not limited to, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, ethacrylic acid, crotonic acid, citraconic acid, cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, trimellitic acid, pyromellitic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, succinic acid, 2,6-naphthalenedicarboxylic acid, glutaric acid, sebacic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarbocylic acid.
- Examples of anhydrides of ethylenically unsaturated dicarboxylic acids include, but are not limited to, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride.
- Examples of esters of ethylenically unsaturated monomers containing at least one carboxylic acid group include, but are not limited to, methyl hydrogen fumarate, benzyl hydrogen maleate, butyl hydrogen maleate, octyl hydrogen itaconate, dodecyl hydrogen citraconate, butyl fumarate, octyl fumarate, octyl maleate, dibutyl maleate, and dioctyl maleate.
- Examples of esters of vinyl alcohol and C2-C18 monocarboxylic acids include, but are not limited to, vinyl acetate, vinyl acetoacetate, vinyl propionate, vinyl n-butyrate, vinyl heptanoate, vinyl perlogonate, vinyl 3,6-dioxaheptanoate, vinyl 3,6,9-trioxanundecanote, vinyl laurate, and vinyl stearate. Examples of esters of allyl alcohol and C1-C18 monocarboxylic acids include, but are not limited to, allyl acetate, allyl propionate, allyl (meth)acrylate, allyl n-butyrate, allyl laurate, allyl stearate, diallyl maleate, and diallyl fumarate.
- Examples of suitable nitriles of ethylenically unsaturated carboxylic acids include, but are not limited to, acrylonitrile and methacrylonitrile. Examples of vinyl aromatics include, but are not limited to, styrene, α-methyl styrene, o-chlorostyrene, chloromethyl styrene, α-phenyl styrene, styrene sulfonic acid, salts of styrene sulfonic acid, para-acetoxystyrene, divinylbenzene, diallyl phthalate, vinyl toluene, and vinyl naphthalene. Examples of dienes include, but are not limited to, butadiene, isoprene, and chloroprene.
- Examples of unsaturated monomers containing at least one sulfonic acid group include, but are not limited to, vinyl sulfonic acid, arylsulfonic acid, sulfopropyl acrylate, (Meth)acryloyloxynaphthalenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and acryloyloxybenzenesulfonic acid.
- Examples of unsaturated monomers containing at least one amide group include, but are not limited to, (meth)acrylamide, dimethyl (meth)acrylamide, N-alkyl (meth)acrylamide, N-butylacrylamide, tetramethylbutylacrylamide, N-alkylol (meth)acrylamide, N-methylol (meth)acrylamide, N-octyl acrylamide, methylene bis acrylamide, diacetoneacrylamide, ethyl imidazolidon (meth)acrylate, and N,N-dimethylaminopropylmethacrylamide.
- As used throughout this specification and claims, nitrogen-containing adhesion monomers are free-radically polymerizable monomers that have at least one of an amino group, a ureido group, a urea group, a thiourea group, and a N-heterocyclic group. Examples of nitrogen-containing adhesion monomers include, but are not limited to, ureido (meth)acrylates, (meth)acrylates with at least one of urea and thiourea in the side chains, acrylic allophanes, aminoethyl acrylate and methacrylate, dimethylaminoethyl acrylate and methacrylate, diethylaminoethyl acrylate and methacrylate, dimethylaminopropyl acrylate and methacrylate, 3-dimethylamino-2,2-dimethylpropyl acrylate and methacrylate, 2-N-morpholinoethyl acrylate and methacrylate, 2-N-piperidinoethyl acrylate and methacrylate, N-(3-dimethylaminopropyl)acrylamide and -methacrylamide, N-dimethylaminoethylacrylamide and -methacrylamide, N-diethylaminoethylacrylamide and -methacrylamide, N-(4-morpholinomethyl)acrylamide and -methacrylamide, vinylimidazole and also monoethylenically unsaturated derivatives of ethyleneurea, such as N-(2-(meth)acryloyloxyethyl)ethyleneurea, N-(β-acrylamidoethyl)ethyleneurea, N-2-(allylcarbamato)aminoethylimidazolidinone, N-vinylethyleneurea, N-(3-allyloxy-2-hydroxypropyl)aminoethylethyleneurea, N-vinyloxyethyleneurea, N-methacryloyloxyacetoxyethylethyleneurea, N-(acrylamidoethylene)ethyleneurea, N-(methacrylamidoethylene)-ethyleneurea, 1-(2-methacryloyloxyethyl)imidazolin-2-one, and N-(methacrylamidoethyl)ethyleneurea.
- Examples of carbonyl-containing monomers include, but are not limited to, acrolein and methacrolein.
- Examples of the monomers containing hydrolyzable Si-organic bonds include, but are not limited to, vinyl silanes, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, methacryloyloxypropyltripropxysilane, methacryloyloxypropyltriisopropxysilane, vinyltrimethoxysilane, vinyl tris (2-methoxyethoxy silane), and vinyl triisopropoxysilane.
- Examples of the phosphate (meth)acrylates include, but are not limited to, sodium phosphate (meth)acrylate, alkylester phosphate (meth)acrylate, and ethoxylated alkylester phosphate (meth)acrylate.
- Other vinyl monomers include, but are not limited to, 1,4-butanediol bisacrylate, vinyl acetoacetamide, vinyl 1,3-diketone, vinyl pyrrolidone, vinyl pyridine, vinyl pyrazine, vinyl piperadiene, vinyl piperidone, vinyl pyrimidine, vinyl pyrrole, vinyl imidazole, vinyl caprolactam, vinyl oxazole, vinyl thiazole, vinyl morpholine, triallyl cyanurate, glycidyl (meth)acrylate, 3-isopropenyl-α-α-dimethylbenzyl isocyanate, ethylene, and propylene.
- In a preferred embodiment, the majority of the at least one additional monomer is not a functional monomer. A functional monomer is a monomer that has a functional group in addition to a carbon-carbon double bond or has at least two sites of ethylenic unsaturation. Functional groups include, but are not limited to, acids, hydroxyls, amides, nitrogen containing groups (such as those in the nitrogen-containing adhesion monomers listed above), silanes. Preferably, the functional monomers in this embodiment are present in an amount from about 0.05 to about 5% by weight based on a total weight of the polymer.
- Examples of functional monomers are given above. Preferred functional monomers include, but are not limited to, mono-ethylenically unsaturated acids and diacids, such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid; nitrogen-containing monomers such as acrylamide, methacrylamide, ureido (meth)acrylate, and ureido (meth)acrylamide; AMPS (acrylamidomethypropylsufonic acid or its salts); silane monomers such as methacryloxypropyl trimethoxysilane, methacryloxypropyl triethoxysilane, methacryloxypropyl tripropoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane; crosslinkers with two or more sites of ethylenic unsaturation, such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butyleneglycol dimethacrylate, and 1,4-butyleneglycol dimethacrylate; ethoxylated vinyl or (meth)acrylic monomers such as PLURIOL® A010R (commercially available from BASF AG),
and BOSOMER™ MPEG 350 MA (commercially available from Laporte), - In the above monomers, references are made to various acids or salts of these acids. When listed, the reference to the acid also includes a reference to its salts. The salts of theses acids include alkali metal salts, alkaline earth metal salts, and ammonium salts.
- The polymers of the present invention can be made in a seedless semi-batch polymerization, an in-situ seeded semi-batch polymerization, a seeded semi-batch polymerization, or a continuous polymerization. In these polymerizations, the polymers of the present invention can be made as a single stage polymer, a gradient or power-feed polymer, or they can be made as a multiple stage polymer.
- The reaction to form the polymers of the present invention can be an emulsion polymerization reaction in which the monomers are emulsified in water with a surface active agent or stabilized by a protective colloid and reacted using emulsion polymerization techniques known in the art. The resulting product of the emulsion polymerization is an aqueous polymer dispersion, also known as a latex.
- The reaction can be started with any initiator. In the reaction, additional materials that are used in emulsion polymerizations can be included. Examples of additional materials include, but are not limited to, electrolytes, chelating agents, dispersing agents, chain transfer agents, and additional seed polymer particles. At the end of the reaction, typically a redox system, which includes an oxidizing agent and a reducing agent, is added to the reaction product to drive the reaction to further completion to reduce the amount of residual monomers. Alternatively, any system that reduces residual monomer content can be used. Examples include, but are not limited to, stripping with steam, vacuum, use of adsorbent materials, and combinations thereof.
- Any temperature that allows the monomers to react to form a polymer can be used as a reaction temperature. Generally, emulsion polymerization reactions have a reaction temperature that ranges from about 3° C. to about 130° C.
- Examples of surface active agents (surfactants) that can be used in the present invention include anionic, cationic, nonionic, amphoteric surfactants, and mixtures thereof.
- Examples of anionic surfactants include, but are not limited to, organosulfates and sulfonates, e.g., sodium and potassium alkyl, aryl, and arylalkyl sulfates and sulfonates, such as sodium 2-ethylhexyl sulfate, potassium 2-ethylhexyl sulfate, sodium nonyl sulfate, sodium lauryl sulfate, potassium methylbenzene sulfonate, sodium dodecylbenzene sulfonate, potassium toluene sulfonate, and sodium xylene sulfonate; higher fatty alcohols, e.g., stearyl, lauryl, etc., which have been ethoxylated and sulfonated; dialkyl esters of alkali metal sulfosuccinic acid salts, such as sodium diamyl sulfosuccinate, sodium dioxtyl sulfosuccinate, and sodium dioctyl sulfosuccinate, formaldehyde-naphthalene sulfonic acid condensation products; and alkali metal salts, partial alkali metal salts, free acids of complex organic phosphate esters, and sodium salt of a fatty alcohol ether sulfate (EMULPHOR™ FAS 30 from BASF AG or DISPONIL™ FES 77 from Cognis, Inc.).
- Examples of cationic surfactants include, but are not limited to, alkylamine salts such as laurylamine acetate, quaternary ammonium salts such as lauryl trimethyl ammonium chloride and alkyl benzyl dimethylammonium chlorides, and polyoxyethylenealkylamines.
- Examples of amphoteric surfactants include, but are not limited to, alkylbetaines such as lauryl-betaine.
- Examples of nonionic surfactants include, but are not limited to, polyethers, e.g., ethylene oxide and propylene oxide condensates that include straight and branched chain alkyl and alkylaryl polyethylene glycol and polypropylene glycol ethers and thioethers; alkylphenoxypoly (ethyleneoxy) ethanols having alkyl groups containing from about 7 to about 18 carbon atoms and having from about 4 to about 240 ethyleneoxy units, such as heptylphenoxypoly (ethyleneoxy) ethanols, nonylphenoxypoly (ethyleneoxy) ethanols; the polyoxyalkylene derivatives of hexitol including sorbitans, sorbides, mannitans and mannides; partial long-chain fatty acids esters, such as the polyoxyalkylene derivatives of sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate and sorbitan trioleate; the condensates of ethylene oxide with a hydrophobic base, the base being formed by condensing propylene oxide with propylene glycol; sulfur containing condensates, e.g., those prepared by condensing ethylene oxide with higher alkyl mercaptans, such as nonyl, dodecyl, or tetradecyl mercaptan, or with alkylthiophenols wherein the alkyl group contains from about 6 to about 15 carbon atoms; ethylene oxide derivatives of long-chain carboxylic acids, such as lauric, myristic, palmitic, or oleic acids or mixtures of acids, such as tall oil fatty acids; ethylene oxide derivatives of long-chain alcohols such as octyl, decyl, lauryl, or cetyl alcohols; and ethylene oxide/propylene oxide copolymers sold under the tradename PLURONIC™ from BASF AG. Another nonionic surfactant is an organosilanol derivative of tung oil, or linseed oil, or high erucic acid rapeseed oil. These surfactant compositions particularly feature high surface activity in forming stable emulsions of organic/water of various difficult to emulsify materials as compared with conventional emulsifying agents. These silanol-based surfactant compositions are described in U.S. Pat. No. 5,807,922.
- Another class of surfactants that can be used are those that are copolymerizable with the monomers described above.
- In emulsion polymerization, the amount of surfactants in the emulsion polymerization reaction range from about 0.01 to about 10 weight percent, preferably about 0.2 to about 5 weight percent based on the total weight of monomers and water.
- Initiators that can be used in a reaction to prepare the polymers of the present invention can be an oxidizer alone or a redox pair of oxidizing and reducing agents. Oxidizers that can be used alone or in the redox system include, but are not limited to, peroxides such as t-butyl hydroperoxide, hydrogen peroxide, pinane hydroperoxide, dibenzoyl peroxide, cumol hydroperoxide, persulfates such as peroxodisulfuric acid, salts of peroxodisulfuric acid, azo compounds such as azobisisobutyronitrile, agents that donate oxygen with free radical formation, alkali metal chlorates, alkali metal perchlorates, transition metal oxide compounds, potassium permaganate, manganese dioxide, lead oxide, lead tetraacetate, iodobenzene. Reducing agents that can be included in the redox system include, but are not limited to, sodium formaldehyde sulfoxylate, erythorbic acid, bisulfites, sodium metabisulfite, sodium bisulfite, adducts of a 3 to 8 carbon ketone with the bisulfite ion, adducts of a 3 to 8 carbon ketone with sulfurous acid, reducing sugars, ascorbic acid, sulfinic acids, hydroxymethane-sulfinic acid, alkane sulfinic acids, isopropane sulfinic acid. Additional redox systems are described in U.S. Pat. No. 5,994,457, which is incorporated herein by reference.
- Additional polymers that can be blended with the polymer compositions of the present invention include, but are not limited to, (meth)acrylates, styrenics, styrene-butadienes, polyurethanes, polyethers, polyesters, melamine-formaldehyde polymers, vinyl halides, vinylidene halides, poly(ethyleneimines), and poly(vinyl amines).
- Before the addition of post reaction additives to prepare specific desired compositions, the reaction products (the aqueous polymer dispersions) of the present invention generally have a total solids content of from about 30% to about 70% and a pH from about 2 to about 7. The pH of the reaction products can be adjusted to above 7 if required using a pH adjusting agent as described below. The particle size can generally range from about 30 nm to about 1000 nm. The particle size distribution can be uni- or multi-modal.
- The compositions of the present invention may further contain additional additives. The additives can be any additive that may be generally included with an emulsion polymerization reaction product or any additive that may be used to make a specific composition. Further additives include, but are not limited to, surfactants, wetting agents, protective colloids, fillers, coloring agents, antiseptics, biocides, dispersing agents, thickening agents, thixotropic agents, antifreezing agents, pH adjusting agents, corrosion inhibitors, ultraviolet light stabilizers, crosslinking promoters, and antioxidants.
- Examples of surfactants and wetting agents include, but are not limited to, the surfactants listed above, sulfosuccinates, fluorinated surfactants, and silicone surfactants.
- Examples of protective colloids are partially and fully hydrolyzed polyvinyl alcohol, hydroxyethyl cellulose, hydroxymethyl cellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose, ethoxylated starch derivatives, polyacrylic acid, alkali metal polyacrylates, polyacrylamide, poly (methyl vinyl ether/maleic anhydride), polyvinylpyrrolidone, water soluble starch, glue, gelatin, water soluble alginates, guar, gum arabic, and gum tragacanth. The amount of protective colloids used in the composition varies depending upon the intended application and generally ranges from about 0.1 weight percent to about 2 weight percent based on the total weight of the composition.
- Examples of fillers include talc, calcium carbonate, diatomaceous earth, mica, kaolin, barium sulfate, magnesium carbonate, fumed silica, vermiculite, graphite, alumina, silica, and rubber powder. Coloring agents such as titanium dioxide and carbon black can also be used as the fillers. The amount of the filler generally ranges from about 5 weight percent to about 50 weight percent based on the total weight of the composition of the present invention.
- Various organic pigments and inorganic pigments may be broadly used as the coloring agents, but non-toxic anticorrosive pigments are preferred. Examples of such pigments are phosphate-type anticorrosive pigments such as zinc phosphate, calcium phosphate, aluminum phosphate, titanium phosphate, silicon phosphate, and ortho- and fused phosphates of these; molybdate-type anticorrosive pigments such as zinc molybdate, calcium molybdate, calcium zinc molybdate, potassium zinc molybdate, potassium zinc phosphomolybdate and potassium calcium phosphomolybdate; and borate-type anticorrosive pigments such as calcium borate, zinc borate, barium borate, barium meta-borate and calcium meta-borate. Also, any color pigment, effect pigment, or color and effect pigment may be used. The amount of the coloring agent used may also be properly selected based on the end-use application of the compositions of the present invention.
- Examples of the antiseptics are pyrrole compounds, imidazole compounds, thiazole compounds, pyridine compounds and organic halogen compounds. The amount of the antiseptic can be suitably selected, and is, for example, up to about 4 percent by weight based on the total weight (as solids content) of the composition.
- Examples of the biocides, which are used either as wet-state protectors or as film protectors of a coating composition, are a wide variety of bactericides, fungicides or algicides, and include, but are not limited to, zinc oxide, cuprous oxide, organotin pigments, copolymers of organotin esters of methacrylic acid with acrylates, tributyl tin oxide, and mixtures thereof. Other examples of biocides particularly useful as wet-state protectors are oxazoladines, organosulfurs, and benzisothiazolins. Any general toxic agent may be suitable as a biocide.
- The dispersing agents include, but are not limited to, sodium salts of polycarboxylic acids, sodium or ammonium salts of fused naphthalene sulfonate, polyoxyalkylene alkyl ethers of phenol ether, sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene styrene phenol, sodium tripolyphosphate and sodium hexametaphosphate. As described above, organosilanol derivatives of tung oil, or linseed oil, or high erucic acid rapeseed oil that are useful as surfactants are also suitable as dispersing agents. The amount of the dispersing agent generally ranges up to about 10 weight percent based on the total weight of the composition.
- The thickening and thixotropic agents may be one and the same or different and may be the same as the protective colloids referred to above. Examples of thickening or thixotropic agents are polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose salt, polyether compounds, urethane modified polyether compounds, polycarboxylic acid compounds, sodium salts of polycarboxylic compounds, polyvinylpyrrolidone, polyoxyethylene derivatives such as polyethylene glycol ether and polyethylene glycol distearate, sodium alginate and inorganic materials such as sodium silicate and bentonite. The amounts of the thickening or the thixotropic agents can be properly chosen depending upon the type of end-application of the composition of the present invention.
- Examples of the pH adjusting agents include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, ammonium hydroxide, ammonia, amines, triethanolamine, and 3-dimethylaminoethanol. The amount of the pH adjusting agent is selected such that the composition has a desired pH.
- Examples of the crosslinking promoters include, but are not limited to, carbodiimides.
- Uses of the compositions of the present invention include, but are not limited to, coatings, including original equipment manufacture (OEM) automotive coatings, refinish automotive coatings, architectural coatings, paper coatings, textile coatings, industrial coatings, furniture coatings, powder coatings, graphic arts, inks, adhesives, binders, nonwovens, paper saturation, medical applications (such as dentifrice, sutures, and bandages), and construction chemicals.
- One or more crosslinking agents or crosslinkers can be added to the polymer composition of the present invention when it is used alone, in a coatings formulation or in a blend with other polymer compositions. Polymer crosslinking provides chemical and stain resistance in coatings as well improved processability, toughness, and service life in other applications. All the chemical compounds known to crosslink with the acetoacetate moiety can be used to effect the crosslinking reaction. Examples of the crosslinking agents include, but not limited to, melamines, isocyanates, electron-deficient olefins, diamines, polyaldehydes. An overview of the various crosslinking possibilities of the acetoacetate moiety is given by Stacey J. Marsh and published in “The Acetoacetate Functionality”, Proceedings of short course on Crosslinking for the Coatings Chemist, 2002 FSCT International Coatings Technology Conference.
- When the polymer composition of the present invention is used alone, in a coatings formulation, or in a blend with other polymer compositions, it can be further crosslinked or cured by at least one of autooxidation and actinic radiation. When cured by actinic radiation, an actinic radiation curing agent can be included. Examples of actinic radiation curing agents include, but are not limited to, benzophenone, 4-methylbenzophenone, benzoyl benzoates, phenylacetophenones, 2,2-dimethoxy-2-phenylacetophenone, and amine modified diacrylates. The amount of actinic radiation curing agents that can be included in the compositions can be any amount that promotes or accelerates curing or hardening of the polymers. Generally, the amount of actinic radiation curing agents ranges from about 0% to about 1% based on the weight of the composition, and preferably from about 0% to about 0.5%.
- The invention is further described in the following examples. The examples are merely illustrative and do not in any way limit the scope of the invention as described and claimed.
- The viscosities of the polymer dispersions were measured throughout using a Brookfield Viscometer (Model RVDV-II+) with either spindle #2 at a speed of 50 rpm for viscosities below about 800 cps or spindle #3 at a speed of 50 rpm for viscosities higher than about 800 cps.
- The preferred emulsion polymerization process is a semi-continuous one in which all or the bulk of the monomers are added over a period of time into the reactor during polymerization. A semi-continuous process may include semi-batch with starved or non-starved monomer feeding, gradient feeding, power feeding, one-stage, multi-stage, swelling polymerization etc. A seed can be used for better control of particle size and/or particle size distribution.
- An amount of a 5% solution of ammonium persulfate initiator was prepared fresh and placed in a feeding vessel. Initiator was added to the polymerization reactor via a feed tube having a valve to control the feed rate.
- To a stirred pre-emulsion vessel were added specified amounts of deionized (DI) water, seed, surfactants, etc. This mixture was agitated to create an emulsion. Additional monomer emulsions or monomer mixtures were optionally prepared in separate vessels and transferred to the pre-emulsion vessel as outlined in the accompanying description. The pre-emulsion vessel was connected to the polymerization reaction via a feeding line with a valve to control the rate of feed.
- Feeding rates of monomer emulsion and initiator were computer-controlled so that exact amounts were delivered into the polymerization reactor. The temperature of the reactor was controlled by a thermostated water bath. Reactor contents were agitated at a sufficient speed so as to provide adequate mixing of reaction components. All reaction conditions are given in the tables below.
- Abbreviations
- MMA: methyl methacrylate
- BA: n-butyl acrylate
- AAEMA: 2-acetoacetoxyethyl methacrylate (from Eastman Chemical)
- MAA: methacrylic acid
- AA: acrylic acid
- IA: itaconic acid
- MMA/BA/AAEMA Copolymer Dispersion Without the Use of a Base During Polymerization
- A polymerization reactor was charged with 407.9 g of water, 10.0 g of PLURIOL® A010R monomer (BASF Corporation) and 47.1 g of a polystyrene seed latex (32.2% by weight; average particle diameter d50=30 nm) and this initial charge was heated to 85° C. Then 3.0 g of a 5.0% strength by weight aqueous solution of ammonium persulfate were added in one portion into the reactor. Commencing simultaneously, the remaining initiator solution was added to the polymerization reactor over the course of 192 minutes and the Monomer Emulsion I was added over 144 minutes. The temperature was maintained at 85° C. After the end of the addition of Monomer Emulsion I, the continuous feed of Monomer Emulsion II was started immediately and lasted 24 minutes. After the end of the addition of Monomer Emulsion II, the reactor was maintained at 85° C. for 30 more minutes and then cooled down to 75° C. 6.43 g of a 28% strength by weight aqueous ammonia and 55 g of water were added. To further reduce the amount of residual monomers, the following chemical stripping process was applied: 21.67 g of a 4.62% strength by weight aqueous solution of t-butyl hydroperoxide and 21.67 g of a 6% strength by weight aqueous solution of sodium acetone bisulfite were fed separately and continuously into the reactor over 30 minutes. The reactor was maintained at 75° C. for 30 more minutes and then cooled down to room temperature. 20.36 g of a 28% strength by weight aqueous ammonia and 6.67 g of a 1.5% strength by weight aqueous solution of a biocide were added. The polymer dispersion was essentially free of coagulum, had a pH of 9.34, solids content of 49.96% by weight and a Brookfield viscosity of 2540 cps. The pH values during emulsion polymerizations were recorded. Table 1 summarizes pH values measured, final latex viscosity, and paint scrub resistance. The compositions of the monomer emulsions were as follows:
Monomer Emulsion I 250.38 g water 33.33 g emulsifier 11 15.63 g emulsifier 22 13.16 g emulsifier 33 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 0.00 g 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 275.00 g MMA -
Monomer Emulsion II 111.67 g of water 33.33 g of emulsifier 11 1.00 g of tert-dodecyl mercaptan 99.00 g of MMA -
- 1Emulsifier 1: A 15% strength aqueous solution of sodium lauryl sulfate under the trade name of TEXAPON™ K12-15 from Cognis Corporation
- 2Emulsifier 2: A 33% strength aqueous solution of sodium lauryl ether sulfate, 30-EO moles under the trade name of DISPONIL™ FES 77 IS from Cognis Corporation
- 3Emulsifier 3: A 38% strength aqueous slurry of sodium aryl sulfonate, under the trade name of CALSOFT™ L-40S from Pilot Chemical Company
- MMA/BA/AAEMA Copolymer Dispersion Prepared by Using a Base During Polymerization
- The polymerization recipe and process is similar to that of CE1, except NaOH was added into the Monomer Emulsion I. The compositions of Emulsion I and II are given below. After the emulsion polymerization and the chemical stripping processes, the polymer dispersion has been cooled down to room temperature, 17.32 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE1 were added. The product was essentially free of coagulum, had a pH of 9.2, solids content of 50.10% by weight and a Brookfield viscosity of 690 cps. The pH values during emulsion polymerizations were recorded. Table 1 summarizes pH values measured, final latex viscosity, and paint scrub resistance. The compositions of the monomer emulsions were as follows:
Monomer Emulsion I 242.73 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g a 50% strength by weight aqueous solution of acrylamide 8.50 g a 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 270.00 g MMA -
Monomer Emulsion II 111.67 g water 33.33 g emulsifier 1 1.00 g tert-dodecyl mercaptan 99.00 g MMA - MMA/BA/AAEMA Copolymer Dispersion Prepared by Using a Base during Polymerization
- The polymerization recipe and process is similar to that of CE1, except NaOH was added into the Monomer Emulsion I. The compositions of Emulsion I and II are given below. After the emulsion polymerization and the chemical stripping processes, the polymer dispersion was cooled down to room temperature, 14.29 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE1 were added. The product was essentially free of coagulum, had a pH of 9.29, solids content of 49.48% by weight and a Brookfield viscosity of 320 cps. The pH values during emulsion polymerizations were recorded. Table 1 summarizes pH values measured, final latex viscosity, and paint scrub resistance. The compositions of the monomer emulsions were as follows:
Monomer Emulsion I 235.08 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 17.00 g 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 275.00 g MMA -
Monomer Emulsion II 111.67 g water 33.33 g emulsifier 1 1.00 g tert-dodecyl mercaptan 99.00 g MMA - Paint Formulation and Evaluation:
- The dispersions of Comparative Example CE1 and Examples E1 and E2 were all formulated into semi-gloss paints using the same formulation as in the following:
Ingredient Parts (g) Semi Gloss Paint Formulation (with about 50 g/L VOC): Water 65.9 Ethylene glycol 13.0 NATROSOL ™ 330 Plus1) 1.0 AMP ™-952) 2.0 Pigment dispersant3) 10.0 Biocide4) 3.0 Defoamer5) 2.0 Extender A6) 50.0 Extender B7) 25.0 Thickner8) 24.0 Titanium Dioxide Slurry9) 294.0 Ground for 20 min. at 1000 RPM and then added the following constituents: Coalescent10) 2.0 Defoamer5) 1.5 Polymer Dispersion (50%) 517.7 Water 61.6
1)NATROSOL ™ 330 Plus thickener from Hercules Inc.
2)AMP-95: Angus Chemical Comapany
3)TAMOL ™ 731 dispersant from Rohm & Haas Comapany
4)PROXEL ™ BD 20 biocide from Avecia Inc.
5)DREWPLUS ™ L-475 defoamer from Ashland Speccialty Chemical
6)BURGESS ™ 28 filler from Burgess Pigment
7)MINEX ™ 7 filler from Unimin Specialty Minerals Corporation
8)AQUAFLOW ™ NHS 310 flow control aid from Hercules Inc.
9)TI-PURE ™ R 746 titanium dioxide pigment from E.I. DuPont de Nemours
10)TEXANOL ™ solvent from Eastman Chemical Company
- The low-shear viscosities of the paints ranged from 100 to 117 K.U. (Krebs Units), whereas the high-shear viscosities ranged from 1.5 to 1.7 poises (measured according to ASTM D4287 and D562-81, respectively).
- The scrub resistance of the paints was tested according to ASTM D-2486 using a “Gardner” scrub machine and the standardized scrub medium SC-2. The paints were applied with the help of a film applicator to the Leneta scrub panels with a wet thickness of about 175 μm. The draw-down films were dried in a climate-controlled room (50% Relative Humidity and 23° C.) for 7 days before the scrub test.
TABLE 1 pH during Polymerization at different times* Final Latex Scrub Neutralizing 0 15 30 60 120 Viscosity Resistance Agent min. min. min. min. min. (cps) (cycles) CE1 No NaOH 3.46 2.95 2.90 2.94 3.14 2540 1220 addition during polymerization E1 0.085%** 3.61 3.56 3.63 3.79 3.91 690 2335 NaOH added during polymerization in Monomer Emulsion 1 E2 0.170%** 3.62 3.58 3.61 3.78 3.91 320 2950 NaOH added during polymerization in Monomer Emulsion 1
*Time from the start of monomer emulsion feed in which different amount of NaOH was added. pH at 0 minute was the value before the start of emulsion feed;
**weight % of NaOH based on total weight of polymer.
- The results in Table 1 indicate that: Examples E1 and E2 had higher pH values after the start of the monomer emulsion feeds (at time >0 minute) due to the use of NaOH during polymerization. The use of the base sodium hydroxide in monomer emulsion during emulsion polymerization resulted in significantly lower latex viscosity (CE1 vs. E1 and E2). Reduced latex viscosity is desirable for ease of manufacturing and transportation. The use of the base sodium hydroxide in monomer emulsion during emulsion polymerization resulted in significantly higher scrub resistance (CE1 vs. E1 and E2). High scrub resistance is a desirable property of latex paint.
- MMA/BA/AAEMA Copolymer Dispersion Without the Use of a Base During Polymerization
- A polymerization reactor was charged with 407.9 g of water, 15.0 g of PLURIOL® A010R monomer (BASF Corporation) and 47.1 g of a polystyrene seed latex (32.2% by weight; average particle diameter d50=30 nm) and this initial charge was heated to 85° C. Then 3.0 g of a 5.0% strength by weight aqueous solution of ammonium persulfate were added in one portion. Commencing simultaneously, the remaining initiator solution was added to the polymerization reactor over the course of 192 minutes and the Monomer Emulsion I was added over 144 minutes. The temperature was maintained at 85° C. After the end of the addition of Monomer Emulsion I, the continuous feed of Monomer Emulsion II was started immediately and lasted 24 minutes. After the end of the addition of Monomer Emulsion II, the reactor was maintained at 85° C. for 30 more minutes and then cooled down to 75° C. 6.43 g of a 28% strength by weight aqueous ammonia and 55 g of water were added. To further reduce the amount of residual monomers, the following chemical stripping process was applied: 21.67 g of a 4.62% strength by weight aqueous solution of t-butyl hydroperoxide and 21.67 g of a 6% strength by weight aqueous solution of sodium acetone bisulfite were fed separately and continuously into the reactor over 30 minutes. The reactor was maintained at 75° C. for 30 more minutes and then cooled down to room temperature. 20.36 g of a 28% strength by weight aqueous ammonia and 6.67 g of a 1.5% strength by weight aqueous solution of a biocide were added. The polymer dispersion was essentially free of coagulum, had a pH of 9.40, solids content of 49.78% by weight, and a Brookfield viscosity of 3030 cps. Some wet properties of the polymer dispersion and the scrub resistance of the semi-gloss paint based on the polymer dispersion are summarized in Table 2. The compositions of the monomer emulsions were as follows:
Monomer Emulsion I 250.38 g water 33.33 g emulsifier 11 15.63 g emulsifier 22 13.16 g emulsifier 33 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 0.00 g 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 270.00 g MMA -
Monomer Emulsion II 111.67 g of water 33.33 g of emulsifier 11 1.00 g of tert-dodecyl mercaptan 99.00 g of MMA - MMA/BA/AAEMA Copolymer Dispersion Prepared by Using a Base During Polymerization
- The polymerization recipe and process is similar to that of CE2, except NaOH was added into the Monomer Emulsion I. The compositions of Emulsion I and II are given below. After the emulsion polymerization and the chemical stripping processes, the polymer dispersion was cooled down to room temperature, 17.32 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE2 were added. The product was essentially free of coagulum, had a pH of 9.33, solids content of 49.56% by weight, and a Brookfield viscosity of 980 cps. Some wet properties of the polymer dispersion and the scrub resistance of the semi-gloss paint based on the polymer dispersion are summarized in Table 2. The compositions of the monomer emulsions were as follows:
Monomer Emulsion I 242.73 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 8.50 g 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 270.00 g MMA -
Monomer Emulsion II 111.67 g water 33.33 g emulsifier 1 1.00 g tert-dodecyl mercaptan 99.00 g MMA - MMA/BA/AAEMA Copolymer Dispersion Without the Use of a Base During Polymerization
- The polymerization recipe and process is similar to that of E3, except no NaOH was added into the Monomer Emulsion I. Instead, the 8.50 g of a 10% aqueous solution of sodium hydroxide was added into the latex after the chemical stripping and cooling down steps. The final product was essentially free of coagulum, had a pH of 9.05, solids content of 49.53% by weight, and a Brookfield viscosity of 2420 cps. Some wet properties of the polymer dispersion are summarized in Table 2.
- MMA/BA/AAEMA Copolymer Dispersion Prepared by Using a Base During Polymerization
- The polymerization recipe and process is similar to that of CE2, except NaOH was added into the Monomer Emulsion I. The compositions of Emulsion I and II are given below. After the emulsion polymerization and the chemical stripping processes, the polymer dispersion was cooled down to room temperature, 14.29 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE2 were added. The product was essentially free of coagulum, had a pH of 9.20, solids content of 49.70% by weight, and a Brookfield viscosity of 390 cps. Some wet properties of the polymer dispersion and the scrub resistance of the semi-gloss paint based on the polymer dispersion are summarized in Table 2. The compositions of the monomer emulsions were as follows:
Monomer Emulsion I 235.08 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 17.00 g 10% strength by weight aqueous solution of sodium hydroxide 40.00 g AAEMA 540.00 g BA 270.00 g MMA -
Monomer Emulsion II 111.67 g water 33.33 g emulsifier 1 1.00 g tert-dodecyl mercaptan 99.00 g MMA - MMA/BA/AAEMA Copolymer Dispersion Without the Use of a Base During Polymerization
- The polymerization recipe and process is similar to that of E4, except no NaOH was added into the Monomer Emulsion I. Instead, the 17.0 g of a 10% aqueous solution of sodium hydroxide was added into the latex after the chemical stripping and cooling down steps. The final product was essentially free of coagulum, had a pH of 8.97, solids content of 49.63% by weight, and a Brookfield viscosity of 2188 cps. Some wet properties of the polymer dispersion are summarized in Table 2.
- Paint Formulation and Evaluation
- The dispersions of Comparative Examples CE2 through CE4, and Examples E3 and E4 were all formulated into semi-gloss paints using the same formulation as shown above. The low-shear viscosities of the paints ranged from 95 to 117 K.U. (Krebs Units), whereas the high-shear viscosities ranged from 1.35 to 1.68 poises (measured according to ASTM D 4287 and D 562-81, respectively). The draw-down films were prepared as described above and scrub test was performed according to ASTM D-2486.
TABLE 2 Latex Latex Vis- Scrub Solids cosity Resistance Neutralizing Agent NaOH (%) (cps) (cycles) Comparative No NaOH addition during 49.8 3030 1500 Example 2 polymerization (CE2) Example 3 0.085%* NaOH added 49.6 980 2330 (E3) during polymerization in Monomer Emulsion 1 Comparative 0.085%* NaOH added after 49.5 2420 Not tested Example 3 the end of polymerization (CE3) Example 4 0.170%* NaOH added 49.7 390 2660 (E4) during polymerization in Monomer Emulsion 1 Comparative 0.170%* NaOH added after 49.6 2190 Not tested Example 4 the end of polymerization (CE4)
*weight % of NaOH based on total weight of copolymer.
- The results in Table 2 indicate that the use of the base sodium hydroxide in monomer emulsion results in significantly lower latex viscosity than the case where no NaOH is used during emulsion polymerization (CE2 vs. E3 and E4). The viscosity of the latex is significantly lower when the base sodium hydroxide is used in emulsion feed during polymerization than when it is used after the polymerization (E3 vs. CE3, and E4 vs. CE4). The use of the base sodium hydroxide in monomer emulsion during emulsion polymerization results in significantly higher scrub resistance (CE2 vs. E3 and E4).
- MMA/BA/AAEMA Copolymer Dispersion Prepared by Using Ammonium Hydroxide During Polymerization
- The polymerization recipe and process is similar to that of CE1, except ammonium hydroxide was added into the Monomer Emulsion I. The compositions of Emulsion I and II are given below. After the emulsion polymerization and the chemical stripping processes, the polymer dispersion was cooled down to room temperature, 14.29 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE1 were added. The product was essentially free of coagulum, had a pH of 9.24, solids content of 49.89% by weight, and a Brookfield viscosity of 160 cps. Table 3 summarizes some properties of the wet latex the the semi-gloss paint based on this latex. The compositions of the monomer emulsions were as follows:
Monomer Emulsion I 246.01 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 6.07 g 28% strength by weight aqueous solution of ammonium hydroxide 40.00 g AAEMA 540.00 g BA 270.00 g MMA -
Monomer Emulsion II 111.67 g water 33.33 g emulsifier 1 1.00 g tert-dodecyl mercaptan 99.00 g MMA - MMA/BA/AAEMA Copolymer Dispersion Prepared by Using Amp (2-Amino-2-Methyl-1-Propanol) During Polymerization
- The polymerization recipe and process is similar to that of CE1, except 2-amino-2-methyl-1-propanol was added into the Monomer Emulsion I. The compositions of Emulsion I and II are given below. After the emulsion polymerization and the chemical stripping processes, the polymer dispersion was cooled down to room temperature, 14.29 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE1 were added. The product was essentially free of coagulum, had a pH of 8.94, solids content of 50.35% by weight, and a Brookfield viscosity of 930 cps. Table 3 summarizes some properties of the wet latex the the semi-gloss paint based on this latex. The compositions of the monomer emulsions were as follows:
Monomer Emulsion I 250.29 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 1.79 g 95% strength by weight aqueous solution of 2-amino-2- methyl-1-propanol 40.00 g AAEMA 540.00 g BA 275.00 g MMA -
Monomer Emulsion II 111.67 g water 33.33 g emulsifier 1 1.00 g tert-dodecyl mercaptan 99.00 g MMA - MMA/BA/AAEMA Copolymer Dispersion Prepared by Using Potassium Hydroxide During Polymerization
- The polymerization recipe and process is similar to that of CE1, except KOH was added into the Monomer Emulsion I. The compositions of Emulsion I and II are given below. After the emulsion polymerization and the chemical stripping processes, the polymer dispersion was cooled down to room temperature, 14.29 g of a 28% strength by weight aqueous ammonia and the same amount of the biocide as in CE1 were added. The product was essentially free of coagulum, had a pH of 8.93, solids content of 50.23% by weight, and a Brookfield viscosity of 1550 cps. Table 3 summarizes some properties of the wet latex the the semi-gloss paint based on this latex. The compositions of the monomer emulsions were as follows:
Monomer Emulsion I 235.08 g water 33.33 g emulsifier 1 15.63 g emulsifier 2 13.16 g emulsifier 3 10.00 g MAA 12.50 g IA 25.00 g 50% strength by weight aqueous solution of acrylamide 17.00 g 10% strength by weight aqueous solution of potassium hydroxide 40.00 g AAEMA 540.00 g BA 275.00 g MMA -
Monomer Emulsion II 111.67 g water 33.33 g emulsifier 1 1.00 g tert-dodecyl mercaptan 99.00 g MMA - Paint Formulation and Evaluation
- The dispersions of Comparative Examples CE1 and Examples E5 and E7 were all formulated into semi-gloss paints using the same formulation as shown above. The low-shear viscosities of the paints ranged from 93 to 121 K.U. (Krebs Units), whereas the high-shear viscosities ranged from 1.2 to 1.7 poises (measured according to ASTM D 4287 and D 562-81, respectively). The draw-down films were prepared as described above and scrub test was performed according to ASTM D-2486.
TABLE 3 Latex Latex Scrub Neutralizing Solids Viscosity Resistance Agent NaOH (%) (cps) (cycles) Comparative No addition of a base 49.8 2540 1220 Example 1 during polymerization (CE1) Example 5 0.170%* NH4OH added 49.9 160 3540 (E5) during polymerization in Monomer Emulsion 1 Example 6 0.170%* AMP (2-amino- 50.4 930 1880 (E6) 2-methyl-1-propanol) added during polymeriza- tion in Monomer Emulsion 1 Example 7 0.170%* KOH added (E7) during polymerization in 50.2 1550 1610 Monomer Emulsion 1
*weight % of the base used based on total weight of copolymer.
- The results in Table 3 indicate that in addition to sodium hydroxide, other bases, such as ammonium hydroxide, AMP, and potassium hydroxide, also reduce latex viscosity when used in monomer emulsion feeds during polymerization (CE1 vs. E5 through E7). Similarly to sodium hydroxide, ammonium hydroxide, AMP, and potassium hydroxide also improve scrub resistance of paint when used in monomer emulsion feeds during polymerization (CE2 vs. E5 through E7).
- It should be appreciated that the present invention is not limited to the specific embodiments described above, but includes variations, modifications and equivalent embodiments defined by the following claims.
Claims (15)
1. A method of making a composition comprising reacting, in a reactor,
a. a non-halogenated acetoacetate group containing monomer,
b. at least one additional monomer, and
c. a base,
wherein at least a portion of the base is fed to the reactor during reaction and wherein the base is added during the reacting step in an amount such that the pH is not higher than 7.
2. The method of claim 1 , wherein one of:
a. none of the base is present in the reactor at the start of the reacting step and the base is mixed with the monomers and is added during the reacting step,
b. none of the base is present in the reactor at the start of the reacting step and the base is fed into the reactor separately from the monomers during the reacting step,
c. none of the base is present in the reactor at the start of the reacting step and the base is fed into the reactor mixed with the monomers and separately from the monomers during the reacting step,
d. less than 50% of the base is present in the reactor at the start of the reacting step and the remainder of the base is mixed with the monomers and is added during the reacting step,
e. less than 50% of the base is present in the reactor at the start of the reacting step and the remainder of the base is fed into the reactor separately from the monomers during the reacting step, or
f. less than 50% of the base is present in the reactor at the start of the reacting step and the remainder of the base is fed into the reactor nixed with the monomers and separately from the monomers during the reacting step.
3. The method of claim 1 , wherein the base is at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, ammonia, ammonium hydroxide, an amine, methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, 2-amino-2-methyl-1-propanol, and triethanolamine.
4. The method of claim 1 , wherein the base is at least one of a compound with buffering capability, an alkali metal carbonate, an alkali metal bicarbonate, ammonium carbonate, ammonium bicarbonate, a monobasic phosphate, an ammonium dibasic phosphate, a tetroxalate of an alkali metal, a tartrate of an alkali metal, ammonium tetroxalate, ammonium tartrate, a phthalate of an alkali metal, and ammonium phthalate.
5. The method of claim 1 , wherein the base is added during the reacting step in an amount to provide a pH that is at least 0.2 units higher than would be obtained if the base were not present.
6. (canceled)
7. The method of claim 1 , wherein the base is added during the reacting step in an amount to provide a pH that is at least 0.2 units higher than would be obtained if the base were not present.
8. The method of claim 1 , wherein the base is used in an amount of from about 0.01 to about 2 weight % based on a total weight of the polymer.
9. The method of claim 1 further comprising reacting a functional monomer with the other monomers to form the polymer, wherein the at least one additional monomer is not a functional monomer, and wherein the functional monomer is a monomer that has at least one of a functional group in addition to a carbon-carbon double bond or has at least two sites of ethylenic unsaturation.
10. The method of claim 9 , wherein the functional monomer is present in an amount from about 0.05 to about 5 weight % based on a total weight of the polymer.
11. The method of claim 9 , wherein the functional monomer is at least one of a mono-ethylenically unsaturated acid, a mono-ethylenically unsaturated diacid, (meth)acrylic acid, itaconic acid, maleic acid, a nitrogen-containing monomer, (meth)acrylamide, ureido (meth)acrylate, ureido (meth)acrylamide, acrylamidomethylpropylsulfonic acid, a salt of acrylamidomethylpropylsulfonic acid, a silane monomer, methacryloxypropyl trimethoxysilane, methacryloxypropyl triethoxysilane, methacryloxypropyl tripropoxysilane, methacryloxypropyl triisopropoxysilane, vinyltrimethoxysilane, vinyltriethyoxysilane, a monomer with at least two sites of ethylenic unsaturation, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butyleneglycol dimethacrylate, 1,4-butyleneglycol dimethacrylate, an ethoxylated vinyl monomer, an ethoxylated (meth)acrylic monomer,
12. The method of claim 1 , wherein the non-halogenated acetoacetate moiety containing monomer is present in an amount from about 0.1 to about 25 weight % based on a total weight of the polymer.
13. The method of claim 1 , wherein the non-halogenated acetoacetate moiety containing monomer is at least one of 2-acetoacetoxyethyl (meth)acrylate, 2-cyanoacetoxyethyl (meth)acrylate, N-(2-acetoacetoxyethyl) (meth)acrylamide, 3-acetoacetoxypropyl (meth)acrylate, 4-acetoacetoxybutyl (meth)acrylate, 3-cyanoacetoxypopyl (meth)acrylate, 4-cyanoacetoxybutyl (meth)acrylate, allyl acetoacetate, 2,3-di(acetoacetoxy)propyl (meth)acrylate, and vinyl acetoacetate.
14. The method of claim 1 , wherein the at least one additional monomer is present in an amount from about 70 to about 99.9 weight % based on a total weight of the polymer.
15-28. (canceled)
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US10/733,895 US20050131176A1 (en) | 2003-12-10 | 2003-12-10 | Process for production of polymer dispersions containing an acetoacetate moiety |
US11/502,500 US7999050B2 (en) | 2003-12-10 | 2006-08-10 | Process for production of polymer dispersions containing an acetoacetate moiety |
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US10/733,895 US20050131176A1 (en) | 2003-12-10 | 2003-12-10 | Process for production of polymer dispersions containing an acetoacetate moiety |
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US20060135684A1 (en) * | 2004-12-17 | 2006-06-22 | Valspar Sourcing, Inc. | Aqueous coating compositions containing acetoacetyl-functional polymers, coatings, and methods |
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US20070191521A1 (en) | 2007-08-16 |
US7999050B2 (en) | 2011-08-16 |
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