US20060189748A1 - Aqueous polymeric composition containing polymeric nanoparticles and treatments prepared therefrom - Google Patents
Aqueous polymeric composition containing polymeric nanoparticles and treatments prepared therefrom Download PDFInfo
- Publication number
- US20060189748A1 US20060189748A1 US10/461,954 US46195403A US2006189748A1 US 20060189748 A1 US20060189748 A1 US 20060189748A1 US 46195403 A US46195403 A US 46195403A US 2006189748 A1 US2006189748 A1 US 2006189748A1
- Authority
- US
- United States
- Prior art keywords
- aqueous
- polymeric composition
- pnps
- polymer particles
- aqueous polymeric
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 197
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 27
- 238000011282 treatment Methods 0.000 title description 16
- 239000002245 particle Substances 0.000 claims abstract description 162
- 239000000178 monomer Substances 0.000 claims abstract description 146
- 229920000642 polymer Polymers 0.000 claims abstract description 121
- 238000000576 coating method Methods 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 239000000049 pigment Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims description 53
- 239000000758 substrate Substances 0.000 claims description 43
- 239000012855 volatile organic compound Substances 0.000 claims description 24
- 239000012736 aqueous medium Substances 0.000 claims description 23
- 230000009477 glass transition Effects 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002023 wood Substances 0.000 abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 61
- -1 aliphatic amines Chemical class 0.000 description 33
- 239000006185 dispersion Substances 0.000 description 29
- 239000002904 solvent Substances 0.000 description 26
- 239000002253 acid Substances 0.000 description 18
- 239000003999 initiator Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 230000003472 neutralizing effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000002609 medium Substances 0.000 description 9
- 230000000149 penetrating effect Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 125000002843 carboxylic acid group Chemical group 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 230000000295 complement effect Effects 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002118 epoxides Chemical group 0.000 description 4
- 229940052303 ethers for general anesthesia Drugs 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 239000004908 Emulsion polymer Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Polymers 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000003139 biocide Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000013772 propylene glycol Nutrition 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
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 2
- CUTWSDAQYCQTGD-UHFFFAOYSA-N 2-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)C(C)OC(=O)C=C CUTWSDAQYCQTGD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004069 aziridinyl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000006254 rheological additive Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FEIQOMCWGDNMHM-KBXRYBNXSA-N (2e,4e)-5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)\C=C\C=C\C1=CC=CC=C1 FEIQOMCWGDNMHM-KBXRYBNXSA-N 0.000 description 1
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- NWRZGFYWENINNX-UHFFFAOYSA-N 1,1,2-tris(ethenyl)cyclohexane Chemical compound C=CC1CCCCC1(C=C)C=C NWRZGFYWENINNX-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- YSZLFZWOEQWOKO-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene 1,2-bis(ethenyl)naphthalene Chemical group CC1=CC=C(C=C)C(C=C)=C1C.C1=CC=CC2=C(C=C)C(C=C)=CC=C21 YSZLFZWOEQWOKO-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- FXLJHFCTYDFUER-UHFFFAOYSA-N 1-bromoprop-2-enylbenzene Chemical compound C=CC(Br)C1=CC=CC=C1 FXLJHFCTYDFUER-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- HLOUDBQOEJSUPI-UHFFFAOYSA-N 1-ethenyl-2,3-dimethylbenzene Chemical class CC1=CC=CC(C=C)=C1C HLOUDBQOEJSUPI-UHFFFAOYSA-N 0.000 description 1
- SKJJTPIEXBJTHM-UHFFFAOYSA-N 1-ethenylimidazol-1-ium-1-sulfonate Chemical compound [O-]S(=O)(=O)[N+]1(C=C)C=CN=C1 SKJJTPIEXBJTHM-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- LEWNYOKWUAYXPI-UHFFFAOYSA-N 1-ethenylpiperidine Chemical class C=CN1CCCCC1 LEWNYOKWUAYXPI-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- FCMUPMSEVHVOSE-UHFFFAOYSA-N 2,3-bis(ethenyl)pyridine Chemical compound C=CC1=CC=CN=C1C=C FCMUPMSEVHVOSE-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- DNYWXJPIRSNXIP-UHFFFAOYSA-N 2-bromo-1,1,1-trichloroethane Chemical compound ClC(Cl)(Cl)CBr DNYWXJPIRSNXIP-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- IWZNLKUVIIFUOG-UHFFFAOYSA-N 2-chloro-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(Cl)=CC1=CC=CC=C1 IWZNLKUVIIFUOG-UHFFFAOYSA-N 0.000 description 1
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- XRASUCAFJRXSGJ-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)propane-1-sulfinic acid Chemical compound OS(=O)CC(C)(C)NC(=O)C=C XRASUCAFJRXSGJ-UHFFFAOYSA-N 0.000 description 1
- GJIIAJVOYIPUPY-UHFFFAOYSA-N 2-methylidenebut-3-enoic acid Chemical compound OC(=O)C(=C)C=C GJIIAJVOYIPUPY-UHFFFAOYSA-N 0.000 description 1
- SBPHKWNOKKNYKP-UHFFFAOYSA-N 2-phenylethenesulfinic acid Chemical compound OS(=O)C=CC1=CC=CC=C1 SBPHKWNOKKNYKP-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- ONPJWQSDZCGSQM-UHFFFAOYSA-N 2-phenylprop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=CC=C1 ONPJWQSDZCGSQM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- 235000007173 Abies balsamea Nutrition 0.000 description 1
- 240000005020 Acaciella glauca Species 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UIAFVUMFKUZIET-UHFFFAOYSA-N CC(=C)C(=O)NCCCC[N+](C)(C)CCS([O-])(=O)=O Chemical compound CC(=C)C(=O)NCCCC[N+](C)(C)CCS([O-])(=O)=O UIAFVUMFKUZIET-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000218645 Cedrus Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 240000005428 Pistacia lentiscus Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 240000002871 Tectona grandis Species 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 241000218685 Tsuga Species 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- LZWJWPDVARVFJI-UHFFFAOYSA-N antimony;nickel;oxotitanium Chemical compound [Ni].[Sb].[Ti]=O LZWJWPDVARVFJI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QRHCILLLMDEFSD-UHFFFAOYSA-N bis(ethenyl)-dimethylsilane Chemical compound C=C[Si](C)(C)C=C QRHCILLLMDEFSD-UHFFFAOYSA-N 0.000 description 1
- JRMHUZLFQVKRNB-UHFFFAOYSA-N bis(ethenyl)-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=C)(C=C)C1=CC=CC=C1 JRMHUZLFQVKRNB-UHFFFAOYSA-N 0.000 description 1
- AMGAACTXBLZKQR-UHFFFAOYSA-N bis(ethenyl)-methyl-phenylsilane Chemical compound C=C[Si](C)(C=C)C1=CC=CC=C1 AMGAACTXBLZKQR-UHFFFAOYSA-N 0.000 description 1
- YQOTVKVZLFHCKW-UHFFFAOYSA-N bis(ethenyl)-methylsilane Chemical compound C=C[SiH](C)C=C YQOTVKVZLFHCKW-UHFFFAOYSA-N 0.000 description 1
- WJNKEHHLMRWLMC-UHFFFAOYSA-N bis(ethenyl)-phenylsilane Chemical compound C=C[SiH](C=C)C1=CC=CC=C1 WJNKEHHLMRWLMC-UHFFFAOYSA-N 0.000 description 1
- PMSZNCMIJVNSPB-UHFFFAOYSA-N bis(ethenyl)silicon Chemical compound C=C[Si]C=C PMSZNCMIJVNSPB-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 239000011093 chipboard Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010219 correlation analysis Methods 0.000 description 1
- 238000005314 correlation function Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HPTMZNZYFRTOKS-UHFFFAOYSA-N ethenesulfinic acid Chemical compound OS(=O)C=C HPTMZNZYFRTOKS-UHFFFAOYSA-N 0.000 description 1
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 description 1
- XEQQKESPDZRKQB-UHFFFAOYSA-N ethenyl-dimethyl-silyloxysilane Chemical compound [SiH3]O[Si](C)(C)C=C XEQQKESPDZRKQB-UHFFFAOYSA-N 0.000 description 1
- MQIGTIFMSSGUBS-UHFFFAOYSA-N ethenylphosphinic acid Chemical compound OP(=O)C=C MQIGTIFMSSGUBS-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000006221 furniture coating Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 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
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940119545 isobornyl methacrylate 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000001565 modulated differential scanning calorimetry Methods 0.000 description 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- BVWUEIUNONATML-UHFFFAOYSA-N n-benzylethenamine Chemical class C=CNCC1=CC=CC=C1 BVWUEIUNONATML-UHFFFAOYSA-N 0.000 description 1
- PZUGJLOCXUNFLM-UHFFFAOYSA-N n-ethenylaniline Chemical class C=CNC1=CC=CC=C1 PZUGJLOCXUNFLM-UHFFFAOYSA-N 0.000 description 1
- AXTLFVLHXSDZOW-UHFFFAOYSA-N n-ethyl-2-methylprop-2-en-1-amine Chemical compound CCNCC(C)=C AXTLFVLHXSDZOW-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 125000001196 nonadecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 230000003287 optical effect Effects 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 235000003499 redwood Nutrition 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000010435 syenite Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- PKRKCDBTXBGLKV-UHFFFAOYSA-N tris(ethenyl)-methylsilane Chemical compound C=C[Si](C)(C=C)C=C PKRKCDBTXBGLKV-UHFFFAOYSA-N 0.000 description 1
- BNCOGDMUGQWFQE-UHFFFAOYSA-N tris(ethenyl)silicon Chemical compound C=C[Si](C=C)C=C BNCOGDMUGQWFQE-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
Definitions
- the present invention relates to an aqueous polymeric composition containing select polymeric nanoparticles.
- the present invention also relates to aqueous polymeric compositions containing a blend of select polymeric nanoparticles and second particles, such as polymer particles or pigment particles.
- the aqueous polymeric composition is useful for preparing coatings with improved properties such as block resistance, print resistance, and dirt pickup resistance.
- the aqueous polymeric composition is also useful in providing compositions that have a low volatile organic content.
- the present invention also relates to methods for using the aqueous polymeric composition to prepare coatings and penetrative treatments.
- coatings is used to refer to compositions that are commonly identified as architectural coatings, such as, for example, flat coatings, semigloss coatings, gloss coatings, primers, topcoats, stain-blocking coatings, elastomeric coatings, mastics, caulks, and sealants, as well as industrial coatings, such as, for example, board and paneling coatings, transportation coatings, furniture coatings, and coil coatings; maintenance coatings such as, for example, bridge and tank coatings, and road marking paints; inks; varnishes; leather coatings and treatments; floor care coatings; paper coatings; personal care coatings such as for hair, skin, and nails; and coatings for woven and nonwoven fabrics, all of which are applied to a variety of substrates.
- Such coatings are characterized by the formation of a substantially continuous film on the surface of the substrate to which they are applied, when in the dry state.
- penetrative treatments is used to refer to substances which, when applied to certain substrates of a porous nature, such as, for example, wood, penetrate into the pores of the substrate rather than form a substantially continuous film on the surface of the substrate.
- treatments is used to generally and broadly refer to both coatings and penetrative treatments, as respectively defined above.
- aqueous polymeric compositions for preparing coatings having certain desired properties in the dry state after application to a substrate that reflect an improvement in at least one purpose for which the coating is applied, such as, for example, improving the block resistance, print resistance, mar resistance, scrub resistance, burnish resistance, dirt pickup resistance, adhesion, gloss, flexibility, toughness, impact resistance, water resistance, heat seal resistance, chemical resistance, and stain resistance of the coated substrate.
- aqueous polymeric compositions for preparing penetrative treatments for protecting certain substrate materials of a porous nature, such as wood, and other natural and engineered cellulosic based substrates are examples of the coatings having certain desired properties in the dry state after application to a substrate, that reflect an improvement in at least one purpose for which the coating is applied, such as, for example, improving the block resistance, print resistance, mar resistance, scrub resistance, burnish resistance, dirt pickup resistance, adhesion, gloss, flexibility, toughness, impact resistance, water resistance, heat seal resistance, chemical resistance, and stain resistance of the coated substrate.
- the present invention is based on our discovery that the incorporation of certain select polymeric nanoparticles into aqueous based treatments greatly improves the properties of both coatings and penetrative treatments.
- compositions including a crosslinking agent and polymeric particles having a mean particle diameter that is most preferably between about 20 and about 40 nanometers, formed in the presence of the reaction product of one or more carboxylic fatty acids and ammonia or one or more polyfunctional aromatic or aliphatic amines, with the dried composition providing a water resistant wood.
- the compositions prepared according to the above are described both as coatings and as being penetrative, although specific improvements to any of the coating properties mentioned above are not disclosed therein.
- certain compositions according to this reference have the disadvantage of involving the use of ammonia in their preparation, which causes certain environmental and health and safety concerns.
- aqueous based coating and penetrative treatment compositions which demonstrate at least one improved property as described above, and which do not involve the use of ammonia. It has now been found that such improvements are provided by aqueous based treatments that include an aqueous dispersion of polymeric particles having a mean diameter of from 1 to 50 nanometers, the particles including, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer.
- PNPs polymeric nanoparticles
- the select PNPs have a mean diameter of from 1 to 50 nanometers (nm) and contain, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer.
- an aqueous polymeric composition includes PNPs dispersed in an aqueous medium, the PNPs having, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer, wherein the PNPs have a mean diameter in the range of from 1 to 50 nm; and second particles, dispersed in the aqueous medium, the second particles being selected from second polymer particles, pigment particles, and mixtures thereof.
- a second aspect of the present invention relates to a method for providing an aqueous polymeric coating composition containing PNPs, the PNPs having, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer, and wherein the PNPs have a mean diameter in the range of from 1 to 50 nm, the method including the steps of: applying the coating onto a substrate and drying or allowing to dry the aqueous polymeric PNP-containing composition to provide a dried coating on the substrate.
- a third aspect of the present invention provides a coating containing PNPs having a mean diameter in the range of from 1 to 50 nm, the PNPs having, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer.
- a fourth aspect of the present invention provides a penetrative treatment composition and method for treating a porous substrate, such as wood, the method including the steps of applying onto the porous substrate an aqueous polymeric composition containing PNPs, the PNPs having, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer, and wherein the PNPs have a mean diameter in the range of from 1 to 50 nm; allowing the aqueous polymeric composition to penetrate into the porous substrate; and drying or allowing to dry the aqueous polymeric composition applied to the porous substrate to provide a treated porous substrate.
- the aqueous polymeric composition of the present invention includes an aqueous dispersion of polymeric particles having a mean diameter in the range of from 1 to 50 nm, the particles including, as polymerized units, at least one multiethylenically unsaturated monomer and at least one ethylenically unsaturated water soluble monomer.
- the term “dispersion” refers to a physical state of matter that includes at least two distinct phases, wherein a first phase is distributed in a second phase, with the second phase being a continuous medium.
- aqueous is used herein to refer to a medium that is from 50 to 100 weight % water, based on the weight of the aqueous medium.
- the PNPs of the present invention are addition polymers which contain, as polymerized units, at least one multiethylenically unsaturated monomer and at least one ethylenically unsaturated water soluble monomer.
- Suitable multiethylenically unsaturated monomers useful in the present invention include di-, tri-, tetra-, and higher multifunctional ethylenically unsaturated monomers, such as, for example, divinyl benzene, trivinylbenzene, divinyltoluene, divinylpyridine, divinylnaphthalene divinylxylene, ethyleneglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethyleneglycol divinyl ether, trivinylcyclohexane, allyl(meth)acrylate, diethyleneglycol di(meth)acrylate, propyleneglycol di(meth)acrylate, 2,2-dimethylpropane
- (meth)acrylic includes both acrylic and methacrylic and the term “(meth)acrylate” includes both acrylate and methacrylate.
- (meth)acrylamide refers to both acrylamide and methacrylamide.
- Alkyl includes straight chain, branched and cyclic alkyl groups.
- the PNPs contain at least 1% by weight, based on the weight of the PNPs, of at least one polymerized multiethylenically unsaturated monomer. Up to and including 99.5 weight % polymerized multiethylenically unsaturated monomer, based on the weight of the PNPs, is effectively used in the particles of the present invention. It is preferred that the amount of polymerized multiethylenically unsaturated monomer is from 1% to 80%, more preferably from 1% to 60%, and most preferably from 1% to 25%, by weight, based on the weight of the PNPs.
- the PNPs further contain, as polymerized units, at least one water soluble monomer.
- water soluble monomer herein is meant a monomer having a solubility in water of at least 7 weight %, preferably at least 9 weight %, and most preferably at least 12 weight %, at a temperature of 25° C. Data for the water solubility of monomers is found, for example, in “Polymer Handbook” (Second Edition, J. Brandrup, E. H. Immergut, Editors, John Wiley & Sons, New York) and “Merck Index” (Eleventh Edition, Merck & Co, Inc., Rahway, N.J.).
- water soluble monomers examples include ethylenically unsaturated ionic monomers and ethylenically unsaturated water soluble nonionic monomers.
- the amount of the polymerized water soluble monomer is at least 0.5 weight %, based on the weight of the PNPs. Up to and including 99 weight % polymerized water soluble monomer, based on the weight of the PNPs, is effectively used in the particles of the present invention.
- Ethylenically unsaturated ionic monomer is a monomer that is capable of bearing an ionic charge in the aqueous medium in which the PNPs are dispersed.
- Suitable ionic monomers include, for example, acid-containing monomers, base-containing monomers, amphoteric monomers; quaternized nitrogen-containing monomers, and other monomers that are subsequently formed into ionic monomers, such as monomers which are neutralized by an acid-base reaction to form an ionic monomer.
- Suitable acid groups include carboxylic acid groups and strong acid groups, such as phosphorus containing acids and sulfur containing acids.
- Suitable base groups include amines.
- the amount of polymerized ionic monomer based on the weight of the PNPs is in the range from 0.5 to 99 weight %, more preferably in the range of from 1 to 50 weight %, even more preferably from 2 to 40 weight %, and most preferably from 3 to 25 weight %.
- Suitable carboxylic acid-containing monomers include carboxylic acid monomers, such as (meth)acrylic acid, acryloxypropionic acid, and crotonic acid; dicarboxylic acid monomers, such as itaconic acid, maleic acid, fumaric acid, and citraconic acid; and monomers which are half esters of dicarboxylic acids, such as monomers containing one carboxylic acid functionality and one C 1-6 ester.
- carboxylic acid monomers such as (meth)acrylic acid, acryloxypropionic acid, and crotonic acid
- dicarboxylic acid monomers such as itaconic acid, maleic acid, fumaric acid, and citraconic acid
- monomers which are half esters of dicarboxylic acids such as monomers containing one carboxylic acid functionality and one C 1-6 ester.
- Preferred are acrylic acid and methacrylic acid.
- Suitable strong acid monomers include sulfur acid monomers, such as 2-acrylamido-2-methyl propane sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, sulfoethyl(meth)acrylate, sulfopropyl(meth)acrylate, 2-acrylamido-2-methyl propane sulfinic acid, styrene sulfinic acid, and vinyl sulfinic acid; and phosphorus acid monomers, such as 2-phosphoethyl(meth)acrylate, vinyl phosphoric acid, and vinyl phosphinic acid.
- Other acid monomers include terminally unsaturated acid containing macromonomers, such as are disclosed in U.S. Pat. No. 5,710,227. Phosphorus acid monomers are desirable as they provide improved adhesion to certain substrates (e.g., metal).
- Suitable base-containing monomers include monomers having amine functionality, which includes N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N-t-butylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylamide, p-aminostyrene, N,N-cyclohexylallylamine, allylamine, diallylamine, dimethylallylamine, N-ethyldimethylallylamine, crotyl amines, and N-ethylmethallylamine; monomers having pyridine functionality, which includes 2-vinylpyridine and 4-vinylpyridine; monomers having piperidine functionality, such as vinylpiperidines; and monomers having imidazole functionality, which includes vinyl imidazole.
- amine functionality which includes N,N-dimethylaminoethyl(me
- Suitable base-containing monomers include oxazolidinylethyl(meth)acrylate, vinylbenzylamines, vinylphenylamines, substituted diallylamines, 2-morpholinoethyl(meth)acrylate, methacrylamidopropyl trimethyl ammonium chloride, diallyl dimethyl ammonium chloride, 2-trimethyl ammonium ethyl methacrylic chloride, and the like.
- Suitable amphoteric monomers include N-vinylimidazolium sulfonate inner salts and N,N-Dimethyl-N-(3-methacrylamidopropyl)-N-(3-sulfopropyl) ammonium betaine.
- Suitable functional monomers in which the functionality is subsequently formed into an acid or base include monomers containing: an epoxide functionality, such as glycidyl(meth)acrylate and allyl glycidyl ether; an anhydride, such as maleic anhydride; an ester such as methyl acrylate; and a halide.
- Suitable halide-containing functional monomers include vinylaromatic halides and halo-alkyl(meth)acrylates.
- Suitable vinylaromatic halides include vinylbenzyl chloride and vinylbenzyl bromide.
- Other suitable functional monomers include allyl chloride, allyl bromide, and (meth)acrylic acid chloride.
- Suitable halo-alkyl(meth)acrylates include chloromethyl(meth)acrylate.
- Suitable functional monomers, in which the functionality is subsequently forming into a nonionic water soluble group include vinyl acetate. Hydrolysis of the polymerized vinyl acetate provides hydroxyl groups to the PNPs.
- Multiethylenically unsaturated monomers that are also water soluble monomers are alternatively used to prepare the PNPs.
- these monomers are classified for the purposes of the present invention as both a multiethylenically unsaturated monomer and a water soluble monomer.
- An example of a water soluble, multiethylenically unsaturated monomer is phosphodi(ethyl methacrylate).
- water soluble nonionic monomers Ethylenically unsaturated water soluble nonionic monomers are referred to herein as “water soluble nonionic monomers”.
- water soluble nonionic monomers include hydroxyalkyl(meth)acrylates, such as hydroxyethyl (meth)acrylate and hydroxypropyl(meth)acrylate; poly(alkylene oxide) esters of (meth)acrylic acid, such as poly(ethylene oxide) 20 methacrylate and poly(propylene oxide) 150 acrylate; acrylamide; and methacrylamide.
- the amount of polymerized water soluble nonionic monomer based on the weight of the PNPs is in the range from 0.5 to 99 weight %, more preferably in the range of from 20 to 90 weight %, even more preferably from 30 to 80 weight %, and most preferably from 40 to 70 weight %.
- the PNPs include, as polymerized units, ionic monomer and nonionic water soluble monomer, lower levels of polymerized nonionic water soluble monomer are preferred.
- the PNPs optionally contain, as polymerized units, one or more third monomers that are not multiethylenically unsaturated monomers and are not water soluble monomers.
- Suitable third monomers include C 1 -C 24 alkyl(meth)acrylates, such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, hexyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, pentadecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, and nonadecyl(
- third monomers include vinyl acetate; vinyl versatate; diisobutylene; ureido containing monomers such as N-(ethyleneureidoethyl)-4-pentenamide, N-(ethylenethioureido-ethyl)-10-undecenamide, butyl ethyleneureido-ethyl fumarate, methyl ethyleneureido-ethyl fumarate, benzyl N-(ethyleneureido-ethyl) fumarate, and benzyl N-(ethyleneureido-ethyl)maleamate; vinylaromatic monomers, such as styrene, ⁇ -methylstyrene, vinyltoluene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylenes, and nonylphenoxy propenyl polyethoxylated alcohol.
- ureido containing monomers such as
- the vinylaromatic monomers also include their corresponding substituted counterparts, such as halogenated derivatives, i.e., containing one or more halogen groups, such as fluorine, chlorine or bromine; and nitro, cyano, (C 1 -C 10 )alkoxy, halo(C 1 -C 10 )alkyl, (C 1 -C 10 )alkoxy, carboxy, and the like.
- halogenated derivatives i.e., containing one or more halogen groups, such as fluorine, chlorine or bromine
- the PNPs have a mean diameter in the range of from 1 to 50 nm, preferably in the range of from 1 to 40 nm, more preferably from 1 to 30 nm, even more preferably from 1 to 25 nm, even further preferably from 1 to 20 nm, and most preferably from 1 to 10 nm. It is further typical that the PNPs have a mean particle diameter of at least 1.5 nm, preferably at least 2 nm.
- One method of determining the particle sizes (mean particle diameter) of the PNPs is by using standard dynamic light scattering techniques, wherein the correlation functions are converted to hydrodynamic sizes using LaPlace inversion methods, such as CONTIN.
- PNPs including, as polymerized units, less than 10 weight % multiethylenically unsaturated monomer have a glass transition temperature from ⁇ 90° C. to 170° C. for the composition in the absence of the polymerized multiethylenically unsaturated monomer, as determined by a modulated differential scanning calorimetry (DSC) measurement.
- DSC modulated differential scanning calorimetry
- the PNPs of the present invention typically have an “apparent weight average molecular weight” in the range of from 5,000 to 1,000,000, preferably in the range of from 10,000 to 500,000, and more preferably in the range of from 15,000 to 100,000.
- “apparent weight average molecular weight” reflects the size of the PNP particles using standard gel permeation chromatography methods, e.g., using THF solvent at 40° C., 3 PlgelTM Columns (Polymer Labs, Amherst, Mass.), 100 Angstrom (10 nm), 103 Angstroms (100 nm), 10 4 Angstroms (1 micron), 30 cm long, 7.8 mm ID, 1 milliliter per minute, 100 microliter injection volume, calibrated to narrow polystyrene standards using Polymer Labs CALIBRETM software.
- the PNPs are further characterizable as having suitable hydrophilicities that allow the PNPs to be dispersed into an aqueous medium.
- One method to characterize the hydrophilicity of the PNPs is to calculate the Hansch parameter, which is actually a measure of hydrophobicity.
- the Hansch parameter is calculated using a group contribution method.
- the monomer units forming the polymer are assigned a hydrophobicity contribution and the relative hydrophobicity of the polymer is calculated based on the weight average of the monomers in the polymer. Hansch and Fujita, J. Amer. Chem. Soc., 86, 1616-1626 (1964); H. Kubinyi, Methods and Principles of Medicinal Chemistry , Volume 1, R.
- Preferred PNPs have a Hansch parameter in the range of from ⁇ 2.5 to 4, preferably from ⁇ 1 to 3.
- Certain embodiments of the PNPs further contain other functional groups, which are provided by the polymerization of monomers containing those groups or precursor groups thereof.
- One method of attaching such other functional groups to the PNPs is by reacting the ionic group of the PNP with a suitable compound.
- PNPs containing carboxylic acid groups are modified to contain pendant hydrophilic groups by reacting carboxylic acid groups with a suitable alcohol, such as a capped polyalkylene oxide.
- functional groups are affixed to the PNPs through non-radical reactions resulting in the formation of ionic or covalent bonds between a modifying compound containing the groups and complementary reactable groups covalently bound to the PNP, such as is taught in U.S. Pat. No. 5,270,380.
- the complementary reactable groups in the PNP and modifying compound provide either ionic or covalent bonding, as appropriate for each reactable group.
- Complementary ionic bonding includes acid-base interaction and ion pair bonding of negatively and positively charged atoms.
- Covalent bonding by complementary reactable groups includes, for example: (a) acetoacetate-aldehyde; (b) acetoacetate-amine; c) amine-aldehyde; (d) amine-anhydride; (e) amine-isocyanate; (f) amine-epoxy; (g) aldehyde-hydrazide; (i) acid-epoxy; j) acid-carbodiimide; (k) acid-chloro methyl ester; (O) acid-chloro methyl amine; (m) acid-anhydride; (n) acid-aziridine; (O) epoxy-mercaptan; and (p) isocyanate-alcohol.
- a suitable method to prepare the aqueous polymeric composition containing the PNPs dispersed in an aqueous medium includes the steps of preparing a nonaqueous PNP dispersion containing the PNPs dispersed in at least one solvent; and combining the nonaqueous PNP dispersion with an aqueous medium.
- nonaqueous herein is meant a medium that contains from zero to less than 50 weight % water, based on the weight of the nonaqueous medium.
- Aqueous polymeric compositions containing PNPs that include, as polymerized units, ionic monomers, are optionally partially or completely neutralized prior to, during, or after combining with the aqueous medium.
- a suitable polymerization process to prepare the nonaqueous PNP dispersion is free radical solution polymerization of at least one multiethylenically unsaturated monomer, at least one water soluble monomer, and, in certain embodiments, at least one third monomer.
- solution polymerization means free radical addition polymerization in a suitable solvent for the polymer.
- suitable solvent for the polymer means that linear random (co)-polymers having substantially similar polymerized monomer units to the PNPs, are soluble in the solvent. Another method for selecting a suitable solvent or mixture of solvents is on the basis of using solubility parameter analysis.
- the suitability of the solvent is determined by substantially matching the solubility parameters of the PNP and of the solvent, such as the Van Krevelen parameters of delta d, delta p, delta h and delta v.
- Van Krevelen et al. Properties of Polymers. Their Estimation and Correlation with Chemical Structure , Elsevier Scientific Publishing Co., 1976; Olabisi et al., Polymer - Polymer Miscibility , Academic Press, NY, 1979; Coleman et al., Specific Interactions and the Miscibility of Polymer Blends , Technomic, 1991; and A. F. M.
- delta d is a measure of dispersive interactions
- delta p is a measure of polar interactions
- delta h is a measure of hydrogen bonding interactions
- delta v is a measure of both dispersive and polar interactions.
- solubility parameters are calculated by alternative methods, such as by the group contribution method, and by experimental determination, as is known in the art.
- a preferred solvent has a delta v parameter within 5 (joule per cubic centimeter) 1/2 , preferably within 1 (Joule per cubic centimeter) 1/2 of the polymer delta v parameter.
- Suitable solvents for the polymerization include organic solvents, such as hydrocarbons; alkanes; halohydrocarbons; chlorinated, fluorinated, and brominated hydrocarbons; aromatic hydrocarbons; ethers; ketones; esters; alcohols; and mixtures thereof.
- Particularly suitable solvents include dodecane, mesitylene, xylenes, diphenyl ether, gamma-butyrolactone, ethyl acetate, ethyl lactate, propyleneglycol monomethyl ether acetate, caprolactone, 2-heptanone, methylisobutyl ketone, acetone, methyl ethyl ketone, diisobutylketone, propyleneglycol monomethyl ether, alkyl-alcohols, such as isopropanol, decanol, and t-butanol; and supercritical carbon dioxide.
- the nonaqueous PNP dispersion is prepared by first charging a heel charge, containing solvent, or alternatively, a mixture of solvent and some portion of the monomers, to a reaction vessel.
- the monomer charge is typically composed of monomers, an initiator, and a chain transfer agent.
- initiation temperatures are in the range of from 55° C. to 125° C., although lower or higher initiator temperatures are possible when using suitable low temperature and high temperature initiators, respectively, as is known in the art.
- the heel charge After the heel charge has reached a temperature sufficient to initiate polymerization, the monomer charge or balance of the monomer charge is added to the reaction vessel.
- the monomer charge time period is typically in the range of from 15 minutes to 4 hours, although both shorter and longer time periods are utilizable.
- the reaction temperature is typically kept constant, although it is also possible to vary the reaction temperature.
- additional initiator in solvent is charged to the reaction and/or the reaction mixture is held for a time.
- Control of PNP particle size and distribution is achieved by choice and control of one or more parameters such as solvent, initiator, total solids level, initiator level, type and amount of multi-functional monomer, type and amount of ionic monomer, type and amount of chain transfer agent, and reaction conditions.
- Initiators useful in the free radical polymerization of the present invention include, for example, one or more of peroxyesters, alkylhydroperoxides, dialkylperoxides, azoinitiators, persulfates, redox initiators and the like.
- the amount of the free radical initiator used is typically from 0.05 to 10% by weight, based on the weight of total monomer.
- chain transfer reagents are used to control the extent of polymerization of the PNPs useful in the present invention.
- Suitable chain transfer agents include, for example: alkyl mercaptans, such as dodecyl mercaptan; aromatic hydrocarbons with activated hydrogens, such as toluene; and alkyl halides, such as bromotrichloroethane.
- the polymerized ionic monomer units of the PNPs is neutralized with at least one neutralizing agent to form an at least partially neutralized nonaqueous PNP dispersion.
- the polymerized ionic monomer units of the PNPs are neutralized in a variety of ways. When the polymerized ionic monomer units are acidic, the neutralizing agent is typically a base. Likewise, when the polymerized ionic monomer units are basic, the neutralizing agent is typically an acid. Suitable bases include inorganic and organic bases.
- Suitable inorganic bases include the full range of the hydroxide, carbonate, bicarbonate, and acetate bases of alkali or alkaline metals.
- Suitable organic bases include ammonia, primary/secondary/tertiary amines, diamines, and triamines.
- Preferred basic neutralizing agents include sodium hydroxide, and ammonium hydroxide.
- Suitable acids include carboxylic acids, such as acetic acid; dicarboxylic acids; (di)carboxylic/hydroxyl acids; aromatic acids, such as benzoic acid; and a variety of other acids, such as boric, carbonic, citric, iodic, nitrous, nitric, periodic, phosphoric, phosphorous, sulfuric, sulfurous, and hydrochloric acid. None of the foregoing categories of bases and acids are deemed to be limiting.
- the amount of neutralizing agent required to neutralize the nonaqueous PNP dispersion is typically determined on a molar basis of neutralizing agent to polymerized ionic monomer units of the PNPs.
- the amount of polymerized ionic monomer units i.e., level of charge
- the amount of polymerized ionic monomer units i.e., level of charge
- the amount of polymerized ionic monomer units i.e., level of charge
- PNP hydrophobicity, Tg, crosslinking level, and type of counter-ion from the neutralizing agent are important variables.
- the polymerized ionic monomer units are preferably at least 20%, more preferably at least 50%, even more preferably at least 80%, and most preferably at least 90% neutralized.
- Neutralizing the PNPs is alternatively carried out in a variety of ways.
- the nonaqueous PNP dispersion is added to a solution containing the neutralizing agent while stirring.
- the neutralizing agent is added as an aqueous solution over time while stirring the nonaqueous PNP dispersion to provide an at least partially neutralized nonaqueous PNP dispersion.
- the at least partially neutralized nonaqueous PNP dispersion is combined with an aqueous medium.
- the aqueous medium optionally contains the neutralizing agent(s) for neutralizing the PNPs, in which case the nonaqueous PNP dispersion is capable of being simultaneously neutralized and combined with an aqueous medium.
- the aqueous medium optionally contains surfactants, which are capable of altering the stability of the PNPs, or of altering other properties of the resulting aqueous PNP dispersion, such as its surface tension.
- the sequence of admixing the partially neutralized nonaqueous PNP dispersion and the aqueous medium is not critical. Various methods and equipment, which are suitable for mixing are described in The Chemical Engineer's Handbook, 5 th Edition, Perry and Chilton, Eds., McGraw-Hill, Ch. 21, 1973. Typically, the aqueous medium is continuously stirred while adding the partially neutralized nonaqueous PNP dispersion to it in order to ensure that the solvent is intimately mixed with the aqueous medium, which minimizes flocculation of the PNPs.
- Suitable weight percentages of the PNPs in the aqueous polymeric composition are typically from 1 to 90 weight %, more typically from 2 to 75 weight %, even more typically from 4 to 65 weight %, further more typically from 8 to 55 weight %, and most typically from 10 to 45 weight %.
- the preparation of the aqueous polymeric composition of the present invention does not require the use of surfactants, and it is typical that the nonaqueous PNP dispersions are substantially free of surfactants, surfactants are included in certain embodiments.
- the amount of surfactants is typically less than 3 weight percent, more typically less than 2 weight percent, even more typically less than 1 weight percent, further typically less than 0.5 weight percent, and even further typically less than 0.2 weight percent, based on total weight of the PNPs.
- the aqueous polymeric composition is optionally treated to remove at least a portion of the solvent, and in certain embodiments, also water, to increase the solids content of the PNPs.
- Suitable methods to concentrate the PNPs include distillation processes, such as forming azeotropes of water and a suitable solvent; evaporation of solvent or water; drying the aqueous polymeric composition by freeze drying or spray drying; solvent extraction techniques; and ultrafiltration techniques.
- the aqueous polymeric composition of this invention is prepared by a method including the steps of preparing a nonaqueous PNP dispersion containing the PNPs dispersed in at least one solvent that is both a suitable solvent for the PNPs and is compatible or miscible in water; and combining the nonaqueous PNP dispersion with an aqueous medium.
- suitable solvents for acrylic-containing PNPs which are also compatible or miscible with water, include isopropanol and ether alcohols (e.g., monobutyl ether of ethylene glycol and monoethyl ether of diethylene glycol).
- the PNPs do not require the addition of neutralizing agents to impart particle stability when combined with water.
- aqueous polymeric compositions of the present invention have a wide range of PNP content.
- the PNP weight fractions range from 0.1 to 99 weight %, more typically from 1 to 90 weight %, even more typically from 2 to 75 weight %, further typically from 5 to 50 weight %, and most typically from 10 to 40 weight %, based on the weight of the aqueous polymeric composition.
- the PNPs are present in the aqueous polymeric composition at a level of from 0.1 to 100 weight % PNPs, based on the total weight of the polymer particles in the aqueous polymeric composition.
- the functional role of the PNPs determines the level of PNPs present. Some of the functional roles of the PNPs are, for example, as additives, as co-binders, as principal binders, and as sole binders. A lower level of PNPs is utilized when the PNPs function as additives and co-binders, while a higher level of PNPs is utilized when the PNPs function as principal binders or sole binders.
- aqueous polymeric compositions of the present invention further contain second particles that are not PNPs, and are second polymer particles, such as emulsion polymer particles, having a mean particle diameter of greater than 50 nm, or are pigment particles.
- second polymer particles such as emulsion polymer particles, having a mean particle diameter of greater than 50 nm, or are pigment particles.
- the second polymer particles are prepared in the presence of the PNPs.
- the PNPs are present in the aqueous polymeric composition at a level of from 1 to 99 weight %, preferably from 5 to 90 weight %, more preferably from 10 to 60 weight %, and most preferably from 20 to 60 weight %, based on the total weight of polymer in the aqueous polymeric composition.
- the glass transition temperatures of the second polymer particles are typically in the range of from ⁇ 60° C. to 120° C., depending upon the intended application of the aqueous polymeric composition containing the second polymer particles. Further, the second polymer particles typically have a mean diameter in the range of from greater than 50 nm up to 2 microns, preferably in the range of from 80 nm to 500 nm, and more preferably, in the range of from 100 nm to 350 nm.
- the second polymer particles are commonly supplied as aqueous dispersions.
- second polymer particles include polymer particles prepared by emulsion polymerization and include crosslinked and uncrosslinked polymer particles, polymer particles containing two or more polymer phases such as core-shell polymer particles, and polymer particles having one or more voids and vesiculated polymer particles as disclosed in U.S. Pat. No. 4,427,835; U.S. Pat. No. 4,920,160; U.S. Pat. No. 4,594,363; U.S. Pat. No. 4,469,825; U.S. Pat. No. 4,468,498; U.S. Pat. No. 4,880,842; U.S. Pat. No. 4,985,064; U.S. Pat. No. 5,157,084; U.S. Pat. No. 5,041,464; U.S. Pat. No. 5,036,109; U.S. Pat. No. 5,409,776; and U.S. Pat. No. 5,510,422.
- second polymer particles are acrylic copolymers, vinyl acetate copolymers, vinyl/acrylic copolymers, styrene/acrylic copolymers, polyurethanes, polyvinyl chlorides, ethylene/vinyl acetate copolymers, styrene/butadiene polymers, and mixtures thereof.
- the second particles are pigment particles.
- pigment particles include inorganic particles such as pigments, extenders, or fillers; and organic colored pigments.
- examples of pigment particles include zinc oxide, antimony oxide, zirconium oxide, chromium oxide, iron oxide, lead oxide, zinc sulfide, lithopone, titanium dioxide including anatase and rutile titanium dioxide, calcium carbonate, calcium sulfate, barium sulfate, mica, clay including delaminated clay, calcined clay, feldspar, nepheline syenite, bismuth vanadate; titanium nickel antimony oxide, cobalt oxides, wollastonite, diatomaceous earth, alumina silicates, carbon black, aluminum oxide, silica, talc, and mixtures thereof.
- the mean diameter of the pigment particles is typically in the range of from 5 nm to greater than 100 microns, preferably in the range of from 20 nm to 20 microns, and more preferably, in the pigment
- the aqueous polymeric composition containing PNPs according to the present invention is useful for treating porous materials including wood substrates.
- Wood substrates are characterized as having a surface containing pores as well as an internal porous structure.
- the PNPs enter into the wood pores and penetrate into the wood substrate.
- a method of treating the wood substrate includes the steps of applying the aqueous polymeric composition of this invention, which contains PNPs, onto a wood substrate; allowing the aqueous polymeric composition to penetrate or to be absorbed into the wood substrate; and drying or allowing to dry the applied aqueous polymeric composition.
- pressure is also applied to increase the penetration of the PNPs into the wood substrate.
- Wood substrates which are capable of being so treated include timber such as, for example, cedar, pine, spruce, fir, redwood, hemlock, teak, oak, cherry, poplar, maple, and walnut; and processed timber, such as including, but not limited to, medium density fiber board, chip board, and laminates such as plywood.
- the aqueous polymeric composition useful for treating wood substrates is provided as a blend further containing second polymer particles.
- the larger second polymer particles are believed to remain at or near the surface of the wood substrate, and to provide protection to the wood substrate surface.
- these second polymer particles have a mean particle diameter in the range of from greater than 50 nm to 500 nm; and they have a glass transition temperature in the range of from 0° C. to 50° C.
- a volatile organic compound is defined herein as a carbon containing compound that has a boiling point below 280° C. at atmospheric pressure. Compounds such as water and ammonia are excluded from the definition of VOC.
- the VOC level of a composition is the total amount of one or more volatile organic compounds contained in the composition.
- VOC is deliberately added to a paint or a coating composition to improve film formation of the resulting coating or to aid in the application properties of the composition employed to prepare the coating.
- VOCs are glycol ethers, organic esters, aromatic compounds, ethylene and propylene glycols, and aliphatic hydrocarbons.
- methods of paint or coating composition preparation frequently introduce adventitious VOCs from various ingredients such as the aqueous dispersion containing the PNPs, and from an optional component such as the aqueous dispersion containing second particles, biocides, soaps, dispersants, and thickeners. These typically account for less than 20 grams (g) VOC per liter of the aqueous polymeric composition.
- the aqueous polymeric composition of this invention is a low VOC composition having a VOC level of less than 150 grams per liter (g/liter) of the aqueous polymeric composition; more preferably the aqueous polymeric composition has a VOC level of less than 100 g/liter of the aqueous polymeric composition; and even more preferably the aqueous polymeric composition has a VOC level of less than 50 g/liter of the aqueous polymeric composition.
- the aqueous polymeric composition contains hard PNPs having a glass transition temperature of at least 50° C. and soft second polymer particles having a glass transition temperature in the range of from ⁇ 40° C. to 70° C.
- the hard PNPs provide one or more improved film properties, such as increased resistance to wear, improved block resistance, improved tint retention, increased elongation of the coating, improved impact resistance, improved adhesion, improved corrosion resistance, improved gloss retention and improved dirt pickup resistance, as compared to a comparative dried coating without the hard PNPs.
- the ratio of the weight of the hard PNPs to the weight of the soft second polymer particles is in the range of from 1:99 to 1:1, preferably in the range of from 1:50 to 1:3, and most preferably in the range of from 1:20 to 1:4.
- Certain embodiments of the aqueous polymeric composition containing the hard PNPs and the soft second polymer particles are provided as a low VOC composition.
- the ratio of the weight of the PNPs to the weight of the second polymer particles is in the range of from 1:20 to 1:3 and more preferably in the range of from 1:9 to 1:5.
- the hard PNPs have a glass transition temperature in the range of 50° C. to 100° C., and preferably in the range of from 60° C. to 80° C.
- a preferred range for the glass transition temperature of soft second polymer particle in the low VOC, hard PNP-containing compositions is from 0° C. to 15° C.
- the aqueous polymeric composition contains PNPs having first reactive groups.
- the first reactive groups are self reactive to form chemical bonds.
- PNPs having self reactive groups is PNPs containing, as polymerized units, methylol acrylamide.
- the aqueous polymeric composition contains second polymer particles having second reactive groups.
- the second reactive groups are self reactive to form chemical bonds.
- An example of second polymer particles having self reactive groups is second polymer particles containing, as polymerized units, methylol (meth)acrylamide.
- the aqueous polymeric composition contains PNPs having first reactive groups and second polymer particles having second reactive groups, wherein the first reactive groups and the second reactive groups are co-reactive to form chemical bonds.
- the aqueous polymeric composition is applied onto a substrate; dried or allowed to dry; and the first reactive groups and the second reactive groups are reacted or allowed to react to form a dried crosslinked coating.
- complementary pairs of first and second reactive groups include, for example, isocyanates and isothiocyanates, which react with reactive groups selected from alcohols, amines, ureas, anhydrides, and mixtures thereof; aldehyde groups, which react with reactive groups selected from acetoacetoxy groups, amine groups, and mixtures thereof; acetoacetoxy groups, which react with reactive groups selected from aldehyde groups, amine groups, and mixtures thereof; epoxides, thioranes, and aziridines, all three of which react with reactive groups selected from alcohol groups, carboxylic acid groups, anhydride groups, amine groups, mercaptan groups, and mixtures thereof; carbodiimides, which react with reactive groups selected from carboxylic acid groups, phosphorus acid groups, alcohol groups, amine groups, mercaptan groups, and mixtures thereof; haloalkane and halomethylphenyl groups, both of which react with reactive groups selected from amine groups, carboxylic acid groups, and
- the first reactive groups and the second reactive groups are the same reactive functionality and are self reactive.
- suitable chemical bonds between the PNPs and the second polymer particles include the following types of linkages: esters, amides, ethers, urethanes, thiol ethers, amines, and ureidos.
- the reaction between the first reactive group and the second reactive group occurs during the drying step. Alternatively, in other embodiments, drying occurs any time prior to film formation, provided that the extent of reaction does not materially impair film formation.
- the reaction of the first reactive group and the second reactive group is conducted in the presence of one or more catalysts. Alternatively, no catalyst is used. Techniques to determine the extent of reaction of the first reactive group and the second reactive group include infrared spectroscopy, nuclear magnetic resonance spectroscopy, and ultraviolet-visible spectroscopy.
- One method to prepare the PNP containing the first reactive group is an addition polymerization process that includes polymerization of at least one monomer containing a select reactive group, wherein the select reactive group is the first reactive group.
- monomers containing a select reactive group include ionic monomers, and isocyanate monomers, such as isocyanato ethyl methacrylate, dimethyl meta-isopropenyl benzyl isocyanate; acetoacetoxy monomers, such as acetoacetoxy ethyl(meth)acrylate; aldehyde monomers, such as acrolein and methacrolein; amine monomers, such as t-butyl aminoethyl(meth)acrylate, dimethyl aminoethyl(meth)acrylate, aminobutyl(meth)acrylate, aminoethyl(meth)acrylate; aminopropyl(meth)acrylate; and oxazolidinoethyl(meth)
- a suitable process to prepare the second polymer particles having at least one second reactive group is addition polymerization of at least one monomer having a select reactive group, wherein the select reactive group is the second reactive group.
- the first reactive group or the second reactive group is generated by functionalization of a precursor group after polymerization of the PNPs or the second polymer particle, respectively.
- Second polymer particles suitable for use in the present embodiment include particles having a single polymer phase and particles having two or more polymer phases, such as core-shell particles, acorn particles having an outer polymer phase partially encapsulating a core polymer phase, and particles having one polymer phase forming multiple domains on or within a second polymer phase.
- the aqueous polymeric composition contains PNPs having first reactive groups and second polymer particles having second reactive groups, wherein the PNPs have a lower glass transition temperature than the second polymer particles.
- the low T g PNPs aid in the film formation of the second polymer particles and allow the aqueous polymeric composition to form a film with a lower amount of coalescent than a film formed from the second polymer particles in the absence of the PNPs.
- the first and second reactive groups react to form crosslinks to provide the film with improved properties than a film absent the crosslinks.
- the PNPs have a T g in the range of from ⁇ 10° C.
- the second polymer particles having second reactive groups have a T g in the range of from 5° C. to 35° C., and more preferably in the range of from 15° C. to 25° C.
- the ratio of the weight of PNPs having first reactive group to the weight of second polymer particles having second reactive groups is in the range of from 1:100 to 1:3, preferably in the range of from 1:25 to 1:4; and more preferably, in the range of from 1:20 to 1:5.
- the aqueous polymeric composition contains a ternary mixture of polymer particles having select particle sizes.
- the ternary mixture includes: a small mode of PNPs having a mean particle diameter in the range of from 10 nm to 20 nm; a medium mode of polymer particles having a mean particle diameter in the range of from 30 nm to 70 nm; and a large mode of second polymer particles having a mean particle diameter in the range of from 100 nm to 200 nm.
- Suitable medium mode polymer particles are PNPs having a mean diameter in the range of from 30 nm to 50 nm, second polymer particles having a mean diameter in the range of greater than 50 nm to 70 nm, and mixtures thereof.
- the ternary mixture has a small mode of PNPs with a T g in the range of from ⁇ 10° C. to 5° C., and more preferably in the range of from ⁇ 5° C. to 0° C.
- the ternary mixture has a medium mode of PNPs with a T g in the range of from 0° C. to 15° C., and more preferably in the range of from 5° C. to 12° C.
- the ternary mixture has a large mode of second polymer particles with a T g in the range of from 5° C. to 20° C., and more preferably in the range of from 10° C. to 15° C.
- the aqueous polymeric composition containing the ternary mixture of polymer particles is useful for preparing coatings having a balance of good film formation and acceptable film properties such as hardness, dirt pickup resistance, scrub resistance, block resistance, or gloss.
- Certain embodiments of aqueous polymeric compositions contains a ternary mixture of polymer particles having select particle sizes are provided as a low VOC composition.
- the total amount of pigment and second polymer particles having a T g of at least 50° C. in the aqueous polymeric composition is defined according to the volume concentration of these components in the dried coating formed from the aqueous polymeric composition or equivalently, by the volume concentration of these components based on the total volume of solids in the aqueous polymeric composition.
- the aqueous polymeric composition of this invention includes compositions having pigment volume concentrations in the range of from 0 to 95% and thereby encompasses coating compositions sometimes described in the art as clear coatings, stains, flat coatings, satin coatings, semi-gloss coatings, gloss coatings, primers, textured coatings, paper coatings, and the like.
- the aqueous polymeric composition of this invention which contains pigment particles
- One method to prepare the aqueous polymeric composition of this invention, which contains pigment particles is by admixing the aqueous polymeric composition containing the PNPs and an aqueous slurry containing dispersed pigment particles. Mixing is typically employed to minimize localized concentrations of either the PNPs or the pigment particles.
- the pigmented aqueous polymeric composition of this invention is prepared by admixing dry pigment particles into the aqueous polymeric composition containing PNPs to disperse the pigment particles into the aqueous medium. Typically, high shear mixing is employed to disperse the dried pigment particles.
- dispersants are added to aid in dispersing or stabilizing the pigment particles in the aqueous medium of the aqueous polymeric composition.
- the aqueous polymeric composition of this invention further contains one of pigment particles, second polymer particles having a T g of at least 50° C., and mixtures thereof.
- This aqueous polymeric composition has a PVC of at least 70%, preferably of at least 75%, and more preferably at least 80%.
- the aqueous polymeric composition of this embodiment is useful as a coating composition suitable for preparing opaque dried coatings, such as a dried flat paint or a dried paper coating.
- the PNPs contained in this aqueous polymeric composition have a T g in the range of from ⁇ 20° C. to 40° C., preferably in the range of from ⁇ 10° C.
- the aqueous polymeric composition of this embodiment typically contains one or more of titanium dioxide, calcium carbonate, and clay, as the pigment particle. Certain other embodiments also still further contain solid bead polymer particles or polymer particles having one or more voids, as the second polymer particles, with a T g of at least 50° C.
- the aqueous polymeric composition contains PNPs and second polymer particles, wherein the second polymer particles are prepared in the presence of the PNPs.
- the PNPs are present in the aqueous polymeric composition at a level of from 1 to 99 weight %, preferably from 5 to 90 weight %, more preferably from 10 to 60 weight %, and most preferably from 20 to 60 weight %, based on the total weight of polymer in the aqueous polymeric composition.
- the second polymer particles are polymerized by aqueous emulsion polymerization. In this process, the PNPs are added to an aqueous reaction medium prior to or during the polymerization of the second polymer particles.
- the PNPs of the present embodiment are believed to act as stabilizers (i.e., dispersants) in the aqueous emulsion polymerization process, such as according to methods which use “high acid” polymeric stabilizers (often referred to as “resin supported emulsion polymerization”, see for example U.S. Pat. No. 4,845,149 and U.S. Pat. No. 6,020,061).
- suitable emulsion polymer compositions any emulsion polymer, copolymer, multi-stage copolymer, interpolymer, core-shell polymer, and the like can be stabilized using the PNPs of the present invention.
- Preferred second polymer particles include, as polymerized units, at least one (meth)acrylic ester monomer.
- the emulsion polymerization process performed in the presence of the PNPs further includes synthesis adjuvants, such as surfactants, initiators, and buffers.
- synthesis adjuvants such as surfactants, initiators, and buffers.
- the resulting aqueous polymeric composition prepared by this process contains PNPs on the second polymer particle surface as well as PNPs dispersed in the aqueous phase.
- the aqueous polymeric composition of this embodiment is useful for preparing coatings having improved properties, such as, gloss.
- the aqueous polymeric composition containing such PNP stabilized second polymer particles displays enhanced colloidal stability relative to analogous blends of PNPs and second polymer particles that are prepared in the absence of PNPs.
- One aspect of the present invention is directed towards a method of preparing a coating from the aqueous polymeric composition containing the PNPs.
- the method includes the steps of applying the aqueous polymeric composition onto a substrate; and drying or allowing to dry the applied aqueous polymeric composition to provide the coating.
- the aqueous polymeric composition is typically applied onto a substrate to prepare a dry coating.
- Suitable techniques for applying the aqueous polymeric composition onto a substrate include brushing, rolling, drawdown, dipping, with a knife or trowel, curtain coating, and spraying methods such as, for example, air-atomized spray, air-assisted spray, airless spray, high volume low pressure spray, and air-assisted airless spray.
- the wet coating thickness of the applied aqueous polymeric composition is commonly in the range of 1 micron to 5 millimeters.
- the aqueous polymeric composition is applied onto a substrate as a single coat and alternatively multiple coats.
- the applied aqueous polymeric composition is typically allowed to dry at ambient conditions and alternatively dried by the application of heat to provide a dry coating. Drying is typically allowed to proceed under ambient conditions such as, for example, at 0° C. to 35° C.
- the method is useful for providing coatings that have at least one improved property compared to a comparative coating prepared in the absence of the PNPs.
- improved properties include block resistance, print resistance, mar resistance, scrub resistance, abrasion resistance, burnish resistance, dirt pickup resistance, adhesion, gloss, flexibility, toughness, impact resistance, reduced coalescent demand, water resistance, chemical resistance, biological fouling resistance, and stain resistance.
- a pigmented coating pigment particles are dispersed within a polymeric film to provide opacity or hiding.
- the opacity of the pigmented coating arises from the scattering of light, which results from differences in the refractive indices of the polymeric film and the pigment particles contained within.
- the pigment particles typically have a refractive index of 1.8 or greater. Refractive indices for polymers are typically in the range of 1.4 to 1.6.
- the improved coating is a pigmented coating that is prepared from an aqueous polymeric composition containing PNPs, second polymer particles, and pigment particles.
- the improved pigmented coating has a polymeric film that is formed from the second polymer particles and the PNPs.
- the polymeric film of the improved pigmented coating has a lower refractive index than a film formed absent the PNPs and thus has a greater difference in the refractive indices of the polymeric film and the pigment contained within.
- the improved pigmented coating provides increased hiding compared to a pigmented coating absent the PNPs.
- the polymer film of the improved pigmented coating typically contains from 2 to 30 weight % PNPs, based on the total weight of the polymeric film.
- aqueous polymeric composition include one or more other components, such as, without limitation, other polymers, surfactants, other pigments, other extenders, dyes, pearlescents, adhesion promoters, crosslinkers, dispersants, defoamers, leveling agents, optical brighteners, ultraviolet stabilizers, absorbing pigments, coalescents, rheology modifiers, preservatives, biocides, and antioxidants.
- other components such as, without limitation, other polymers, surfactants, other pigments, other extenders, dyes, pearlescents, adhesion promoters, crosslinkers, dispersants, defoamers, leveling agents, optical brighteners, ultraviolet stabilizers, absorbing pigments, coalescents, rheology modifiers, preservatives, biocides, and antioxidants.
- An aqueous polymeric composition is prepared by admixing an aqueous dispersion containing PNPs with an aqueous dispersion containing second polymer particles.
- the PNPs contain, as polymerized units, 60 weight % methyl methacrylate, 30 weight % acrylic acid, and 10 weight % trimethylolpropane triacrylate.
- the PNPs have a T g above 50° C. and a mean particle diameter of 12 nm.
- the second polymer particles are acrylic copolymer particles having a T g of 3° C. and a mean particle diameter of 155 nm.
- the aqueous polymeric composition, Example 1.1 contains 15 weight % PNPs and 85 weight % second polymer particles, and has a total polymer solids content of 33 weight %.
- a pigmented aqueous polymeric composition and a comparative composition are prepared by combining the ingredients in Table 2.1 in the order listed.
- Ingredient Example 1.2 Comparative A titanium dioxide dispersion 344.07 g 344.07 g (77 weight %) Water 20.00 g 20.00 g propylene glycol 16.50 g 16.50 g
- Example 1.1 (33 weight % 537.65 g — solids)
- Dry coating samples are prepared from the pigmented aqueous polymeric composition, Example 1.2, and the comparative composition, Comparative A, and are evaluated according to the procedure for the scrub resistance test.
- the two compositions are applied in such a way that the two compositions are placed side by side and drawn together by a single drawing with a 0.0762 mm (3 mil) film applicator 152.4 mm (6 inch) in width.
- Each composition forms a 7.5 cm (3 inch) wide coating on a single vinyl chart, and the two compositions have the same coating thickness.
- the samples are allowed to dry at 23° C. and 50% relative humidity for 7 days.
- Abrasive scrub resistance is measured with a scrub machine using 10 g scrub medium and 5 ml water.
- a piece of 0.0254 mm (1 mil) thick and 76.2 mm wide vinyl shim is placed underneath the sample vinyl chart. The two side edges of the shim are in the center of each coating. The number of cycles required to completely cut through each coating is recorded.
- the coating prepared from the pigmented aqueous polymeric composition of Example 1.2 requires 750 cycles to cut through the coating.
- the coating prepared from the pigment comparative composition of Comparative A requires 360 cycles to cut through the coating.
- the results show that the aqueous polymeric composition of this invention is useful for preparing coatings with improved scrub resistance.
- PNPs are prepared containing, as polymerized units, 35 weight % methyl methacrylate, 35 weight % butyl acrylate, 20 weight % acrylic acid, and 10 weight % trimethylolpropane triacrylate.
- the PNPs are prepared according to the following process: A 5-liter reactor is fitted with a thermocouple, a temperature controller, a purge gas inlet, a water-cooled reflux condenser with purge gas outlet, a stirrer, and a monomer feed line.
- a monomer mixture (A) is prepared by admixing 157.5 g methyl methacrylate, 157.5 g butyl acrylate, 90.0 g acrylic acid, and 45.0 g trimethylolpropane triacrylate.
- an initiator mix (B) is prepared by admixing 18.00 g of a 75% solution of t-amyl peroxypivalate in mineral spirits and 112.50 g isopropyl alcohol. A charge of 2325 g isopropyl alcohol is added to the reactor. Nitrogen gas is flowed through the reactor for approximately 30 minutes. Next, the contents of the reactor are heated to 79° C. while maintaining the flow of nitrogen gas.
- a dual feed of the monomer mixture (A) and the initiator mix (B) are added to the reactor.
- the two mixtures are feed uniformly using feed pumps over an addition period of 120 minutes.
- the contents of the reactor are maintained at 79° C. for 30 minutes.
- the first of three additional initiator charges each containing 9.00 g of a 75% solution of t-amyl peroxypivalate in mineral spirits, and 22.50 g isopropyl alcohol, is added.
- a second initiator charge is added 30 minutes after the first initiator charge addition.
- the final initiator charge is added 30 minutes after the second initiator charge addition.
- the contents of the reactor are then held at a temperature of 79° C.
- aqueous polymeric composition Example 2.1, contains PNPs with a mean particle diameter of 5 nm and has a pH of 8.5.
- PNPs containing, as polymerized units, 35 weight % methyl methacrylate, 35 weight % butyl acrylate, 20 weight % acrylic acid, and 10 weight % trimethylolpropane triacrylate are prepared according to the general procedure for preparing Example 2.1.
- the resulting aqueous polymeric composition contains PNPs having a mean particle diameter of 5 nm and has a solids level of 25 weight %.
- Second polymer particles are prepared by emulsion polymerization in the presence of PNPs.
- the reaction vessel is a 2-liter, 4 neck round bottom flask equipped with a side arm, condenser, stirrer, and thermocouple.
- aqueous polymeric composition of Example 2.1 is added to the flask.
- the contents of the flask is heated to 85° C. under a nitrogen atmosphere.
- a monomer mixture containing 175.0 g butyl acrylate and 175.0 g methyl methacrylate is added over a 1.5 hour period, while coadding a separate solution of 2.63 g ammonium persulfate in 100.0 g deionized water and 0.22 g of 28% ammonium hydroxide over a 2 hour time period.
- the persulfate containing cofeed is continued for 30 minutes.
- the contents of the flask is maintained at a temperature of 85° C. for 60 minutes.
- the contents of the flask is allowed to cool to 25° C. and is filtered through a 100/325 mesh set of stacked screens, yielding a negligible quantity of coagulated polymer.
- the resulting filtered emulsion polymerization product an aqueous polymeric composition containing PNPs and second polymer particles, has a total polymer solids content of 55.04%, a pH of 7.5, second polymer particles with a mean diameter of 128 nm, and a viscosity of 1.09 pascal second.
- the aqueous polymeric composition of Example 3.1 contains 20 weight % PNP and 80 weight % second polymer particles, based on the total weight of polymer.
- Second polymer particles are prepared in the presence of PNPs according to the general procedure for Example 3.1.
- the resulting aqueous polymeric composition of Example 3.2 contains 50 weight % PNPs of Example 3.1 and 50 weight % second polymer particles containing, as polymerized units, 65 weight % butyl acrylate and 35 weight % methacrylic acid, based on the total weight of polymer.
Abstract
Description
- The present invention relates to an aqueous polymeric composition containing select polymeric nanoparticles. The present invention also relates to aqueous polymeric compositions containing a blend of select polymeric nanoparticles and second particles, such as polymer particles or pigment particles. The aqueous polymeric composition is useful for preparing coatings with improved properties such as block resistance, print resistance, and dirt pickup resistance. The aqueous polymeric composition is also useful in providing compositions that have a low volatile organic content. The present invention also relates to methods for using the aqueous polymeric composition to prepare coatings and penetrative treatments.
- As used herein, “coatings” is used to refer to compositions that are commonly identified as architectural coatings, such as, for example, flat coatings, semigloss coatings, gloss coatings, primers, topcoats, stain-blocking coatings, elastomeric coatings, mastics, caulks, and sealants, as well as industrial coatings, such as, for example, board and paneling coatings, transportation coatings, furniture coatings, and coil coatings; maintenance coatings such as, for example, bridge and tank coatings, and road marking paints; inks; varnishes; leather coatings and treatments; floor care coatings; paper coatings; personal care coatings such as for hair, skin, and nails; and coatings for woven and nonwoven fabrics, all of which are applied to a variety of substrates. Such coatings are characterized by the formation of a substantially continuous film on the surface of the substrate to which they are applied, when in the dry state.
- As used herein, “penetrative treatments” is used to refer to substances which, when applied to certain substrates of a porous nature, such as, for example, wood, penetrate into the pores of the substrate rather than form a substantially continuous film on the surface of the substrate.
- Unless specifically indicated to the contrary, as used herein, the term “treatments” is used to generally and broadly refer to both coatings and penetrative treatments, as respectively defined above.
- There has long been and there is an ongoing need in the art for aqueous polymeric compositions for preparing coatings having certain desired properties in the dry state after application to a substrate, that reflect an improvement in at least one purpose for which the coating is applied, such as, for example, improving the block resistance, print resistance, mar resistance, scrub resistance, burnish resistance, dirt pickup resistance, adhesion, gloss, flexibility, toughness, impact resistance, water resistance, heat seal resistance, chemical resistance, and stain resistance of the coated substrate. There has also been and there is an ongoing need in the art for aqueous polymeric compositions for preparing penetrative treatments for protecting certain substrate materials of a porous nature, such as wood, and other natural and engineered cellulosic based substrates.
- The present invention is based on our discovery that the incorporation of certain select polymeric nanoparticles into aqueous based treatments greatly improves the properties of both coatings and penetrative treatments.
- Published PCT Patent Application WO 99/01522 discloses a composition including a crosslinking agent and polymeric particles having a mean particle diameter that is most preferably between about 20 and about 40 nanometers, formed in the presence of the reaction product of one or more carboxylic fatty acids and ammonia or one or more polyfunctional aromatic or aliphatic amines, with the dried composition providing a water resistant wood. The compositions prepared according to the above are described both as coatings and as being penetrative, although specific improvements to any of the coating properties mentioned above are not disclosed therein. Moreover, certain compositions according to this reference have the disadvantage of involving the use of ammonia in their preparation, which causes certain environmental and health and safety concerns.
- Accordingly, it is still desired to provide aqueous based coating and penetrative treatment compositions which demonstrate at least one improved property as described above, and which do not involve the use of ammonia. It has now been found that such improvements are provided by aqueous based treatments that include an aqueous dispersion of polymeric particles having a mean diameter of from 1 to 50 nanometers, the particles including, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer.
- Improvements in the aforementioned coating and penetrative treatment properties are obtained in treatments according to the present prepared from aqueous polymeric compositions including select polymeric nanoparticles (PNPs). The select PNPs have a mean diameter of from 1 to 50 nanometers (nm) and contain, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer.
- According to a first aspect of the present invention, an aqueous polymeric composition includes PNPs dispersed in an aqueous medium, the PNPs having, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer, wherein the PNPs have a mean diameter in the range of from 1 to 50 nm; and second particles, dispersed in the aqueous medium, the second particles being selected from second polymer particles, pigment particles, and mixtures thereof.
- A second aspect of the present invention relates to a method for providing an aqueous polymeric coating composition containing PNPs, the PNPs having, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer, and wherein the PNPs have a mean diameter in the range of from 1 to 50 nm, the method including the steps of: applying the coating onto a substrate and drying or allowing to dry the aqueous polymeric PNP-containing composition to provide a dried coating on the substrate.
- A third aspect of the present invention provides a coating containing PNPs having a mean diameter in the range of from 1 to 50 nm, the PNPs having, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer.
- A fourth aspect of the present invention provides a penetrative treatment composition and method for treating a porous substrate, such as wood, the method including the steps of applying onto the porous substrate an aqueous polymeric composition containing PNPs, the PNPs having, as polymerized units, at least one multiethylenically unsaturated monomer and at least one water soluble monomer, and wherein the PNPs have a mean diameter in the range of from 1 to 50 nm; allowing the aqueous polymeric composition to penetrate into the porous substrate; and drying or allowing to dry the aqueous polymeric composition applied to the porous substrate to provide a treated porous substrate.
- The aqueous polymeric composition of the present invention includes an aqueous dispersion of polymeric particles having a mean diameter in the range of from 1 to 50 nm, the particles including, as polymerized units, at least one multiethylenically unsaturated monomer and at least one ethylenically unsaturated water soluble monomer. As used herein, the term “dispersion” refers to a physical state of matter that includes at least two distinct phases, wherein a first phase is distributed in a second phase, with the second phase being a continuous medium. The term “aqueous” is used herein to refer to a medium that is from 50 to 100 weight % water, based on the weight of the aqueous medium.
- The PNPs of the present invention are addition polymers which contain, as polymerized units, at least one multiethylenically unsaturated monomer and at least one ethylenically unsaturated water soluble monomer. Suitable multiethylenically unsaturated monomers useful in the present invention include di-, tri-, tetra-, and higher multifunctional ethylenically unsaturated monomers, such as, for example, divinyl benzene, trivinylbenzene, divinyltoluene, divinylpyridine, divinylnaphthalene divinylxylene, ethyleneglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethyleneglycol divinyl ether, trivinylcyclohexane, allyl(meth)acrylate, diethyleneglycol di(meth)acrylate, propyleneglycol di(meth)acrylate, 2,2-dimethylpropane-1,3-di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylates, such as polyethylene glycol 200 di(meth)acrylate and polyethylene glycol 600 di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, poly(butanediol) di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, glyceryl propoxy tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, divinyl silane, trivinyl silane, dimethyl divinyl silane, divinyl methyl silane, methyl trivinyl silane, diphenyl divinyl silane, divinyl phenyl silane, trivinyl phenyl silane, divinyl methyl phenyl silane, tetravinyl silane, dimethyl vinyl disiloxane, poly(methyl vinyl siloxane), poly(vinyl hydro siloxane), poly(phenyl vinyl siloxane), and mixtures thereof. As used herein, the term “(meth)acrylic” includes both acrylic and methacrylic and the term “(meth)acrylate” includes both acrylate and methacrylate. Likewise, the term “(meth)acrylamide” refers to both acrylamide and methacrylamide. “Alkyl” includes straight chain, branched and cyclic alkyl groups.
- Typically, the PNPs contain at least 1% by weight, based on the weight of the PNPs, of at least one polymerized multiethylenically unsaturated monomer. Up to and including 99.5 weight % polymerized multiethylenically unsaturated monomer, based on the weight of the PNPs, is effectively used in the particles of the present invention. It is preferred that the amount of polymerized multiethylenically unsaturated monomer is from 1% to 80%, more preferably from 1% to 60%, and most preferably from 1% to 25%, by weight, based on the weight of the PNPs.
- The PNPs further contain, as polymerized units, at least one water soluble monomer. By “water soluble monomer” herein is meant a monomer having a solubility in water of at least 7 weight %, preferably at least 9 weight %, and most preferably at least 12 weight %, at a temperature of 25° C. Data for the water solubility of monomers is found, for example, in “Polymer Handbook” (Second Edition, J. Brandrup, E. H. Immergut, Editors, John Wiley & Sons, New York) and “Merck Index” (Eleventh Edition, Merck & Co, Inc., Rahway, N.J.). Examples of water soluble monomers include ethylenically unsaturated ionic monomers and ethylenically unsaturated water soluble nonionic monomers. Typically, the amount of the polymerized water soluble monomer is at least 0.5 weight %, based on the weight of the PNPs. Up to and including 99 weight % polymerized water soluble monomer, based on the weight of the PNPs, is effectively used in the particles of the present invention.
- Ethylenically unsaturated ionic monomer, referred to herein as “ionic monomer”, is a monomer that is capable of bearing an ionic charge in the aqueous medium in which the PNPs are dispersed. Suitable ionic monomers include, for example, acid-containing monomers, base-containing monomers, amphoteric monomers; quaternized nitrogen-containing monomers, and other monomers that are subsequently formed into ionic monomers, such as monomers which are neutralized by an acid-base reaction to form an ionic monomer. Suitable acid groups include carboxylic acid groups and strong acid groups, such as phosphorus containing acids and sulfur containing acids. Suitable base groups include amines. It is preferred that the amount of polymerized ionic monomer based on the weight of the PNPs is in the range from 0.5 to 99 weight %, more preferably in the range of from 1 to 50 weight %, even more preferably from 2 to 40 weight %, and most preferably from 3 to 25 weight %.
- Suitable carboxylic acid-containing monomers include carboxylic acid monomers, such as (meth)acrylic acid, acryloxypropionic acid, and crotonic acid; dicarboxylic acid monomers, such as itaconic acid, maleic acid, fumaric acid, and citraconic acid; and monomers which are half esters of dicarboxylic acids, such as monomers containing one carboxylic acid functionality and one C1-6 ester. Preferred are acrylic acid and methacrylic acid. Suitable strong acid monomers include sulfur acid monomers, such as 2-acrylamido-2-methyl propane sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, sulfoethyl(meth)acrylate, sulfopropyl(meth)acrylate, 2-acrylamido-2-methyl propane sulfinic acid, styrene sulfinic acid, and vinyl sulfinic acid; and phosphorus acid monomers, such as 2-phosphoethyl(meth)acrylate, vinyl phosphoric acid, and vinyl phosphinic acid. Other acid monomers include terminally unsaturated acid containing macromonomers, such as are disclosed in U.S. Pat. No. 5,710,227. Phosphorus acid monomers are desirable as they provide improved adhesion to certain substrates (e.g., metal).
- Suitable base-containing monomers include monomers having amine functionality, which includes N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N-t-butylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylamide, p-aminostyrene, N,N-cyclohexylallylamine, allylamine, diallylamine, dimethylallylamine, N-ethyldimethylallylamine, crotyl amines, and N-ethylmethallylamine; monomers having pyridine functionality, which includes 2-vinylpyridine and 4-vinylpyridine; monomers having piperidine functionality, such as vinylpiperidines; and monomers having imidazole functionality, which includes vinyl imidazole. Other suitable base-containing monomers include oxazolidinylethyl(meth)acrylate, vinylbenzylamines, vinylphenylamines, substituted diallylamines, 2-morpholinoethyl(meth)acrylate, methacrylamidopropyl trimethyl ammonium chloride, diallyl dimethyl ammonium chloride, 2-trimethyl ammonium ethyl methacrylic chloride, and the like.
- Suitable amphoteric monomers include N-vinylimidazolium sulfonate inner salts and N,N-Dimethyl-N-(3-methacrylamidopropyl)-N-(3-sulfopropyl) ammonium betaine.
- Suitable functional monomers, in which the functionality is subsequently formed into an acid or base include monomers containing: an epoxide functionality, such as glycidyl(meth)acrylate and allyl glycidyl ether; an anhydride, such as maleic anhydride; an ester such as methyl acrylate; and a halide. Suitable halide-containing functional monomers include vinylaromatic halides and halo-alkyl(meth)acrylates. Suitable vinylaromatic halides include vinylbenzyl chloride and vinylbenzyl bromide. Other suitable functional monomers include allyl chloride, allyl bromide, and (meth)acrylic acid chloride. Suitable halo-alkyl(meth)acrylates include chloromethyl(meth)acrylate. Suitable functional monomers, in which the functionality is subsequently forming into a nonionic water soluble group include vinyl acetate. Hydrolysis of the polymerized vinyl acetate provides hydroxyl groups to the PNPs.
- Multiethylenically unsaturated monomers that are also water soluble monomers are alternatively used to prepare the PNPs. In such embodiments, these monomers are classified for the purposes of the present invention as both a multiethylenically unsaturated monomer and a water soluble monomer. An example of a water soluble, multiethylenically unsaturated monomer is phosphodi(ethyl methacrylate).
- Ethylenically unsaturated water soluble nonionic monomers are referred to herein as “water soluble nonionic monomers”. Examples of water soluble nonionic monomers include hydroxyalkyl(meth)acrylates, such as hydroxyethyl (meth)acrylate and hydroxypropyl(meth)acrylate; poly(alkylene oxide) esters of (meth)acrylic acid, such as poly(ethylene oxide)20 methacrylate and poly(propylene oxide)150 acrylate; acrylamide; and methacrylamide. It is preferred that the amount of polymerized water soluble nonionic monomer based on the weight of the PNPs is in the range from 0.5 to 99 weight %, more preferably in the range of from 20 to 90 weight %, even more preferably from 30 to 80 weight %, and most preferably from 40 to 70 weight %. When the PNPs include, as polymerized units, ionic monomer and nonionic water soluble monomer, lower levels of polymerized nonionic water soluble monomer are preferred.
- The PNPs optionally contain, as polymerized units, one or more third monomers that are not multiethylenically unsaturated monomers and are not water soluble monomers. Suitable third monomers include C1-C24 alkyl(meth)acrylates, such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, hexyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, pentadecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, and nonadecyl(meth)acrylate, and mixtures thereof. Other suitable third monomers include vinyl acetate; vinyl versatate; diisobutylene; ureido containing monomers such as N-(ethyleneureidoethyl)-4-pentenamide, N-(ethylenethioureido-ethyl)-10-undecenamide, butyl ethyleneureido-ethyl fumarate, methyl ethyleneureido-ethyl fumarate, benzyl N-(ethyleneureido-ethyl) fumarate, and benzyl N-(ethyleneureido-ethyl)maleamate; vinylaromatic monomers, such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylenes, and nonylphenoxy propenyl polyethoxylated alcohol. The vinylaromatic monomers also include their corresponding substituted counterparts, such as halogenated derivatives, i.e., containing one or more halogen groups, such as fluorine, chlorine or bromine; and nitro, cyano, (C1-C10)alkoxy, halo(C1-C10)alkyl, (C1-C10)alkoxy, carboxy, and the like.
- The PNPs have a mean diameter in the range of from 1 to 50 nm, preferably in the range of from 1 to 40 nm, more preferably from 1 to 30 nm, even more preferably from 1 to 25 nm, even further preferably from 1 to 20 nm, and most preferably from 1 to 10 nm. It is further typical that the PNPs have a mean particle diameter of at least 1.5 nm, preferably at least 2 nm. One method of determining the particle sizes (mean particle diameter) of the PNPs is by using standard dynamic light scattering techniques, wherein the correlation functions are converted to hydrodynamic sizes using LaPlace inversion methods, such as CONTIN.
- Typically, PNPs including, as polymerized units, less than 10 weight % multiethylenically unsaturated monomer, have a glass transition temperature from −90° C. to 170° C. for the composition in the absence of the polymerized multiethylenically unsaturated monomer, as determined by a modulated differential scanning calorimetry (DSC) measurement. PNPs containing, as polymerized units, at least 50 weight % multiethylenically unsaturated monomer are considered to have glass transition temperatures of at least 50° C.
- The PNPs of the present invention typically have an “apparent weight average molecular weight” in the range of from 5,000 to 1,000,000, preferably in the range of from 10,000 to 500,000, and more preferably in the range of from 15,000 to 100,000. As used herein, “apparent weight average molecular weight” reflects the size of the PNP particles using standard gel permeation chromatography methods, e.g., using THF solvent at 40° C., 3 Plgel™ Columns (Polymer Labs, Amherst, Mass.), 100 Angstrom (10 nm), 103 Angstroms (100 nm), 104 Angstroms (1 micron), 30 cm long, 7.8 mm ID, 1 milliliter per minute, 100 microliter injection volume, calibrated to narrow polystyrene standards using Polymer Labs CALIBRE™ software.
- The PNPs are further characterizable as having suitable hydrophilicities that allow the PNPs to be dispersed into an aqueous medium. One method to characterize the hydrophilicity of the PNPs is to calculate the Hansch parameter, which is actually a measure of hydrophobicity. The Hansch parameter is calculated using a group contribution method. The monomer units forming the polymer are assigned a hydrophobicity contribution and the relative hydrophobicity of the polymer is calculated based on the weight average of the monomers in the polymer. Hansch and Fujita, J. Amer. Chem. Soc., 86, 1616-1626 (1964); H. Kubinyi, Methods and Principles of Medicinal Chemistry, Volume 1, R. Mannhold et al., Eds., VCH, Weinheim (1993); C. Hansch and A. Leo, Substituent Constants for Correlation Analysis in Chemistry and Biology, Wiley, New York (1979); and C. Hansch, P. Maloney, T. Fujita, and R. Muir, Nature, 194. 178-180 (1962).
- Values of the hydrophobicity contributions for several monomers are listed in Table 1.
TABLE 1 Monomer Hydrophobicity Contribution ethyl acrylate 2.11 butyl acrylate 3.19 2-ethyl hexylacrylate 5.22 styrene 4.29 methyl methacrylate 1.89 ethyl methacrylate 2.43 butyl methacrylate 3.51 isobornyl methacrylate 5.0 butadiene 4.0 acrylic acid −2.52 methacrylic acid −2.2 maleic anhydride −3.5
Preferred PNPs have a Hansch parameter in the range of from −2.5 to 4, preferably from −1 to 3. - Certain embodiments of the PNPs further contain other functional groups, which are provided by the polymerization of monomers containing those groups or precursor groups thereof. One method of attaching such other functional groups to the PNPs is by reacting the ionic group of the PNP with a suitable compound. For example, PNPs containing carboxylic acid groups are modified to contain pendant hydrophilic groups by reacting carboxylic acid groups with a suitable alcohol, such as a capped polyalkylene oxide. Alternatively, functional groups are affixed to the PNPs through non-radical reactions resulting in the formation of ionic or covalent bonds between a modifying compound containing the groups and complementary reactable groups covalently bound to the PNP, such as is taught in U.S. Pat. No. 5,270,380.
- The complementary reactable groups in the PNP and modifying compound provide either ionic or covalent bonding, as appropriate for each reactable group. Complementary ionic bonding includes acid-base interaction and ion pair bonding of negatively and positively charged atoms. Covalent bonding by complementary reactable groups includes, for example: (a) acetoacetate-aldehyde; (b) acetoacetate-amine; c) amine-aldehyde; (d) amine-anhydride; (e) amine-isocyanate; (f) amine-epoxy; (g) aldehyde-hydrazide; (i) acid-epoxy; j) acid-carbodiimide; (k) acid-chloro methyl ester; (O) acid-chloro methyl amine; (m) acid-anhydride; (n) acid-aziridine; (O) epoxy-mercaptan; and (p) isocyanate-alcohol. One of the first and second reactable groups in each pair is present either in the PNP or, alternatively, in the modifying compound.
- A suitable method to prepare the aqueous polymeric composition containing the PNPs dispersed in an aqueous medium includes the steps of preparing a nonaqueous PNP dispersion containing the PNPs dispersed in at least one solvent; and combining the nonaqueous PNP dispersion with an aqueous medium. By “nonaqueous” herein is meant a medium that contains from zero to less than 50 weight % water, based on the weight of the nonaqueous medium. Aqueous polymeric compositions containing PNPs that include, as polymerized units, ionic monomers, are optionally partially or completely neutralized prior to, during, or after combining with the aqueous medium.
- A suitable polymerization process to prepare the nonaqueous PNP dispersion is free radical solution polymerization of at least one multiethylenically unsaturated monomer, at least one water soluble monomer, and, in certain embodiments, at least one third monomer. As used herein, “solution polymerization” means free radical addition polymerization in a suitable solvent for the polymer. As used herein, “suitable solvent for the polymer” means that linear random (co)-polymers having substantially similar polymerized monomer units to the PNPs, are soluble in the solvent. Another method for selecting a suitable solvent or mixture of solvents is on the basis of using solubility parameter analysis. According to such methods, the suitability of the solvent is determined by substantially matching the solubility parameters of the PNP and of the solvent, such as the Van Krevelen parameters of delta d, delta p, delta h and delta v. See, for example, Van Krevelen et al., Properties of Polymers. Their Estimation and Correlation with Chemical Structure, Elsevier Scientific Publishing Co., 1976; Olabisi et al., Polymer-Polymer Miscibility, Academic Press, NY, 1979; Coleman et al., Specific Interactions and the Miscibility of Polymer Blends, Technomic, 1991; and A. F. M. Barton, CRC Handbook of Solubility Parameters and Other Cohesion Parameters, 2nd Ed., CRC Press, 1991. Delta d is a measure of dispersive interactions, delta p is a measure of polar interactions, delta h is a measure of hydrogen bonding interactions, and delta v is a measure of both dispersive and polar interactions. Such solubility parameters are calculated by alternative methods, such as by the group contribution method, and by experimental determination, as is known in the art. A preferred solvent has a delta v parameter within 5 (joule per cubic centimeter)1/2, preferably within 1 (Joule per cubic centimeter)1/2 of the polymer delta v parameter. Suitable solvents for the polymerization include organic solvents, such as hydrocarbons; alkanes; halohydrocarbons; chlorinated, fluorinated, and brominated hydrocarbons; aromatic hydrocarbons; ethers; ketones; esters; alcohols; and mixtures thereof. Particularly suitable solvents, depending on the composition of the PNP, include dodecane, mesitylene, xylenes, diphenyl ether, gamma-butyrolactone, ethyl acetate, ethyl lactate, propyleneglycol monomethyl ether acetate, caprolactone, 2-heptanone, methylisobutyl ketone, acetone, methyl ethyl ketone, diisobutylketone, propyleneglycol monomethyl ether, alkyl-alcohols, such as isopropanol, decanol, and t-butanol; and supercritical carbon dioxide.
- The nonaqueous PNP dispersion is prepared by first charging a heel charge, containing solvent, or alternatively, a mixture of solvent and some portion of the monomers, to a reaction vessel. The monomer charge is typically composed of monomers, an initiator, and a chain transfer agent. Typically, initiation temperatures are in the range of from 55° C. to 125° C., although lower or higher initiator temperatures are possible when using suitable low temperature and high temperature initiators, respectively, as is known in the art. After the heel charge has reached a temperature sufficient to initiate polymerization, the monomer charge or balance of the monomer charge is added to the reaction vessel. The monomer charge time period is typically in the range of from 15 minutes to 4 hours, although both shorter and longer time periods are utilizable. During the monomer charge, the reaction temperature is typically kept constant, although it is also possible to vary the reaction temperature. After completing the monomer mixture addition, additional initiator in solvent is charged to the reaction and/or the reaction mixture is held for a time.
- Control of PNP particle size and distribution is achieved by choice and control of one or more parameters such as solvent, initiator, total solids level, initiator level, type and amount of multi-functional monomer, type and amount of ionic monomer, type and amount of chain transfer agent, and reaction conditions.
- Initiators useful in the free radical polymerization of the present invention include, for example, one or more of peroxyesters, alkylhydroperoxides, dialkylperoxides, azoinitiators, persulfates, redox initiators and the like. The amount of the free radical initiator used is typically from 0.05 to 10% by weight, based on the weight of total monomer. According to certain embodiments, chain transfer reagents are used to control the extent of polymerization of the PNPs useful in the present invention. Suitable chain transfer agents include, for example: alkyl mercaptans, such as dodecyl mercaptan; aromatic hydrocarbons with activated hydrogens, such as toluene; and alkyl halides, such as bromotrichloroethane.
- In one method of preparing the aqueous polymeric composition of the present invention, at least a portion of the polymerized ionic monomer units of the PNPs is neutralized with at least one neutralizing agent to form an at least partially neutralized nonaqueous PNP dispersion. The polymerized ionic monomer units of the PNPs are neutralized in a variety of ways. When the polymerized ionic monomer units are acidic, the neutralizing agent is typically a base. Likewise, when the polymerized ionic monomer units are basic, the neutralizing agent is typically an acid. Suitable bases include inorganic and organic bases. Suitable inorganic bases include the full range of the hydroxide, carbonate, bicarbonate, and acetate bases of alkali or alkaline metals. Suitable organic bases include ammonia, primary/secondary/tertiary amines, diamines, and triamines. Preferred basic neutralizing agents include sodium hydroxide, and ammonium hydroxide. Suitable acids include carboxylic acids, such as acetic acid; dicarboxylic acids; (di)carboxylic/hydroxyl acids; aromatic acids, such as benzoic acid; and a variety of other acids, such as boric, carbonic, citric, iodic, nitrous, nitric, periodic, phosphoric, phosphorous, sulfuric, sulfurous, and hydrochloric acid. None of the foregoing categories of bases and acids are deemed to be limiting.
- The amount of neutralizing agent required to neutralize the nonaqueous PNP dispersion is typically determined on a molar basis of neutralizing agent to polymerized ionic monomer units of the PNPs. Without being bound to a particular theory, the amount of polymerized ionic monomer units (i.e., level of charge) needed to stabilize the PNPs (i.e., maintain particle size during conversion from non-aqueous to aqueous medium) varies as PNP composition and properties are varied. It is believed that the PNP hydrophobicity, Tg, crosslinking level, and type of counter-ion from the neutralizing agent are important variables. For providing stable aqueous PNP dispersions (i.e., wherein flocculation of the PNPs is minimized), the polymerized ionic monomer units are preferably at least 20%, more preferably at least 50%, even more preferably at least 80%, and most preferably at least 90% neutralized.
- Neutralizing the PNPs is alternatively carried out in a variety of ways. In one method, the nonaqueous PNP dispersion is added to a solution containing the neutralizing agent while stirring. Preferably, the neutralizing agent is added as an aqueous solution over time while stirring the nonaqueous PNP dispersion to provide an at least partially neutralized nonaqueous PNP dispersion.
- In one method of preparing the aqueous polymeric composition containing dispersed PNPs, the at least partially neutralized nonaqueous PNP dispersion is combined with an aqueous medium. The aqueous medium optionally contains the neutralizing agent(s) for neutralizing the PNPs, in which case the nonaqueous PNP dispersion is capable of being simultaneously neutralized and combined with an aqueous medium. The aqueous medium optionally contains surfactants, which are capable of altering the stability of the PNPs, or of altering other properties of the resulting aqueous PNP dispersion, such as its surface tension.
- The sequence of admixing the partially neutralized nonaqueous PNP dispersion and the aqueous medium is not critical. Various methods and equipment, which are suitable for mixing are described in The Chemical Engineer's Handbook, 5th Edition, Perry and Chilton, Eds., McGraw-Hill, Ch. 21, 1973. Typically, the aqueous medium is continuously stirred while adding the partially neutralized nonaqueous PNP dispersion to it in order to ensure that the solvent is intimately mixed with the aqueous medium, which minimizes flocculation of the PNPs.
- Suitable weight percentages of the PNPs in the aqueous polymeric composition, based on total weight of the aqueous polymeric composition, are typically from 1 to 90 weight %, more typically from 2 to 75 weight %, even more typically from 4 to 65 weight %, further more typically from 8 to 55 weight %, and most typically from 10 to 45 weight %.
- While the preparation of the aqueous polymeric composition of the present invention does not require the use of surfactants, and it is typical that the nonaqueous PNP dispersions are substantially free of surfactants, surfactants are included in certain embodiments. When present, the amount of surfactants is typically less than 3 weight percent, more typically less than 2 weight percent, even more typically less than 1 weight percent, further typically less than 0.5 weight percent, and even further typically less than 0.2 weight percent, based on total weight of the PNPs.
- The aqueous polymeric composition is optionally treated to remove at least a portion of the solvent, and in certain embodiments, also water, to increase the solids content of the PNPs. Suitable methods to concentrate the PNPs include distillation processes, such as forming azeotropes of water and a suitable solvent; evaporation of solvent or water; drying the aqueous polymeric composition by freeze drying or spray drying; solvent extraction techniques; and ultrafiltration techniques. Preferably at least 25 weight %, more preferably at least 50 weight %, even more preferably at least 75 weight %, and most preferably 100 weight % of the solvent is exchanged with water. Removal of the solvent is preferably carried out under conditions that minimize destabilization (i.e., flocculation) of the PNPs.
- In an alternative method, the aqueous polymeric composition of this invention is prepared by a method including the steps of preparing a nonaqueous PNP dispersion containing the PNPs dispersed in at least one solvent that is both a suitable solvent for the PNPs and is compatible or miscible in water; and combining the nonaqueous PNP dispersion with an aqueous medium. Examples of such suitable solvents for acrylic-containing PNPs, which are also compatible or miscible with water, include isopropanol and ether alcohols (e.g., monobutyl ether of ethylene glycol and monoethyl ether of diethylene glycol). In this method, the PNPs do not require the addition of neutralizing agents to impart particle stability when combined with water.
- Alternative embodiments of the aqueous polymeric compositions of the present invention have a wide range of PNP content. Typically, the PNP weight fractions range from 0.1 to 99 weight %, more typically from 1 to 90 weight %, even more typically from 2 to 75 weight %, further typically from 5 to 50 weight %, and most typically from 10 to 40 weight %, based on the weight of the aqueous polymeric composition.
- The PNPs are present in the aqueous polymeric composition at a level of from 0.1 to 100 weight % PNPs, based on the total weight of the polymer particles in the aqueous polymeric composition. The functional role of the PNPs determines the level of PNPs present. Some of the functional roles of the PNPs are, for example, as additives, as co-binders, as principal binders, and as sole binders. A lower level of PNPs is utilized when the PNPs function as additives and co-binders, while a higher level of PNPs is utilized when the PNPs function as principal binders or sole binders.
- Certain embodiments of the aqueous polymeric compositions of the present invention further contain second particles that are not PNPs, and are second polymer particles, such as emulsion polymer particles, having a mean particle diameter of greater than 50 nm, or are pigment particles.
- In one embodiment, the second polymer particles are prepared in the presence of the PNPs. In this embodiment, the PNPs are present in the aqueous polymeric composition at a level of from 1 to 99 weight %, preferably from 5 to 90 weight %, more preferably from 10 to 60 weight %, and most preferably from 20 to 60 weight %, based on the total weight of polymer in the aqueous polymeric composition.
- The glass transition temperatures of the second polymer particles are typically in the range of from −60° C. to 120° C., depending upon the intended application of the aqueous polymeric composition containing the second polymer particles. Further, the second polymer particles typically have a mean diameter in the range of from greater than 50 nm up to 2 microns, preferably in the range of from 80 nm to 500 nm, and more preferably, in the range of from 100 nm to 350 nm. The second polymer particles are commonly supplied as aqueous dispersions.
- Examples of second polymer particles include polymer particles prepared by emulsion polymerization and include crosslinked and uncrosslinked polymer particles, polymer particles containing two or more polymer phases such as core-shell polymer particles, and polymer particles having one or more voids and vesiculated polymer particles as disclosed in U.S. Pat. No. 4,427,835; U.S. Pat. No. 4,920,160; U.S. Pat. No. 4,594,363; U.S. Pat. No. 4,469,825; U.S. Pat. No. 4,468,498; U.S. Pat. No. 4,880,842; U.S. Pat. No. 4,985,064; U.S. Pat. No. 5,157,084; U.S. Pat. No. 5,041,464; U.S. Pat. No. 5,036,109; U.S. Pat. No. 5,409,776; and U.S. Pat. No. 5,510,422.
- Specific examples of second polymer particles are acrylic copolymers, vinyl acetate copolymers, vinyl/acrylic copolymers, styrene/acrylic copolymers, polyurethanes, polyvinyl chlorides, ethylene/vinyl acetate copolymers, styrene/butadiene polymers, and mixtures thereof.
- Alternatively, the second particles are pigment particles. As used herein, pigment particles include inorganic particles such as pigments, extenders, or fillers; and organic colored pigments. Examples of pigment particles include zinc oxide, antimony oxide, zirconium oxide, chromium oxide, iron oxide, lead oxide, zinc sulfide, lithopone, titanium dioxide including anatase and rutile titanium dioxide, calcium carbonate, calcium sulfate, barium sulfate, mica, clay including delaminated clay, calcined clay, feldspar, nepheline syenite, bismuth vanadate; titanium nickel antimony oxide, cobalt oxides, wollastonite, diatomaceous earth, alumina silicates, carbon black, aluminum oxide, silica, talc, and mixtures thereof. The mean diameter of the pigment particles is typically in the range of from 5 nm to greater than 100 microns, preferably in the range of from 20 nm to 20 microns, and more preferably, in the range of from 50 nm to 10 microns.
- The aqueous polymeric composition containing PNPs according to the present invention is useful for treating porous materials including wood substrates. Wood substrates are characterized as having a surface containing pores as well as an internal porous structure. The PNPs enter into the wood pores and penetrate into the wood substrate. A method of treating the wood substrate includes the steps of applying the aqueous polymeric composition of this invention, which contains PNPs, onto a wood substrate; allowing the aqueous polymeric composition to penetrate or to be absorbed into the wood substrate; and drying or allowing to dry the applied aqueous polymeric composition. According to certain embodiments of the method, pressure is also applied to increase the penetration of the PNPs into the wood substrate. Treatment of the wood substrate with the aqueous polymeric composition provides increased protection against weathering caused by conditions such as exposure to moisture or sunlight. Treatment of the wood substrate with the aqueous polymeric composition also improves the aesthetic appearance of the wood substrate. Wood substrates which are capable of being so treated include timber such as, for example, cedar, pine, spruce, fir, redwood, hemlock, teak, oak, cherry, poplar, maple, and walnut; and processed timber, such as including, but not limited to, medium density fiber board, chip board, and laminates such as plywood.
- According to certain embodiments, the aqueous polymeric composition useful for treating wood substrates is provided as a blend further containing second polymer particles. Without wishing to be limited to a particular theory, the larger second polymer particles are believed to remain at or near the surface of the wood substrate, and to provide protection to the wood substrate surface. Preferably, these second polymer particles have a mean particle diameter in the range of from greater than 50 nm to 500 nm; and they have a glass transition temperature in the range of from 0° C. to 50° C.
- A volatile organic compound (“VOC”) is defined herein as a carbon containing compound that has a boiling point below 280° C. at atmospheric pressure. Compounds such as water and ammonia are excluded from the definition of VOC. The VOC level of a composition is the total amount of one or more volatile organic compounds contained in the composition.
- Frequently a VOC is deliberately added to a paint or a coating composition to improve film formation of the resulting coating or to aid in the application properties of the composition employed to prepare the coating. Examples of VOCs are glycol ethers, organic esters, aromatic compounds, ethylene and propylene glycols, and aliphatic hydrocarbons. Additionally, methods of paint or coating composition preparation frequently introduce adventitious VOCs from various ingredients such as the aqueous dispersion containing the PNPs, and from an optional component such as the aqueous dispersion containing second particles, biocides, soaps, dispersants, and thickeners. These typically account for less than 20 grams (g) VOC per liter of the aqueous polymeric composition. Steam stripping and choice of low VOC containing additives for those additives such as biocides, defoamers, soaps, dispersants, and thickeners, are some alternative methods commonly used to further reduce VOC content of the aqueous polymeric composition to less than 5 g VOC per liter of the aqueous polymeric composition.
- Preferably, the aqueous polymeric composition of this invention is a low VOC composition having a VOC level of less than 150 grams per liter (g/liter) of the aqueous polymeric composition; more preferably the aqueous polymeric composition has a VOC level of less than 100 g/liter of the aqueous polymeric composition; and even more preferably the aqueous polymeric composition has a VOC level of less than 50 g/liter of the aqueous polymeric composition.
- In certain embodiments, the aqueous polymeric composition contains hard PNPs having a glass transition temperature of at least 50° C. and soft second polymer particles having a glass transition temperature in the range of from −40° C. to 70° C. In dried coatings prepared from the aqueous polymeric composition of such embodiments, the hard PNPs provide one or more improved film properties, such as increased resistance to wear, improved block resistance, improved tint retention, increased elongation of the coating, improved impact resistance, improved adhesion, improved corrosion resistance, improved gloss retention and improved dirt pickup resistance, as compared to a comparative dried coating without the hard PNPs. In this embodiment, the ratio of the weight of the hard PNPs to the weight of the soft second polymer particles is in the range of from 1:99 to 1:1, preferably in the range of from 1:50 to 1:3, and most preferably in the range of from 1:20 to 1:4. Certain embodiments of the aqueous polymeric composition containing the hard PNPs and the soft second polymer particles are provided as a low VOC composition. Preferably, in such low VOC embodiments of the hard PNP-containing composition, the ratio of the weight of the PNPs to the weight of the second polymer particles is in the range of from 1:20 to 1:3 and more preferably in the range of from 1:9 to 1:5. Further, it is preferred that the hard PNPs have a glass transition temperature in the range of 50° C. to 100° C., and preferably in the range of from 60° C. to 80° C. A preferred range for the glass transition temperature of soft second polymer particle in the low VOC, hard PNP-containing compositions is from 0° C. to 15° C.
- In certain embodiments, the aqueous polymeric composition contains PNPs having first reactive groups. In such embodiments, the first reactive groups are self reactive to form chemical bonds. An example of PNPs having self reactive groups is PNPs containing, as polymerized units, methylol acrylamide.
- In certain other embodiments, the aqueous polymeric composition contains second polymer particles having second reactive groups. In this embodiment, the second reactive groups are self reactive to form chemical bonds. An example of second polymer particles having self reactive groups is second polymer particles containing, as polymerized units, methylol (meth)acrylamide.
- In still certain other embodiments, the aqueous polymeric composition contains PNPs having first reactive groups and second polymer particles having second reactive groups, wherein the first reactive groups and the second reactive groups are co-reactive to form chemical bonds. In this embodiment, the aqueous polymeric composition is applied onto a substrate; dried or allowed to dry; and the first reactive groups and the second reactive groups are reacted or allowed to react to form a dried crosslinked coating. Examples of complementary pairs of first and second reactive groups include, for example, isocyanates and isothiocyanates, which react with reactive groups selected from alcohols, amines, ureas, anhydrides, and mixtures thereof; aldehyde groups, which react with reactive groups selected from acetoacetoxy groups, amine groups, and mixtures thereof; acetoacetoxy groups, which react with reactive groups selected from aldehyde groups, amine groups, and mixtures thereof; epoxides, thioranes, and aziridines, all three of which react with reactive groups selected from alcohol groups, carboxylic acid groups, anhydride groups, amine groups, mercaptan groups, and mixtures thereof; carbodiimides, which react with reactive groups selected from carboxylic acid groups, phosphorus acid groups, alcohol groups, amine groups, mercaptan groups, and mixtures thereof; haloalkane and halomethylphenyl groups, both of which react with reactive groups selected from amine groups, carboxylic acid groups, and mixtures thereof; amines and thiols, both of which react with reactive groups selected from epoxide groups, aziridine groups, thiorane groups, acetoacetoxy groups, isocyanate groups, isothiocyanate groups, carbodiimide groupd, and mixtures thereof; and carboxylic acids, which react with reactive groups selected from epoxide groups, aziridine groups, thiorane groups, carbodiimide groups, and mixtures thereof. Alternatively, the first reactive groups and the second reactive groups are the same reactive functionality and are self reactive. Examples of suitable chemical bonds between the PNPs and the second polymer particles include the following types of linkages: esters, amides, ethers, urethanes, thiol ethers, amines, and ureidos. In certain embodiments, the reaction between the first reactive group and the second reactive group occurs during the drying step. Alternatively, in other embodiments, drying occurs any time prior to film formation, provided that the extent of reaction does not materially impair film formation. According to certain embodiments, the reaction of the first reactive group and the second reactive group is conducted in the presence of one or more catalysts. Alternatively, no catalyst is used. Techniques to determine the extent of reaction of the first reactive group and the second reactive group include infrared spectroscopy, nuclear magnetic resonance spectroscopy, and ultraviolet-visible spectroscopy.
- One method to prepare the PNP containing the first reactive group is an addition polymerization process that includes polymerization of at least one monomer containing a select reactive group, wherein the select reactive group is the first reactive group. Examples of monomers containing a select reactive group include ionic monomers, and isocyanate monomers, such as isocyanato ethyl methacrylate, dimethyl meta-isopropenyl benzyl isocyanate; acetoacetoxy monomers, such as acetoacetoxy ethyl(meth)acrylate; aldehyde monomers, such as acrolein and methacrolein; amine monomers, such as t-butyl aminoethyl(meth)acrylate, dimethyl aminoethyl(meth)acrylate, aminobutyl(meth)acrylate, aminoethyl(meth)acrylate; aminopropyl(meth)acrylate; and oxazolidinoethyl(meth)acrylate; epoxy monomers, such as glycidyl(meth)acrylate; carboxylic acid monomers, such as (meth)acrylic acid, itaconic acid, fumaric acid, maleic acid, α-acryloxypropionic acid, ethacrylic acid, α-chloroacrylic acid, α-vinylacrylic acid, crotonic acid, α-phenylacrylic acid, cinnamic acid, chlorocinnamic acid, and β-styrylacrylic acid; hydroxy containing monomers, such as hydroxyalkyl(meth)acrylates including 2-hydroxyethyl(meth)acrylate and 3-hydroxypropyl(meth)acrylate; halogenated monomers, such as bromopropyl(meth)acrylate; and halomethyl-styrene. A suitable process to prepare the second polymer particles having at least one second reactive group is addition polymerization of at least one monomer having a select reactive group, wherein the select reactive group is the second reactive group. Alternatively, either the first reactive group or the second reactive group is generated by functionalization of a precursor group after polymerization of the PNPs or the second polymer particle, respectively. Second polymer particles suitable for use in the present embodiment include particles having a single polymer phase and particles having two or more polymer phases, such as core-shell particles, acorn particles having an outer polymer phase partially encapsulating a core polymer phase, and particles having one polymer phase forming multiple domains on or within a second polymer phase.
- In yet other embodiments, the aqueous polymeric composition contains PNPs having first reactive groups and second polymer particles having second reactive groups, wherein the PNPs have a lower glass transition temperature than the second polymer particles. While not wanting to be bound by a particular theory, it is believed that the low Tg PNPs aid in the film formation of the second polymer particles and allow the aqueous polymeric composition to form a film with a lower amount of coalescent than a film formed from the second polymer particles in the absence of the PNPs. After film formation, the first and second reactive groups react to form crosslinks to provide the film with improved properties than a film absent the crosslinks. Preferably, the PNPs have a Tg in the range of from −10° C. to 15° C., and more preferably in the range of from 0° C. to 5° C. Preferably, the second polymer particles having second reactive groups have a Tg in the range of from 5° C. to 35° C., and more preferably in the range of from 15° C. to 25° C. The ratio of the weight of PNPs having first reactive group to the weight of second polymer particles having second reactive groups is in the range of from 1:100 to 1:3, preferably in the range of from 1:25 to 1:4; and more preferably, in the range of from 1:20 to 1:5. Certain embodiments of such aqueous polymeric compositions containing PNPs having first reactive groups and second polymer particles having second reactive groups, wherein the PNPs have a lower glass transition temperature than the second polymer particles, are provided as low VOC compositions.
- In yet still other certain embodiments of the present invention, the aqueous polymeric composition contains a ternary mixture of polymer particles having select particle sizes. The ternary mixture includes: a small mode of PNPs having a mean particle diameter in the range of from 10 nm to 20 nm; a medium mode of polymer particles having a mean particle diameter in the range of from 30 nm to 70 nm; and a large mode of second polymer particles having a mean particle diameter in the range of from 100 nm to 200 nm. Suitable medium mode polymer particles are PNPs having a mean diameter in the range of from 30 nm to 50 nm, second polymer particles having a mean diameter in the range of greater than 50 nm to 70 nm, and mixtures thereof. Preferably, the ternary mixture has a small mode of PNPs with a Tg in the range of from −10° C. to 5° C., and more preferably in the range of from −5° C. to 0° C. Preferably the ternary mixture has a medium mode of PNPs with a Tg in the range of from 0° C. to 15° C., and more preferably in the range of from 5° C. to 12° C. Preferably the ternary mixture has a large mode of second polymer particles with a Tg in the range of from 5° C. to 20° C., and more preferably in the range of from 10° C. to 15° C. The aqueous polymeric composition containing the ternary mixture of polymer particles is useful for preparing coatings having a balance of good film formation and acceptable film properties such as hardness, dirt pickup resistance, scrub resistance, block resistance, or gloss. Certain embodiments of aqueous polymeric compositions contains a ternary mixture of polymer particles having select particle sizes are provided as a low VOC composition.
- The total amount of pigment and second polymer particles having a Tg of at least 50° C. in the aqueous polymeric composition is defined according to the volume concentration of these components in the dried coating formed from the aqueous polymeric composition or equivalently, by the volume concentration of these components based on the total volume of solids in the aqueous polymeric composition. The percent total volume concentration of the pigment and second polymer particles having a Tg of at least 50° C., referred to herein as the “pigment volume concentration” or “PVC” is calculated by the following formula:
PVC(%)=100×[V 1 +V 2 ]/V T
wherein V1 is the volume of the pigment(s), V2 is the volume of second polymer particles with a Tg of at least 50° C., and VT is the volume solids of the aqueous polymeric composition. The aqueous polymeric composition of this invention includes compositions having pigment volume concentrations in the range of from 0 to 95% and thereby encompasses coating compositions sometimes described in the art as clear coatings, stains, flat coatings, satin coatings, semi-gloss coatings, gloss coatings, primers, textured coatings, paper coatings, and the like. - One method to prepare the aqueous polymeric composition of this invention, which contains pigment particles, is by admixing the aqueous polymeric composition containing the PNPs and an aqueous slurry containing dispersed pigment particles. Mixing is typically employed to minimize localized concentrations of either the PNPs or the pigment particles. Alternatively, the pigmented aqueous polymeric composition of this invention is prepared by admixing dry pigment particles into the aqueous polymeric composition containing PNPs to disperse the pigment particles into the aqueous medium. Typically, high shear mixing is employed to disperse the dried pigment particles. In certain embodiments, dispersants are added to aid in dispersing or stabilizing the pigment particles in the aqueous medium of the aqueous polymeric composition.
- In certain other embodiments, the aqueous polymeric composition of this invention further contains one of pigment particles, second polymer particles having a Tg of at least 50° C., and mixtures thereof. This aqueous polymeric composition has a PVC of at least 70%, preferably of at least 75%, and more preferably at least 80%. The aqueous polymeric composition of this embodiment is useful as a coating composition suitable for preparing opaque dried coatings, such as a dried flat paint or a dried paper coating. The PNPs contained in this aqueous polymeric composition have a Tg in the range of from −20° C. to 40° C., preferably in the range of from −10° C. to 30° C., and more preferably in the range of from −5° C. to 25° C. The aqueous polymeric composition of this embodiment, which is suitable as a paint or a paper coating composition, typically contains one or more of titanium dioxide, calcium carbonate, and clay, as the pigment particle. Certain other embodiments also still further contain solid bead polymer particles or polymer particles having one or more voids, as the second polymer particles, with a Tg of at least 50° C.
- In yet still certain other embodiments, the aqueous polymeric composition contains PNPs and second polymer particles, wherein the second polymer particles are prepared in the presence of the PNPs. In this embodiment, the PNPs are present in the aqueous polymeric composition at a level of from 1 to 99 weight %, preferably from 5 to 90 weight %, more preferably from 10 to 60 weight %, and most preferably from 20 to 60 weight %, based on the total weight of polymer in the aqueous polymeric composition. Preferably, the second polymer particles are polymerized by aqueous emulsion polymerization. In this process, the PNPs are added to an aqueous reaction medium prior to or during the polymerization of the second polymer particles. The PNPs of the present embodiment are believed to act as stabilizers (i.e., dispersants) in the aqueous emulsion polymerization process, such as according to methods which use “high acid” polymeric stabilizers (often referred to as “resin supported emulsion polymerization”, see for example U.S. Pat. No. 4,845,149 and U.S. Pat. No. 6,020,061). Among suitable emulsion polymer compositions, any emulsion polymer, copolymer, multi-stage copolymer, interpolymer, core-shell polymer, and the like can be stabilized using the PNPs of the present invention. Preferred second polymer particles include, as polymerized units, at least one (meth)acrylic ester monomer.
- According to certain embodiments, the emulsion polymerization process performed in the presence of the PNPs, further includes synthesis adjuvants, such as surfactants, initiators, and buffers. The resulting aqueous polymeric composition prepared by this process contains PNPs on the second polymer particle surface as well as PNPs dispersed in the aqueous phase. The aqueous polymeric composition of this embodiment is useful for preparing coatings having improved properties, such as, gloss. Also, the aqueous polymeric composition containing such PNP stabilized second polymer particles, displays enhanced colloidal stability relative to analogous blends of PNPs and second polymer particles that are prepared in the absence of PNPs.
- One aspect of the present invention is directed towards a method of preparing a coating from the aqueous polymeric composition containing the PNPs. The method includes the steps of applying the aqueous polymeric composition onto a substrate; and drying or allowing to dry the applied aqueous polymeric composition to provide the coating. The aqueous polymeric composition is typically applied onto a substrate to prepare a dry coating. Suitable techniques for applying the aqueous polymeric composition onto a substrate include brushing, rolling, drawdown, dipping, with a knife or trowel, curtain coating, and spraying methods such as, for example, air-atomized spray, air-assisted spray, airless spray, high volume low pressure spray, and air-assisted airless spray. The wet coating thickness of the applied aqueous polymeric composition is commonly in the range of 1 micron to 5 millimeters. The aqueous polymeric composition is applied onto a substrate as a single coat and alternatively multiple coats. The applied aqueous polymeric composition is typically allowed to dry at ambient conditions and alternatively dried by the application of heat to provide a dry coating. Drying is typically allowed to proceed under ambient conditions such as, for example, at 0° C. to 35° C. The method is useful for providing coatings that have at least one improved property compared to a comparative coating prepared in the absence of the PNPs. Examples of improved properties include block resistance, print resistance, mar resistance, scrub resistance, abrasion resistance, burnish resistance, dirt pickup resistance, adhesion, gloss, flexibility, toughness, impact resistance, reduced coalescent demand, water resistance, chemical resistance, biological fouling resistance, and stain resistance.
- In a pigmented coating, pigment particles are dispersed within a polymeric film to provide opacity or hiding. The opacity of the pigmented coating arises from the scattering of light, which results from differences in the refractive indices of the polymeric film and the pigment particles contained within. The pigment particles typically have a refractive index of 1.8 or greater. Refractive indices for polymers are typically in the range of 1.4 to 1.6. In one embodiment, the improved coating is a pigmented coating that is prepared from an aqueous polymeric composition containing PNPs, second polymer particles, and pigment particles. The improved pigmented coating has a polymeric film that is formed from the second polymer particles and the PNPs. The polymeric film of the improved pigmented coating has a lower refractive index than a film formed absent the PNPs and thus has a greater difference in the refractive indices of the polymeric film and the pigment contained within. The improved pigmented coating provides increased hiding compared to a pigmented coating absent the PNPs. The polymer film of the improved pigmented coating typically contains from 2 to 30 weight % PNPs, based on the total weight of the polymeric film.
- Yet still other certain embodiments of the aqueous polymeric composition include one or more other components, such as, without limitation, other polymers, surfactants, other pigments, other extenders, dyes, pearlescents, adhesion promoters, crosslinkers, dispersants, defoamers, leveling agents, optical brighteners, ultraviolet stabilizers, absorbing pigments, coalescents, rheology modifiers, preservatives, biocides, and antioxidants.
- The following examples are presented to illustrate the composition and the process of the invention. These examples are intended to aid those skilled in the art in understanding the present invention. The present invention is, however, in no way limited thereby.
- An aqueous polymeric composition is prepared by admixing an aqueous dispersion containing PNPs with an aqueous dispersion containing second polymer particles. The PNPs contain, as polymerized units, 60 weight % methyl methacrylate, 30 weight % acrylic acid, and 10 weight % trimethylolpropane triacrylate. The PNPs have a Tg above 50° C. and a mean particle diameter of 12 nm. The aqueous dispersion containing the PNPs is provided at pH=8 with ammonia. The second polymer particles are acrylic copolymer particles having a Tg of 3° C. and a mean particle diameter of 155 nm. The aqueous polymeric composition, Example 1.1, contains 15 weight % PNPs and 85 weight % second polymer particles, and has a total polymer solids content of 33 weight %.
- A pigmented aqueous polymeric composition and a comparative composition are prepared by combining the ingredients in Table 2.1 in the order listed.
Ingredient Example 1.2 Comparative A titanium dioxide dispersion 344.07 g 344.07 g (77 weight %) Water 20.00 g 20.00 g propylene glycol 16.50 g 16.50 g Example 1.1 (33 weight % 537.65 g — solids) Aqueous dispersion of second — 537.65 g polymer particles (33 weight % solids) surfactant 1.00 g 1.00 g ammonia (28%) 0.70 g 0.70 g Acrysol ™ RM-2020 NPR 29.00 g 29.00 g rheology modifier (Rohm and Haas Co.) Acrysol ™ RM-8W rheology 5.60 g 5.60 g modifier (Rohm and Haas Co.) Water 104.2 g 113.62 g VOC (weight %) <2.25 <2.25 - Dry coating samples are prepared from the pigmented aqueous polymeric composition, Example 1.2, and the comparative composition, Comparative A, and are evaluated according to the procedure for the scrub resistance test. The two compositions are applied in such a way that the two compositions are placed side by side and drawn together by a single drawing with a 0.0762 mm (3 mil) film applicator 152.4 mm (6 inch) in width. Each composition forms a 7.5 cm (3 inch) wide coating on a single vinyl chart, and the two compositions have the same coating thickness. The samples are allowed to dry at 23° C. and 50% relative humidity for 7 days. Abrasive scrub resistance is measured with a scrub machine using 10 g scrub medium and 5 ml water. A piece of 0.0254 mm (1 mil) thick and 76.2 mm wide vinyl shim is placed underneath the sample vinyl chart. The two side edges of the shim are in the center of each coating. The number of cycles required to completely cut through each coating is recorded.
- The coating prepared from the pigmented aqueous polymeric composition of Example 1.2 requires 750 cycles to cut through the coating. In contrast, the coating prepared from the pigment comparative composition of Comparative A requires 360 cycles to cut through the coating. The results show that the aqueous polymeric composition of this invention is useful for preparing coatings with improved scrub resistance.
- PNPs are prepared containing, as polymerized units, 35 weight % methyl methacrylate, 35 weight % butyl acrylate, 20 weight % acrylic acid, and 10 weight % trimethylolpropane triacrylate. The PNPs are prepared according to the following process: A 5-liter reactor is fitted with a thermocouple, a temperature controller, a purge gas inlet, a water-cooled reflux condenser with purge gas outlet, a stirrer, and a monomer feed line. To a first additional vessel, 450.0 g of a monomer mixture (A) is prepared by admixing 157.5 g methyl methacrylate, 157.5 g butyl acrylate, 90.0 g acrylic acid, and 45.0 g trimethylolpropane triacrylate. To a second additional vessel, an initiator mix (B) is prepared by admixing 18.00 g of a 75% solution of t-amyl peroxypivalate in mineral spirits and 112.50 g isopropyl alcohol. A charge of 2325 g isopropyl alcohol is added to the reactor. Nitrogen gas is flowed through the reactor for approximately 30 minutes. Next, the contents of the reactor are heated to 79° C. while maintaining the flow of nitrogen gas. Next, a dual feed of the monomer mixture (A) and the initiator mix (B) are added to the reactor. The two mixtures are feed uniformly using feed pumps over an addition period of 120 minutes. At the end of the monomer and initiator feeds, the contents of the reactor are maintained at 79° C. for 30 minutes. Next, the first of three additional initiator charges, each containing 9.00 g of a 75% solution of t-amyl peroxypivalate in mineral spirits, and 22.50 g isopropyl alcohol, is added. A second initiator charge is added 30 minutes after the first initiator charge addition. Similarly, the final initiator charge is added 30 minutes after the second initiator charge addition. The contents of the reactor are then held at a temperature of 79° C. for a period of 150 minutes. Next, contents of the reactor are neutralized with a mixture of 42.5 g of aqueous ammonia (28% active) and 450.0 g water. Solvent is removed from the contents of the reactor by using a roto-evaporator at 35° C. and at reduced pressure. Next, water is added to dilute the concentration of the resulting PNPs to 25.6 weight %. The resulting aqueous polymeric composition, Example 2.1, contains PNPs with a mean particle diameter of 5 nm and has a pH of 8.5.
- PNPs containing, as polymerized units, 35 weight % methyl methacrylate, 35 weight % butyl acrylate, 20 weight % acrylic acid, and 10 weight % trimethylolpropane triacrylate are prepared according to the general procedure for preparing Example 2.1. The resulting aqueous polymeric composition contains PNPs having a mean particle diameter of 5 nm and has a solids level of 25 weight %.
- Preparation of Second Polymer Particles in the Presence of PNPs Second polymer particles are prepared by emulsion polymerization in the presence of PNPs. The reaction vessel is a 2-liter, 4 neck round bottom flask equipped with a side arm, condenser, stirrer, and thermocouple.
- To the flask, 342 g of the aqueous polymeric composition of Example 2.1 is added. The contents of the flask is heated to 85° C. under a nitrogen atmosphere. Next, a monomer mixture containing 175.0 g butyl acrylate and 175.0 g methyl methacrylate is added over a 1.5 hour period, while coadding a separate solution of 2.63 g ammonium persulfate in 100.0 g deionized water and 0.22 g of 28% ammonium hydroxide over a 2 hour time period. After the addition of the monomer mixture is complete, the persulfate containing cofeed is continued for 30 minutes. Next, the contents of the flask is maintained at a temperature of 85° C. for 60 minutes. The contents of the flask is allowed to cool to 25° C. and is filtered through a 100/325 mesh set of stacked screens, yielding a negligible quantity of coagulated polymer. The resulting filtered emulsion polymerization product, an aqueous polymeric composition containing PNPs and second polymer particles, has a total polymer solids content of 55.04%, a pH of 7.5, second polymer particles with a mean diameter of 128 nm, and a viscosity of 1.09 pascal second. The aqueous polymeric composition of Example 3.1 contains 20 weight % PNP and 80 weight % second polymer particles, based on the total weight of polymer.
- Second polymer particles are prepared in the presence of PNPs according to the general procedure for Example 3.1. The resulting aqueous polymeric composition of Example 3.2 contains 50 weight % PNPs of Example 3.1 and 50 weight % second polymer particles containing, as polymerized units, 65 weight % butyl acrylate and 35 weight % methacrylic acid, based on the total weight of polymer.
Claims (12)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/461,954 US7091275B1 (en) | 2002-06-14 | 2003-06-13 | Aqueous polymeric composition containing polymeric nanoparticles and treatments prepared therefrom |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US38904302P | 2002-06-14 | 2002-06-14 | |
US41458902P | 2002-09-30 | 2002-09-30 | |
US10/461,954 US7091275B1 (en) | 2002-06-14 | 2003-06-13 | Aqueous polymeric composition containing polymeric nanoparticles and treatments prepared therefrom |
Publications (2)
Publication Number | Publication Date |
---|---|
US7091275B1 US7091275B1 (en) | 2006-08-15 |
US20060189748A1 true US20060189748A1 (en) | 2006-08-24 |
Family
ID=36781717
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/461,954 Expired - Fee Related US7091275B1 (en) | 2002-06-14 | 2003-06-13 | Aqueous polymeric composition containing polymeric nanoparticles and treatments prepared therefrom |
Country Status (1)
Country | Link |
---|---|
US (1) | US7091275B1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040063867A1 (en) * | 2002-09-30 | 2004-04-01 | Cruz Carlos Alfonso | Plastic composition |
WO2008054922A1 (en) * | 2006-10-30 | 2008-05-08 | Genovique Specialties Holdings Corporation | Aqueous film-forming compositions containing reduced levels of volatile organic compounds |
US20080182929A1 (en) * | 2006-10-30 | 2008-07-31 | Velsicol Chemical Corporation | Aqueous Coating Compositions Exhibiting Increased Open Time With Reduced Levels Of Volatile Organic Compounds |
US9983327B2 (en) * | 2012-10-26 | 2018-05-29 | Board Of Regents, The University Of Texas System | Polymer coated nanoparticles |
WO2019152577A1 (en) * | 2018-01-31 | 2019-08-08 | Precision Fabrics Group, Inc. | Porous polymer coatings |
US10563068B2 (en) | 2013-10-31 | 2020-02-18 | Precision Fabrics Group, Inc. | Porous polymer coatings |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100810947B1 (en) * | 2005-01-28 | 2008-03-10 | 롬 앤드 하아스 컴패니 | Medical films and articles prepared from emulsion polymers |
US7538151B2 (en) | 2005-08-22 | 2009-05-26 | Rohm And Haas Company | Coating compositions and methods of coating substrates |
US8288453B2 (en) * | 2008-06-26 | 2012-10-16 | Ccp Composites Us | Process to disperse organic microparticles/nanoparticles into non-aqueous resin medium |
DE102009003281A1 (en) | 2009-05-20 | 2010-11-25 | Wacker Chemie Ag | Use of polymeric nanoparticles e.g. in the form of aqueous dispersion, in construction adhesive i.e. tile adhesive, where the nanoparticle is obtained by radically initiated microemulsion polymerization of ethylenically unsaturated monomer |
US8143348B2 (en) * | 2009-09-01 | 2012-03-27 | Ppg Industries Ohio, Inc. | Waterborne coating compositions, related methods and coated substrates |
US8461253B2 (en) * | 2010-01-15 | 2013-06-11 | Ppg Industries Ohio, Inc. | One-component, ambient curable waterborne coating compositions, related methods and coated substrates |
US8999361B2 (en) * | 2011-10-25 | 2015-04-07 | Jack L. Mathis | Silane modified diatomaceous earth mechanical insecticide |
KR101947421B1 (en) * | 2014-10-20 | 2019-02-14 | (주)엘지하우시스 | Aqueous composition for coating a surface and a seat cover for automobile applied the same |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4560714A (en) * | 1982-12-16 | 1985-12-24 | Celanese Corporation | Water-swellable crosslinked polymeric microgel particles and aqueous dispersions of organic film-forming resins containing the same |
US5212273A (en) * | 1991-06-20 | 1993-05-18 | Ppg Industries, Inc. | Crosslinked polymeric microparticles; their method of preparation and use in coating compositions |
US5536628A (en) * | 1994-12-08 | 1996-07-16 | Eastman Kodak Company | Aqueous coating compositions containing dye-impregnated polymers |
US5539073A (en) * | 1995-04-12 | 1996-07-23 | Eastman Chemical Company | Waterborne polymers having pendant allyl groups |
US5712339A (en) * | 1995-04-05 | 1998-01-27 | Sartomer Company | Aqueous polymer dispersions |
US5863996A (en) * | 1980-12-30 | 1999-01-26 | National Research Development Corporation | Solution polymerization to form sol of crosslinked particles |
US5910359A (en) * | 1995-10-04 | 1999-06-08 | Fuji Photo Film Co., Ltd. | Recording sheet and image forming method |
US6028155A (en) * | 1997-05-21 | 2000-02-22 | Eastman Chemical Company | Surfactant-containing acetoacetoxy-functional and enamine-functional polymers |
US6130014A (en) * | 1999-07-15 | 2000-10-10 | Eastman Kodak Company | Overcoat material as protecting layer for image recording materials |
US6268222B1 (en) * | 1998-01-22 | 2001-07-31 | Luminex Corporation | Microparticles attached to nanoparticles labeled with flourescent dye |
US6329446B1 (en) * | 1997-06-05 | 2001-12-11 | Xerox Corporation | Ink composition |
US20020065208A1 (en) * | 2000-08-25 | 2002-05-30 | Eric Aubay | Composition based on nanoparticles or a nanolatex of polymers for fabric care |
US20030059599A1 (en) * | 2001-03-30 | 2003-03-27 | Beckley Ronald Scott | Coating and coating composition |
US6646041B2 (en) * | 2001-09-25 | 2003-11-11 | Imperial Chemical Industries Plc | Aqueous dispersion of addition polymer particles |
US20030232914A1 (en) * | 2002-06-14 | 2003-12-18 | Wayne Devonport | Aqueous composition containing polymeric nanoparticles |
US20030232918A1 (en) * | 2002-06-14 | 2003-12-18 | Amick David Richard | Aqueous nanaoparticle dispersions |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2691969B1 (en) | 1992-06-04 | 1994-09-23 | Prolabo Sa | Nanoparticles of functionalized polymers, their preparation process and their use. |
US6465556B1 (en) | 1997-07-01 | 2002-10-15 | Rhodia Inc. | Latex made with crosslinkable surface active agent |
FR2791689B1 (en) | 1999-03-31 | 2001-06-08 | Cray Valley Sa | CROSSLINKED MICROPARTICLES, PROCESS FOR THEIR PREPARATION AND APPLICATIONS |
DE19961277A1 (en) | 1999-12-18 | 2001-06-21 | Cognis Deutschland Gmbh | Use of nanoscale polymers |
CA2309575A1 (en) | 2000-05-26 | 2001-11-26 | James E. Guillet | Internally cross-linked macromolecules |
GB0023514D0 (en) * | 2000-09-26 | 2000-11-08 | Ici Plc | Aqueous dispersion of addition polymer particles |
-
2003
- 2003-06-13 US US10/461,954 patent/US7091275B1/en not_active Expired - Fee Related
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5863996A (en) * | 1980-12-30 | 1999-01-26 | National Research Development Corporation | Solution polymerization to form sol of crosslinked particles |
US4560714A (en) * | 1982-12-16 | 1985-12-24 | Celanese Corporation | Water-swellable crosslinked polymeric microgel particles and aqueous dispersions of organic film-forming resins containing the same |
US5212273A (en) * | 1991-06-20 | 1993-05-18 | Ppg Industries, Inc. | Crosslinked polymeric microparticles; their method of preparation and use in coating compositions |
US5536628A (en) * | 1994-12-08 | 1996-07-16 | Eastman Kodak Company | Aqueous coating compositions containing dye-impregnated polymers |
US5712339A (en) * | 1995-04-05 | 1998-01-27 | Sartomer Company | Aqueous polymer dispersions |
US5539073A (en) * | 1995-04-12 | 1996-07-23 | Eastman Chemical Company | Waterborne polymers having pendant allyl groups |
US5910359A (en) * | 1995-10-04 | 1999-06-08 | Fuji Photo Film Co., Ltd. | Recording sheet and image forming method |
US6028155A (en) * | 1997-05-21 | 2000-02-22 | Eastman Chemical Company | Surfactant-containing acetoacetoxy-functional and enamine-functional polymers |
US6329446B1 (en) * | 1997-06-05 | 2001-12-11 | Xerox Corporation | Ink composition |
US6268222B1 (en) * | 1998-01-22 | 2001-07-31 | Luminex Corporation | Microparticles attached to nanoparticles labeled with flourescent dye |
US6130014A (en) * | 1999-07-15 | 2000-10-10 | Eastman Kodak Company | Overcoat material as protecting layer for image recording materials |
US20020065208A1 (en) * | 2000-08-25 | 2002-05-30 | Eric Aubay | Composition based on nanoparticles or a nanolatex of polymers for fabric care |
US20030059599A1 (en) * | 2001-03-30 | 2003-03-27 | Beckley Ronald Scott | Coating and coating composition |
US6646041B2 (en) * | 2001-09-25 | 2003-11-11 | Imperial Chemical Industries Plc | Aqueous dispersion of addition polymer particles |
US20030232914A1 (en) * | 2002-06-14 | 2003-12-18 | Wayne Devonport | Aqueous composition containing polymeric nanoparticles |
US20030232918A1 (en) * | 2002-06-14 | 2003-12-18 | Amick David Richard | Aqueous nanaoparticle dispersions |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040063867A1 (en) * | 2002-09-30 | 2004-04-01 | Cruz Carlos Alfonso | Plastic composition |
WO2008054922A1 (en) * | 2006-10-30 | 2008-05-08 | Genovique Specialties Holdings Corporation | Aqueous film-forming compositions containing reduced levels of volatile organic compounds |
US20080182929A1 (en) * | 2006-10-30 | 2008-07-31 | Velsicol Chemical Corporation | Aqueous Coating Compositions Exhibiting Increased Open Time With Reduced Levels Of Volatile Organic Compounds |
US9983327B2 (en) * | 2012-10-26 | 2018-05-29 | Board Of Regents, The University Of Texas System | Polymer coated nanoparticles |
US10563068B2 (en) | 2013-10-31 | 2020-02-18 | Precision Fabrics Group, Inc. | Porous polymer coatings |
WO2019152577A1 (en) * | 2018-01-31 | 2019-08-08 | Precision Fabrics Group, Inc. | Porous polymer coatings |
Also Published As
Publication number | Publication date |
---|---|
US7091275B1 (en) | 2006-08-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7071261B2 (en) | Aqueous composition containing polymeric nanoparticles | |
EP1371685A2 (en) | Aqueous polymeric composition containing polymeric nanoparticles and treatments prepared therefrom | |
US7091275B1 (en) | Aqueous polymeric composition containing polymeric nanoparticles and treatments prepared therefrom | |
AU2003243988B2 (en) | Polymer particles having select pendant groups and composition prepared therefrom | |
AU2005277927B2 (en) | Exterior paint formulation | |
EP1273636A2 (en) | Coating with improved hiding compositions prepared therewith, and processes for the preparation thereof | |
US7138438B2 (en) | Polymeric nanoparticle formulations and their use for improving the dirt pick up resistance of a coating | |
US20040063831A1 (en) | Polymeric nanoparticle and bioactive coating formulations | |
JP2002502442A (en) | Surfactant-containing acetoacetoxy-functional and enamine-functional polymers | |
US20120142850A1 (en) | Organic-inorganic composite particles | |
EP1511816B2 (en) | Coating composition having polyvinyl chloride extender particles | |
US20230075015A1 (en) | Latex polymer with improved washability and block resistance | |
EP1371694B1 (en) | Polymeric nanoparticle formulations and their use for improving the dirt pick up resistance of a coating | |
KR0163760B1 (en) | Cationic latex paint compositions | |
JP4167945B2 (en) | Polymer nanoparticles and bioactive coating formulations | |
EP1371690A2 (en) | Polymeric nanoparticle formulations and their use in microbe repellent coatings | |
EP3289030B1 (en) | Low sheen paint composition with effective opacity | |
CN1498929A (en) | Polymer nano particle formulation and its use in protecting paint for microbion |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ROHM AND HAAS COMPANY, PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:AMICK, DAVID RICHARD;DEVONPORT, WAYNE;VAN DYK, ANTONY KEITH;AND OTHERS;REEL/FRAME:017803/0643;SIGNING DATES FROM 20030303 TO 20030331 |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FEPP | Fee payment procedure |
Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.) |
|
LAPS | Lapse for failure to pay maintenance fees |
Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20180815 |