CN102015796B - 可溶于水和可溶于溶剂的非离子的添加剂 - Google Patents
可溶于水和可溶于溶剂的非离子的添加剂 Download PDFInfo
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- CN102015796B CN102015796B CN200980115977.5A CN200980115977A CN102015796B CN 102015796 B CN102015796 B CN 102015796B CN 200980115977 A CN200980115977 A CN 200980115977A CN 102015796 B CN102015796 B CN 102015796B
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- multipolymer
- alkyl
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 14
- 239000002904 solvent Substances 0.000 title description 11
- 239000000654 additive Substances 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 64
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- -1 oxypropylene unit Chemical group 0.000 claims description 43
- 239000006185 dispersion Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000000049 pigment Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- ILZXXGLGJZQLTR-UHFFFAOYSA-N 2-phenylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=CC=C1 ILZXXGLGJZQLTR-UHFFFAOYSA-N 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 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 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001421 myristyl 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])[H] 0.000 claims 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 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 125000002947 alkylene group Chemical group 0.000 abstract 3
- 238000002360 preparation method Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical class CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- RZBBHEJLECUBJT-UHFFFAOYSA-N 6-methylheptyl 2-sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS RZBBHEJLECUBJT-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical class CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- 239000003960 organic solvent Substances 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
Description
技术领域
本发明涉及作为水基和溶剂基颜料制剂的分散剂用的新型非离子共聚物,以及生产这些共聚物的方法。
背景技术
对于在液体介质中分散颜料而言一般需要分散剂。通过适当的表面活性剂(又称润湿剂)辅助的分散剂,作为表面活性剂促进润湿待分散的颜料,并且在生产颜料分散体时使得团聚物和附聚物的破碎变得容易,这种破碎通常借助于碾磨操作而实现。分散剂可以是阴离子、阳离子、两性或中性结构的。它们可以是低分子量性质的,或者表示由无规的、交替的、嵌段的、梳状或星型排布结构的聚合的单体组成的高分子聚合物。例如对于在制造颜料浓缩物过程中颜料的分散而言,分散剂具有特别的商业意义,所述颜料浓缩物用于分散色料和清漆色料(Lackfarben)、刷涂剂、涂料和印刷油墨的着色,以及用于纸张、纸板和织物的着色。近来,在寻找这样的分散剂和添加剂,其在液体分散体的干燥工艺之后,确保干燥的粉末或颗粒在施用介质中快速溶解。梳形聚合物在此处可能是有用的。梳形聚合物通常使用基于单(甲基)丙烯酸酯作为共聚单体的大分子单体来制备,并且它们不同于其它聚合物分散剂之处在于它们具有明显有序的结构,因为疏水性和亲水性或者极性可以分配在主链和侧链上。
EP 1 293 523描述了一种分散剂,其为具有约5000到100 000的重均分子量且包含20重量%到80重量%的亲水骨架和80重量%到20重量%的大分子单体侧链的聚合物。基于骨架的重量计,该骨架有多达70重量%到98重量%由不含羧基的聚合的烯属不饱和单体,以及有2重量%到30重量%由带有羧基的聚合的烯属不饱和单体组成,其中将至少10%的羧基用胺或无机碱中和。骨架与侧链相比具有亲水性质。侧链由聚合的烯属不饱和单体的大分子单体组成。
EP 1 081 169描述了衍生自以下单体混合物的支化聚合物:
(A)50重量%到93重量%的至少一种烯属不饱和单体,
(B)2重量%到25重量%的至少一种分子量为1000到20000的烯属不饱和大分子单体,以及
(C)5重量%到25重量%的至少一种可聚合的咪唑衍生物。
EP 1 562 696描述了在水性乳液聚合中使用由聚亚烷基二醇-单(甲基)丙烯酸酯组成的大分子单体而合成制备的聚合物分散剂。该聚合物的主链必须包含具有至少一个氨基的烯属不饱和单体。
DE 10 2005 019 384描述了由烯属不饱和单体如(甲基)丙烯酸烷基酯和(甲基)丙烯酸芳基酯与纯的聚乙二醇-单(甲基)丙烯酸酯结合而合成的并用作分散剂的梳形聚合物。
EP 1 323 789描述了包含聚氧化亚烷基-单(甲基)丙烯酸酯单元,但是是非水溶性的梳形聚合物。其目标是提供水性油墨。EP 1 491 598类似地包含聚氧化亚烷基-单(甲基)丙烯酸酯单元和成盐单体;该聚合物用于水性油墨。
发明内容
现在已经令人惊奇地发现,借助于由聚乙二醇/聚丙二醇-单(甲基)丙烯酸酯构成的大分子单体制备的特定非离子的梳形共聚物达到了上述目标,即通用的可分散性。
本发明的主题因此在于可通过单体(A)、(B)、(C)和(D)的聚合而获得的共聚物,其中
(A)是式(I)的单体
其中
A表示C2-至C4-亚烷基,和
B表示不同于A的C2-至C4-亚烷基,
R表示氢或甲基,
m为从1到500,优选1到50的数值;
n为从1到500,优选1到50的数值,
其中m+n的总和为从2到1000;
(B)是式(II)的单体
其中
D表示C3-亚烷基和
R表示氢或甲基,
o为从2到500,优选2到100,特别是2到50,特别优选5到25的数值;
(C)是包含芳基的烯属不饱和单体;以及
(D)是包含烷基的烯属不饱和单体。
本发明的共聚物具有通过自由基聚合反应的引发或通过链转移反应或通过链终止反应而形成的通常末端的基团,例如质子、来自自由基引发剂的基团或来自链转移试剂的含硫基团。
单体的摩尔比例优选为对于单体(A)0.1到90%,对于单体(B)0.1到90%,对于单体(C)0.1到90%以及对于单体(D)0.1到90%,摩尔比例的总和为100%。
单体的摩尔比例特别优选的是对于单体(A)0.1到70%,对于单体(B)10到80%,对于单体(C)0.1到50%以及对于单体(D)0.1到50%。
单体(A)的氧化亚烷基单元(A-O)m和(B-O)n可以无规地排布或在优选实施方案情况中以嵌段方式排布存在。
在一个优选具体实施方案中,(A-O)m表示氧化亚丙基单元和(B-O)n表示氧化亚乙基单元,或者(A-O)m表示氧化亚乙基单元和(B-O)n表示氧化亚丙基单元,其中氧化亚乙基单元的摩尔比例基于氧化亚乙基单元和氧化亚丙基单元的总和(100%)计优选为50到98%,更优选60到95%以及特别优选70到95%。
氧化亚烷基单元的总和原则上可以为n+m=2到1000,优选2到500,特别是2到100以及特别优选5到50。
优选的单体(C)可由式(IIIa)或(IIIb)来描述:
其中
Xa表示具有3到30个碳原子的芳香族或芳脂族基团,其任选包含一个或多个例如1、2或3个杂原子N、O和S,
Za表示H或(C1-C4)-烷基,
Zb表示H或(C1-C4)-烷基,以及
Zc表示H或(C1-C4)-烷基;
其中
R1表示氢或甲基,
Xb表示具有3到30个碳原子的芳香族或芳脂族基团,其任选包含一个或多个例如1、2或3个杂原子N、O和S,
Wa表示氧或NH基团。
单体(C)包括例如丙烯酸和甲基丙烯酸的以下酯和酰胺:苯基、苄基、甲苯基、2-苯氧基乙基、苯乙基。
其他的单体(C)是乙烯基芳族单体如苯乙烯及其衍生物如乙烯基甲苯、α-甲基苯乙烯。该芳香族单元还可以涉及杂芳族化合物,例如在1-乙烯基咪唑中的。
特别优选的单体(C)可以是:苯乙烯、1-乙烯基咪唑、甲基丙烯酸苄基酯、甲基丙烯酸2-苯氧基乙酯和甲基丙烯酸苯乙酯。
优选的单体(D)可由式(IV)描述:
其中
R2表示氢或甲基,
Y表示具有1到30个碳原子,优选6到30,特别是9到20个碳原子的脂肪族烃基,其可以是线型或支化的或者环状的,以及其可包含杂原子O、N和/或S且还可以是不饱和的,
Wb表示氧或NH基团。
单体(D)包括例如丙烯酸和甲基丙烯酸的以下酯和酰胺:甲基-、乙基-、丙基-、异丙基-、正丁基-、异丁基-、叔丁基-、戊基-、己基-、2-乙基己基-、3,3-二甲基丁基-、庚基-、辛基-、异辛基-、壬基-、月桂基-、十六烷基-、十八烷基-、二十二烷基-、环己基-、三甲基环己基-、叔丁基环己基-、冰片基-、异冰片基-、金刚烷基-、(2,2-二甲基-1-甲基)丙基-、环戊基-、4-乙基-环己基-、2-乙氧基乙基-、四氢糠基-以及四氢吡喃基。
优选的单体(D)是丙烯酸和甲基丙烯酸的以下烷基酯或烷基酰胺:甲基-、乙基-、丙基-、丁基-、异丁基-、2-乙氧基乙基-、肉豆蔻基-、十八基-和特别优选2-乙基己基-和月桂基-。
本发明的共聚物具有103g/mol到109g/mol的分子量,更优选103到107g/mol以及甚至更优选103到105g/mol。
本发明的共聚物能通过自由基聚合来制备。聚合反应可以连续、非连续或半连续的方式进行。
该聚合反应有利地作为沉淀聚合、乳液聚合、溶液聚合、本体聚合或凝胶聚合进行。溶液聚合对于本发明共聚物的性能曲线是特别有利的。
作为用于聚合反应的溶剂,可以使用所有对于自由基聚合反应是基本上惰性的有机或无机溶剂,例如乙酸乙酯、乙酸正丁酯或1-甲氧基-2-丙基乙酸酯,以及醇如乙醇、异丙醇、正丁醇、2-乙基己醇或1-甲氧基-2-丙醇,同样还有二醇如乙二醇和丙二醇。使用酮如丙酮、丁酮、戊酮、己酮和甲乙酮,乙酸、丙酸和丁酸的烷基酯例如乙酸乙酯、乙酸丁酯和乙酸戊酯,醚如四氢呋喃、二乙醚和乙二醇-和聚乙二醇-单烷基醚和二烷基醚同样是可行的。使用芳香族溶剂例如甲苯、二甲苯或更高沸点的烷基苯同样是可行的。同样可以使用溶剂混合物,在这样的情况下,溶剂(一种或多种)的选择取决于本发明的共聚物的使用目的。优选使用水;低级醇;优选甲醇、乙醇、丙醇、异-丁醇、仲-丁醇和叔-丁醇、2-乙基己醇、丁二醇和丁基二甘醇,尤其优选异丙醇、叔丁醇、2-乙基己醇、丁二醇和丁基二甘醇;具有5到30个碳原子的烃及前述化合物的混合物和乳液。
聚合反应优选在0和180℃之间、更优选10和100℃之间的温度范围内进行,不仅在常压下也可在提高的压力或减少的压力下进行。若适当,该聚合还可以在保护性气体气氛,优选在氮气中进行。
该聚合可采用高能的电磁辐射、机械能或常规的化学聚合引发剂如有机过氧化物例如过氧化苯甲酰、叔丁基氢过氧化物、甲乙酮过氧化物、枯酰基过氧化物、二月桂酰过氧化物(DLP)或偶氮引发剂例如偶氮二异丁腈(AIBN)、偶氮二酰氨基丙基氢氯化物(ABAH)和2,2′-偶氮二(2-甲基丁腈)(AMBN)来诱发。同样合适的是无机过氧化物,例如(NH4)2S2O8、K2S2O8或H2O2,并任选地与还原剂(例如亚硫酸氢钠、抗坏血酸、硫酸铁(II))相组合或包含脂肪族的或芳香族的磺酸(例如苯磺酸、甲苯磺酸)作为还原性组分的氧化还原体系。
作为分子量调节剂采用常规的一些化合物。合适的已知的调节剂是例如醇如甲醇、乙醇、丙醇、异丙醇、正丁醇、仲丁醇和戊醇,醛,酮,烷基硫醇例如十二烷基硫醇和叔十二烷基硫醇,巯基乙酸,巯基乙酸异辛酯和一些卤素化合物如四氯化碳、氯仿和二氯甲烷。
本发明的再一个主题是本发明的共聚物作为分散剂,特别是用于颜料和填料的分散剂的用途,例如在制备用于分散色料和清漆色料、刷涂剂、涂料和印刷油墨的着色,以及用于纸张、纸板和织物的着色的水基或溶剂基的颜料浓缩物时。
合成方案1:
在装有搅拌器、回流冷凝器、内温度计和氮气导入管的烧瓶中按照下表中指出的重量份预置入在溶剂中的单体A、单体B、单体C、单体D和分子量调节剂,同时导入氮气。然后使温度在搅拌下达到80℃以及在一小时内计量加入引发剂的溶液。在此温度下进一步搅拌2小时,然后将溶剂在减压下除去。
下表包含了类似于上述一般合成方案的合成实施例。
单体A的组成:
Polyglykol 1
聚亚烷基二醇单甲基丙烯酸酯(式(I),m=2、n=3-4;(A-O)对应于[CH2CH(CH3)O)]、(B-O)对应于(CH2CH2O)),摩尔质量约350g/mol
Polyglykol 2
聚亚烷基二醇单甲基丙烯酸酯(式(I),m=2、n=12-13;(A-O)对应于(CH2CH(CH3)O))、(B-O)对应于(CH2CH2O)),摩尔质量约750g/mol
Polyglykol 3
聚亚烷基二醇单甲基丙烯酸酯(式(I),m=2、n=17-19;(A-O)对应于(CH2CH(CH3)O))、(B-O)对应于(CH2CH2O)),摩尔质量约1000g/mol
Polyglykol 4
聚亚烷基二醇单甲基丙烯酸酯(式(I),m=2、n=40-42;(A-O)对应于[CH2CH(CH3)O)]、(B-O)对应于(CH2CH2O)),摩尔质量约2000g/mol
单体B的组成:
Polyglykol 5
聚丙二醇单甲基丙烯酸酯(式(II),o=4-5;(D-O)对应于[CH2CH(CH3)O)],摩尔质量约350g/mol
Polyglykol 6
聚丙二醇单甲基丙烯酸酯(式(II),o=15-16;(D-O)对应于[CH2CH(CH3)O)],摩尔质量约1000g/mol
AMBN=2,2′-偶氮(2-甲基丁腈)
用途实施例
颜料制剂的制备
将以粉末、颗粒或者压饼形式的颜料在去离子水中与分散剂和其它助剂一起糊化(angeteigt),然后采用溶解器(例如来自VMA-GetzmannGmbH公司的,AE3-M1型)或其他适当的设备来均化和预分散。随后采用珠磨机(例如采用来自VMA-Getzmann的AE3-M1)或其它的适当的分散装置进行精细分散,其中研磨用大小为d=1mm的硅石英(Siliquarzit-)珠粒或锆混合氧化物珠粒在冷却下进行,直到获得所期望的色强度和色彩。之后,将研磨体分离掉,将颜料制剂分离以及用去离子水调整到约20%的浓度并通过来自Büchi公司的喷雾干燥器(Büchi 190)来干燥。获得干燥的粉末。
颜料制剂的评价
色强度和色调按照DIN 55986来测定。在用于室内刷涂的传统水基分散色料和传统的含溶剂漆料中测试水性颜料分散体和干粉(色强度和与要着色的介质的相容性)。为进行“擦去测试”(“Rub-Out-Test”),在与颜料分散体混合之后将色漆(Farbe)涂覆到涂漆卡片(Lackkarte)上。接着,用手指在涂漆卡片的下半部进行后擦拭。如果经后擦拭的区域比没有后处理过的相邻区域的着色更强,则存在不相容性(“擦去测试”描述在DE 2 638 946中)。
使用来自Haake公司的锥板粘度计(Roto Visco 1)在20℃下测定粘度(钛圆锥体:φ60mm,1°),所研究的粘度对剪切梯度的应变关系在0和200s-1之间的范围。粘度在60s-1的剪切梯度下测量。
为了评价分散体的储存稳定性,在制得制剂后直接地以及在于50℃下存放四周后,测量粘度。
接下来的实施例中描述的颜料制剂通过如上所述的方法来制备,以下组分以所述的用量使用以形成100份的颜料制剂。在接下来的实施例中,份数是重量份:
35份 C.I.颜料黄74
14份 来自合成实施例11的聚合物(表)
1份 润湿剂
50份 水
干燥之后,颜料制剂具有以下组成,在此忽略约1%的残余水含量:
70份 C.I.颜料黄74
28份 来自合成实施例11的聚合物(表)
2份 润湿剂
该颜料制剂在白色分散体和在漆料中具有很高的色强度并且是稳定的。擦去测试表明与经后擦拭的区域相比没有色强度差别。该分散体经证明是能流动的且是稳定的,因为它在50℃下存储28天之后仍然是能流动的。干燥的粉末能自动拌和入水基白色分散体和含溶剂的漆料中。手工搅拌3分钟。两个颜色体系中都实现了高色强度及无斑点不絮凝的涂覆。擦去试验未显示出与经后擦拭的区域相比有色强度差别。
Claims (8)
1.可通过单体(A)、(B)、(C)和(D)的聚合获得的共聚物,
其中
(A)是式(I)的单体
其中
R表示氢或甲基,
m为从1到500的数值;
n为从1到500的数值,
其中m+n的总和为从2到1000;
并且其中单体(A)中(A-O)m表示氧化亚丙基单元和(B-O)n表示氧化亚乙基单元,或者(A-O)m表示氧化亚乙基单元和(B-O)n表示氧化亚丙基单元,
并且在单体(A)中氧化亚乙基单元的摩尔比为基于氧化亚乙基和氧化亚丙基单元的总和计50到98%;
(B)是式(I I)的单体
其中
D表示C3-亚烷基和
R表示氢或甲基,
o为从2到500的数值;
(C)是包含芳基的烯属不饱和单体,所述单体(C)是式(IIIa)或(IIIb)的化合物:
其中
Xa表示具有3到30个碳原子的芳香族或芳脂族基团,其任选包含选自N、O和S的杂原子,
Za表示H或(C1-C4)-烷基,
Zb表示H或(C1-C4)-烷基,以及
Zc表示H或(C1-C4)-烷基;
其中
R1表示氢或甲基,
Xb表示具有3到30个碳原子的芳香族或芳脂族基团,其任选包含选自N、O和S的杂原子,
Wa表示氧或NH基团;以及
(D)是包含烷基的烯属不饱和单体,所述单体(D)是式(IV)的化合物:
其中
R2表示氢或甲基,
Y表示具有1到30个碳原子的脂肪族烃基,其可以是线型或支化的或者环状的,以及其可包含选自O、N和S的杂原子且可以是不饱和的,
Wb表示氧或NH基团;
其中,单体(A)的摩尔比例为0.1到90%,单体(B)为0.1到90%,单体(C)为0.1到90%以及单体(D)为0.1到90%,其中摩尔比例的总和为100%。
2.权利要求1所述的共聚物,其特征在于,单体(A)的摩尔比例为0.1到70%,单体(B)为10到80%,单体(C)为0.1到50%以及单体(D)为0.1到50%,其中摩尔比例的总和为100%。
3.权利要求1或2所述的共聚物,其特征在于,氧化亚烷基单元(A-O)m和(B-O)n是嵌段状排布的。
4.如权利要求1或2所述的共聚物,其特征在于,所述单体(C)是苯乙烯、1-乙烯基咪唑、甲基丙烯酸苄基酯、甲基丙烯酸2-苯氧基乙基酯或甲基丙烯酸苯乙酯。
5.如权利要求1或2所述的共聚物,其特征在于,所述单体(D)是丙烯酸或甲基丙烯酸的烷基酯或烷基酰胺,其中“烷基”含义为甲基、乙基、丙基、丁基、异丁基、肉豆蔻基、十八基、2-乙基己基或月桂基,或是丙烯酸或甲基丙烯酸的2-乙氧基乙基酯或2-乙氧基乙基酰胺。
6.一种制备如权利要求1到5任一项所述的共聚物的方法,其中使单体(A)、(B)、(C)和(D)自由基聚合。
7.权利要求1到5任一项所述的共聚物作为分散剂的用途。
8.如权利要求7所述的用途,其中所述分散剂是用于颜料和填料的分散剂。
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DE102008038072.5 | 2008-08-16 | ||
PCT/EP2009/005198 WO2010020314A1 (de) | 2008-08-16 | 2009-07-17 | Nichtionische wasser- und lösungsmittellösliche additive |
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DE102008038071A1 (de) * | 2008-08-16 | 2010-02-18 | Clariant International Limited | Anionische wasser- und lösungsmittellösliche Additive |
DE102008037973A1 (de) | 2008-08-16 | 2010-02-18 | Clariant International Limited | Trockene Pigmentpräparationen mit anionischen Additiven |
DE102009030339A1 (de) | 2009-06-25 | 2011-01-05 | Clariant International Ltd. | Additive zur Inhibierung der Gashydratbildung |
DE102010022759A1 (de) | 2010-06-04 | 2011-12-08 | Clariant International Ltd. | Additive zur Inhibierung der Gashydratbildung |
US9556322B2 (en) | 2013-08-13 | 2017-01-31 | Colormatrix Holdings, Inc. | Liquid pigment dispersions |
CN107868189B (zh) * | 2016-09-28 | 2020-06-09 | 中国石油化工股份有限公司 | 一种丙烯酰胺共聚物及其制备方法与应用 |
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DE102008038072A1 (de) | 2010-02-18 |
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JP2012500288A (ja) | 2012-01-05 |
ES2593118T3 (es) | 2016-12-05 |
KR20110056511A (ko) | 2011-05-30 |
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