NZ622068B2 - Composition comprising a non-ionic surfactant and an ionic polymer - Google Patents
Composition comprising a non-ionic surfactant and an ionic polymer Download PDFInfo
- Publication number
- NZ622068B2 NZ622068B2 NZ622068A NZ62206812A NZ622068B2 NZ 622068 B2 NZ622068 B2 NZ 622068B2 NZ 622068 A NZ622068 A NZ 622068A NZ 62206812 A NZ62206812 A NZ 62206812A NZ 622068 B2 NZ622068 B2 NZ 622068B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- ionic
- water
- alkyl
- monomer
- monomers
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 112
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 42
- 239000002736 nonionic surfactant Substances 0.000 title claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 108
- 238000000034 method Methods 0.000 claims abstract description 35
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- -1 alkali metal salts Chemical class 0.000 claims description 90
- 239000011780 sodium chloride Substances 0.000 claims description 56
- 125000002091 cationic group Chemical group 0.000 claims description 54
- 239000002270 dispersing agent Substances 0.000 claims description 52
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- 238000006116 polymerization reaction Methods 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 38
- 125000000129 anionic group Chemical group 0.000 claims description 36
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 30
- 230000003311 flocculating Effects 0.000 claims description 23
- 239000011541 reaction mixture Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 21
- 238000004132 cross linking Methods 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 17
- 150000003863 ammonium salts Chemical class 0.000 claims description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 150000003926 acrylamides Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 230000000996 additive Effects 0.000 claims description 3
- 239000003651 drinking water Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 235000012206 bottled water Nutrition 0.000 claims description 2
- 230000003750 conditioning Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005188 flotation Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000002577 pseudohalo group Chemical group 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims 5
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 2
- 238000005189 flocculation Methods 0.000 abstract description 20
- 230000016615 flocculation Effects 0.000 abstract description 20
- 239000010802 sludge Substances 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 9
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000008247 solid mixture Substances 0.000 abstract description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 239000000499 gel Substances 0.000 description 30
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 29
- 150000003839 salts Chemical class 0.000 description 28
- 239000000047 product Substances 0.000 description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 239000004971 Cross linker Substances 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 14
- 229960004063 Propylene glycol Drugs 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 13
- 239000006260 foam Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- 241000196324 Embryophyta Species 0.000 description 11
- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 125000004432 carbon atoms Chemical group C* 0.000 description 9
- 150000002191 fatty alcohols Chemical class 0.000 description 9
- 238000005755 formation reaction Methods 0.000 description 9
- 125000003827 glycol group Chemical group 0.000 description 9
- 239000000123 paper Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 229920001519 homopolymer Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tBuOOH Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 8
- 101700082413 tant Proteins 0.000 description 8
- NEHMKBQYUWJMIP-UHFFFAOYSA-N Chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 7
- 229940050176 Methyl Chloride Drugs 0.000 description 7
- 238000007792 addition Methods 0.000 description 7
- 239000002518 antifoaming agent Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000004815 dispersion polymerization Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 101700000038 mpas Proteins 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N Dodecanol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 5
- 229940035295 Ting Drugs 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000001530 fumaric acid Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 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 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 4
- 125000005916 2-methylpentyl group Chemical group 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N Itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N Oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L Sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 230000002378 acidificating Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000006085 branching agent Substances 0.000 description 4
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- XVOUMQNXTGKGMA-UHFFFAOYSA-N glutaconic acid Chemical compound OC(=O)CC=CC(O)=O XVOUMQNXTGKGMA-UHFFFAOYSA-N 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 230000001264 neutralization Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N Crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- ADTJPOBHAXXXFS-UHFFFAOYSA-N N-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene (PE) Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000005591 charge neutralization Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000001809 detectable Effects 0.000 description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000001771 impaired Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000002829 reduced Effects 0.000 description 3
- 238000005549 size reduction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000005208 trialkylammonium group Chemical group 0.000 description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N 1,2-Butanediol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N 2,3-Butanediol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-Ethylhexanol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide Chemical compound NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- BPAZNZINLQSFMN-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1H-imidazole;dihydrochloride Chemical compound Cl.Cl.CC(C)C1=NCCN1 BPAZNZINLQSFMN-UHFFFAOYSA-N 0.000 description 2
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N Benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N Cetyl alcohol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N Linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N N,N'-Methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- HKTGZPQHFCONFD-UHFFFAOYSA-N N-[(dimethylamino)methyl]-2-methylprop-2-enamide Chemical compound CN(C)CNC(=O)C(C)=C HKTGZPQHFCONFD-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N Palmitic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N Pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N Stearyl alcohol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N Vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000003254 anti-foaming Effects 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 229920003118 cationic copolymer Polymers 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 125000006264 diethylaminomethyl group Chemical group [H]C([H])([H])C([H])([H])N(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 125000006222 dimethylaminomethyl group Chemical class [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 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 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052500 inorganic mineral Chemical class 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 210000001699 lower leg Anatomy 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- HPKNNSJBWTXMHS-UHFFFAOYSA-N potassium;prop-2-enoic acid Chemical compound [K].OC(=O)C=C HPKNNSJBWTXMHS-UHFFFAOYSA-N 0.000 description 2
- MHWRYTCHHJGQFQ-UHFFFAOYSA-M prop-2-enoate;hydrate Chemical compound [OH-].OC(=O)C=C MHWRYTCHHJGQFQ-UHFFFAOYSA-M 0.000 description 2
- 230000001902 propagating Effects 0.000 description 2
- KOODSCBKXPPKHE-UHFFFAOYSA-N propanethioic S-acid Chemical compound CCC(S)=O KOODSCBKXPPKHE-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003638 reducing agent Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- NNNVXFKZMRGJPM-KHPPLWFESA-N sapienic acid Chemical compound CCCCCCCCC\C=C/CCCCC(O)=O NNNVXFKZMRGJPM-KHPPLWFESA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- UNHKSXOTUHOTAB-UHFFFAOYSA-N sodium;sulfane Chemical compound [Na].S UNHKSXOTUHOTAB-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- 239000010959 steel Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- ZTUXEFFFLOVXQE-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCC(O)=O ZTUXEFFFLOVXQE-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/547—Tensides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
Abstract
Disclosed herein are compositions, preferably solid compositions, comprising a non-ionic surfactant R1-O-A-O-R2, wherein the residue -O-A-O- is derived from a polyalkylene glycol HO-A-OH that comprises monomer units derived from an (C2-C6)-alkylene glycol or a mixture of at least two different (C2-C6)-alkylene glycols; and R1 is selected from the group consisting of -H, -(C8-C20)-alkyl, -(C8-C20)-alkenyl, -(C=O)-(C8-C20)-alkyl and -(C=O)-(C8-C20)-alkenyl, and R2 is selected from the group consisting of -H, -(C1-C6)-alkyl, -benzyl, -(C=O)(C8-C20)-alkyl and -(C=O)-(C8-C20)-alkenyl; and and a water-soluble ionic polymer, methods for their preparation and their use. The compositions are useful inter alia as flocculation auxiliaries for solid-liquid separation processes, for example in sludge dewate ring/waste water purification and as retention aids or other additives in paper manufacture. 6)-alkylene glycols; and R1 is selected from the group consisting of -H, -(C8-C20)-alkyl, -(C8-C20)-alkenyl, -(C=O)-(C8-C20)-alkyl and -(C=O)-(C8-C20)-alkenyl, and R2 is selected from the group consisting of -H, -(C1-C6)-alkyl, -benzyl, -(C=O)(C8-C20)-alkyl and -(C=O)-(C8-C20)-alkenyl; and and a water-soluble ionic polymer, methods for their preparation and their use. The compositions are useful inter alia as flocculation auxiliaries for solid-liquid separation processes, for example in sludge dewate ring/waste water purification and as retention aids or other additives in paper manufacture.
Description
W0 20132057267
Composition comprising a non-ionic surfactant and an ionic polymer
The invention relates to compositions, preferably solid compositions, comprising a non—ionic
surfactant and an ionic polymer, methods for their preparation and their use. The
compositions are useful inter alia as flocculation auxiliaries for solid-liquid separation
ses, for example in sludge dewatering/waste water purification and as retention aids
or other ves in paper manufacture.
In the practice of solid-liquid tion the object is to achieve, by addition of flocculating
auxiliaries, the best possible result in terms of the parameters dry nce of the solid and
clarity of the filtrate, or in other words to bring about the most complete separation possible
of solid from the liquid phase. Sludge dewatering on a chamber-type filter or in a decanter
centrifuge can be ed as examples of the importance of these parameters. Since the
dried sludge must be transported and often put to beneficial use by thermal processing, the
highest le content of solid (dry-substance content) is desired. In addition, the
separated filtrate must be delivered to disposal. The quality and simplicity of such disposal
increase as the y of the filtrate increases, or in other words as the content of
unflocculated solids remaining in the filtrate becomes lower. In such a case the te can be
discharged directly from a clarifying plant to the environment, and does not have to pass
through the clarifying plant once again.
Flocculating auxiliaries are produced in the form of powdery granules or water-in-water
r dispersions or water-in—oil emulsions, and prior to their use are added in dilute
aqueous solutions to the medium to be flocculated. Powdery granules are preferred, since
they can be transported more inexpensively by virtue of their almost anhydrous condition
and, as in the water-in-oil emulsions, do not contain any oil or solvent constituents that are
insoluble in water. Typically, solutions having a concentration of 0.01 to 0.5 wt.-% are
prepared.
It is known from the prior art to employ water-in-water polymer dispersions containing ionic
rylamide derivatives as flocculating agents in solid/liquid separation processes. For
example, , and describe the use of
cationic in-water polymer dispersions as flocculation auxiliaries in solid ntation
processes. The use of c water-in-water r dispersions as flocculating agents in
WO 2013057267
such ations is known from WO 2005/092954. Powdery, soluble, cationic
polymers for solid-liquid separation are known from .
However, in case of using solid forms, which are often preferred over the liquid ones due to
lower transportation costs and higher storage stability, some of these show a clear tendency
to cause or stabilize foam during their make-down or in the application processes, such as
solid/liquid separation processes. These foams can slow the processes down, disturb them
or even make the use of ed flocculation auxiliaries impossible. Therefore, in a lot of
these applications an additional defoaming aid has to be used.
These additional defoaming aids typically t predominantly of mineral oils and require
an onal e. Mixing such defoaming agent with a solid flocculating auxiliary impairs
the ility of the flocculating auxiliary and may even result in a complete loss of
flowability. Consequently, these defoaming agents have to be introduced into the centrate
(filtrate) via additional dosing points, eg. an additional pump. The necessity to use an
additional defoaming agent is thus always associated with costly installation efforts and
considerable additional costs.
Flocculating auxiliaries that are commercially available in form of water-in-oil emulsions do
not have such disadvantages since they already n such mineral oil with ing
properties. However, these water-in-oil emulsions have the disadvantage that they do not
contain the flocculating auxiliary in concentrated form. Therefore, much larger volumes have
to be ed, transported and stored. Further, the storage stability of such water-in-oil
polymer ons is typically reduced compared to solid forms of polymeric flocculating
auxiliaries.
Anti-foaming agents based on oil-in—water emulsions are known from patent applications US
2006/0111453 and US 2010/0212847.
US 5,684,107 discloses the cture of agglomerated polymer les of finely divided
polymers by azeotropic dewatering of in-oil emulsions of polymers in the presence of
polyalkylene glycols. The polymers are preferably cross—linked by adding considerable
amounts of linkers, preferably 50 to 5,000 ppm. A skilled artisan is fully aware that
under the conditions of azeotropic dewatering (which is generally a thermal process) in
presence of polyalkylene glycol crosslinking and thereby gel formation takes place with
anionic polymers such as polyacrylic acid, as the polyalkylene glycol reacts with the acid
groups at the polymer backbone. Thus, even if no cross-linker is added to the reaction
mixtures, the anionic products ing to US 5,684,107 exhibit a comparatively high
degree of branching and cross-linking. Furthermore, the agglomerated polymer particles
always contain residual amounts of oil, which is detrimental for s reasons, in particular
ecological reasons.
it is an object of the invention to provide compositions containing ionic polymeric flocculation
auxiliaries which have advantages compared to the compositions of the prior art. in
particular, the handling and metering of the composition should be simple and the
composition should not have any negative influences on the performance or application
properties of flocculating auxiliary contained therein. The foregoing object should be read
disjunctively with the object of at least providing the public with a useful .
it has been surprisingly found that le non~ionic surfactants with anti—foaming ties
and suitable ionic polymer flocculating auxiliaries can be combined in form of a composition,
preferably a solid composition, without ing the performance of the dual
components. Further, it has been surprisingly found that the relative weight ratio of the non-
ionic surfactant to the ionic polymer can be specifically tailored so that g can be
efficiently suppressed at minimized consumption of non-ionic surfactant. Thus, separate
addition and individual dose adjustment of non-ionic surfactant is not necessary when
utilizing the composition according to the invention.
Figure 1 shows the foam height versus time as determined in a comparative foaming test
between the ition according to the invention (Example) and a commercial flocculating
auxiliary (comparative Example).
Figure 2 shows the gel formation of various polymer compositions in dependence on the
content of cross—linkers.
A first aspect of the invention relates to a composition comprising
(i) a non-ionic surfactant R1-O—A-O~R2, wherein
— the residue -O-A—O- is derived from a polyalkylene glycol HO-A-OH that comprises
monomer units derived from an (Cg-Ce)-a|kylene glycol or a e of at least two
different (C2-C5)-alkylene glycols; and
— R1 is selected from the group consisting of —H, zo)-alkyl, zo)-alkenyl,
-(C=O)—(C3—C20)-alky| and -(C=O)-(Cg-Cgo)-alkenyl, and
— R2 is selected from the group consisting of -H, -(C1—C6)-alkyl, -benzyl, -(C=O)-(03‘C20)'
alkyl and —(C=O)-(Cg-Cgo)-alkenyl; and
(ii)a water-soluble or water-swellable ionic polymer, which is preferably derived from a
monomer composition (i) not sing any cross-linking monomers, or (ii) containing not
more than 50 ppm cross-linking monomers, relative to the total content of monomers in
the monomer composition. ln this regard, when cross—linking is achieved after
polymerization of the monomers, i.e. by adding further reactants in a polymer-analogous
reaction, the amount of said reactants is at most 50 ppm relative to the total content of
rs in the monomer composition.
When the r composition contains cross-linking monomers or when after
rization of the monomers further reactants are added in order to achieve cross-linking
in a polymer-analogous reaction, the content of said cross-linking monomers and nts,
respectively, is preferably at most 45 ppm, more preferably at most 40 ppm, still more
preferably at most 40 ppm, yet more preferably at most 35 ppm, even more preferably at
most 30 ppm, most preferably at most 25 ppm, and in particular at most 20 ppm, ve to
the total content of monomers in the monomer composition.
in a preferred embodiment, the ition is a liquid, preferably an aqueous composition,
in particular a water-in-water polymer dispersion.
in-water polymer dispersions are well known in the art. in this regard it can be referred
to, e.g., H. Xu et al., Drug Dev Ind Pharm., 2001, 27(2), pp 171-4; K.A. Simon et al.,
Langmuir., 2007, 30;23(3), 1453-8; P. Hongsprabhas, International Journal of Food e
& Technology, 2007, 42(6), 8; D. Gudlauski, Paper Age, May/June 2005, pp 36 f, US—
A 2004/0034145, US—A 2004/0046158, US-A 2004/0211932, US—A 242045, US-A
2006/0112824 and US-A 2007/0203290.
The water content of the water-in-water polymer dispersion may vary from 0.01 to 99.99 wt.-
%. In a preferred embodiment, the water t is at most 65 wt.-%, more preferably at
most 60 wt.-%, still more preferably at most 55 wt.-%, yet more preferably at most 50 wt.-%,
most preferably below 50 wt.-%, an in particular at most 45 wt.-%, based on the total weight
of the water-in-water polymer dispersion.
In an especially red embodiment, however, the composition is a solid, in particular in
form of a powder or granules. in this embodiment, the moisture content is preferably
not exceeding 12 wt.-%, and particularly preferably not exceeding 10 wt.-%.
According to the invention, the composition comprises a non-ionic surfactant R1-O-A-O—R2,
wherein the residue - is d from a poiyalkylene glycol HO-A-OH that comprises
monomer units derived from an (Cg-CB)-alkylene glycol or a mixture of at least two ent
(Cg-Ce)-a|kylene glycols.
in this regard, "monomer units derived from" means that the poiyalkylene glycol HO-A-OH
comprises repetition units, i.e., repetition units are incorporated in the polymer backbone of
the poiyalkylene glycol HO-A—OH, which repetition units can be imagined to be formed from
the ponding monomers in the course of a ndensation on. This does not
mean that such polycondensation can actually take place, but shall only mean that such
polycondensation reaction can be performed by imagination. For example, when the
poiyalkylene glycol HO-A-OH is derived from ethylene glycol and propylene glycol, the
following repetition units are incorporated in the polymer backbone:
ear war
The non-ionic surfactant A-O-Fi2 can preferably also be regarded as being consisting of
a polyoxyalkylene chain terminated at one chain end with the substituent Ft1 and at the other
chain end with the substituent R2.
For the purpose of the specification, the term "alkylene" shall mean any ted linear or
branched hydrocarbon having two binding partners, such as -CH2CH2-, ~CH20HQCH2- and
-CH2CH(CH3)CH2-.
For the e of the specification, "alkyl" shall mean any saturated linear or branched
hydrocarbon having a single binding partner, such as methyl, ethyl, n-propyl, iso-propyl, n-
butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, n—heptyl, 2-methylhexyl, 3-methylhexyl, 3—
thylpentyl, 2,2—, 2,3-, 2,4- and 3,3-dimethylpentyl, n-octyl, 4-methylheptyl, 2,2,3-, ,
2,3,3-, and 2,3,4-trimethylpentyl, 2-ethylhexyl, n-nonyl, l, isodecyl, n-undecyl, n-
dodecyl (lauryl), n-tridecyl, isotridecyl, n-tetradecyl (myristyl), n-pentadecyl, n—hexadecyl
(cetyl), adecyl (margarinyl), n-octadecyl (stearyl), 16-methylheptadecyl (isostearyl), n-
nonadecyl, n-eicosyl (arachinyl), and the like.
For the purpose of the specification, "alkenyl" shall mean any linear or branched hydrocarbon
comprising one or more double bonds and having a single binding partner, including CH-
alkenyls such as ethenyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylpropenyl, 1-
pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, i-methyl-i-butenyl, 2-methylbutenyl, 3-
methyl-i-butenyl, 1-methylbutenyl, 2-methylbutenyl, 3-methylbutenyl, 1-methyl
butenyl, 2-methylbutenyl, 3-methylbutenyl, 1,1-dimethyl—2-propenyl, 1,2-dimethyl
propenyl, methyl-2—propenyl, l-ethyl-i-propenyl, l-ethyl-Z-propenyl, l-hexenyl, 2-
hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1—heptenyl, and the like; and including 08-20—
alkenyls such as nyl, nyl, i-decenyl, cenyl, 1-dodecenyl, 9-cis-dodecenyl
(lauroleyl), 1-tridecenyl, 1-tetradecenyl, 9-cis-tetradecenyl (myristoleyl), 1-pentadecenyl, i—
hexadecenyl, 9-cis-hexadecenyl (palmitoleinyl), t-heptadecenyl, 1-octadecenyl, 6-cis-
cenyl (petroselinyl), 6-trans-octadecenyl (petroselaidinyl), 9-cis-octadecenyl (oleyl), 9-
trans-octadecenyl (elaidinyl), 11-cis-octadecenyl (vaccenyl), 9-ciscis-octadecadienyl
(linoleyl), 9-trans-12—trans-octadecadienyl (elaidolinoleyl), 9-cis-12—ciscis-octadecatrienyl
-linolenyl), 6-ciscis-12—cis-octadecatrienyl (gamma-linolenyl), 8-transtrans
cis-octadecatrienyl, 9-transtrans—l5-trans-octadecatrienyl (elaidolinolenyl), 9-cis
transtrans-octadecatrienyl (alpha-eleostearinyl), s-1 i-tran s-1 3-trans-octadeca—
trienyl (beta-eleostearinyl), 9-cistrans-‘l3-cis-octadecatrienyl (punicyl), 9-,11-,13-,15-
octadecatetraenyl aryl), t-nonadecenyl, 11-cis-eicosenyl (icosenyl), 9-cis—eicosenyl
(gadoleinyl), 5-,11-,14-eicosatrienyl, all-cis,8-,11-,14-eicosatetraenyl (arachidonyl), and all-
Cis,8-,11-,14-,17-eicosapentaenyl (timnodonyl) and the like.
if monomers units derived from a mixture of at least two different (C2-Cs)-alkylene glycols are
present, the monomer units can be t in any order. In a preferred embodiment, the two
different monomer units are present in form of two or more, preferably two or three separate
blocks, i.e. the polyalkylene glycol HO-A—OH from which the residue ~O-A—O- is derived from
is preferably a k copolymer or a ck copolymer. The separate blocks can be
regarded as homopolymer subunits linked to each other by covalent bonds.
Especially preferred are )-alkylene glycols selected from the group ting of
ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,2-pentylene
glycol, 2,3-pentylene glycol, 3-methylbutane-i,2-diol, xylene glycol and 4-
methylpentane-2,3-dio|, and mixtures thereof.
Preferably, the residue -O-A-O- is derived from a polyalkylene glycol H that
comprises monomer units derived from an (Cg-C4)—alkylene glycol or a mixture of at least two
different (Cg-C4)-alkylene glycols, in ular those derived from ethylene glycol, 1,2-
propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol and mixtures thereof.
In a preferred embodiment, the residue -O-A-O- is derived from a polyalkylene glycol HO-A—
OH that comprises monomer units derived from ethylene glycol or a mixture of ethylene
glycol and propylene glycol.
In an especially preferred embodiment, the e — is derived from a kylene
glycol HO-A—OH that ses 2—130 monomer units derived from ethylene glycol and 0-60
monomer units derived from propylene glycol. In this embodiment, if R1 and R2 both are
hydrogen, the residue —O—A-O— is preferably d from a polyalkylene glycol HO—A—OH that
preferably comprises at least one r unit derived from propylene glycol.
In a preferred embodiment, the residue -O-A-O— is derived from a polyalkylene glycol HO-A-
OH that comprises 2-130 monomer units derived from ethylene glycol and 1-60 r
units derived from propylene glycol.
Preferably, the relative weight ratio of the monomer units derived from ethylene glycol and
the monomer units derived from propylene glycol is within the range of from 99:1 to 1:99,
more preferably within the range of from 75:1 to 1:75, still more preferably within the range of
from 50:1 to 1:50, yet more preferably within the range of from 20:1 to 1:20, and most
preferably within the range of from 10:1 to 1:10.
If monomers units derived from ethylene glycol and propylene glycol are present, the
monomer units can be present in any order or in form of two or more, ably two or three
separate blocks.
In a preferred embodiment, the r units are present in form of two blocks, one block
comprising only monomer units derived from ethylene glycol and the other block comprising
only monomer units derived from ene glycol.
In another preferred embodiment, the monomer units are present in form of three blocks, one
middle block comprising only monomer units derived from propylene glycol and two outer
blocks comprising only monomer units derived from ethylene glycol.
In still another preferred embodiment, the monomer units are present in form of three blocks,
one middle block comprising only monomer units derived from ne glycol and two outer
blocks comprising only monomer units derived from propylene glycol.
2012/070786
Especially preferred non-ionic surfactants FT-O-A-O-Ft2 are selected from the group
consisting of
(0 ethoxylated, saturated or unsaturated (Cs‘Cgo)'fatty alcohols, ably obtainable by
etherifying saturated or unsaturated (Cg-Cgo)-fatty alcohols with ethylene oxide so that a
polyethylene glycol moiety is linked to the hydroxyl group of the saturated or unsaturated
(Cg-Cgo)-fatty alcohols via an ether bond; wherein the hylene glycol moiety
preferably comprises 2 to 25 ethylene oxide units (‘CHQCH20'), more preferably 2 to 20
ethylene oxide units;
ethoxylated and ylated, saturated or unsaturated (Cg-Cgo)-fatty alcohols,
preferably able by etherifying saturated or unsaturated (Cs‘C20)'fatty alcohols with
ethylene oxide and propylene oxide, sequentially or aneously, so that a
polyalkylene glycol moiety is linked to the yl group of the saturated or rated
(Ca'Cgo)‘fatty alcohols via an ether bond; wherein the polyalkylene glycol moiety
preferably ses 2 to 130 ethylene oxide units (-CHQCH20-) and 1 to 60 propylene
oxide units (-CHZCH(CH3)O—); wherein the units (‘CHQCH20') and
(-CHQCH(CH3)O-) can be present in any order or in form of two separate blocks;
surfactants of this type are e.g. known and commercially available known under the
trade names "Antispumin® HE" and "P|urafac®";
(iii) ethoxylated, saturated or unsaturated (Cg-Cgo)-fatty alcohols of type (i) and/or the
ethoxylated and propoxylated saturated or unsaturated (C5'C2o)'fatty alcohols of type (ii)
end-capped by a -(Ci-C6)—alkyl or benzyl group, preferably n-butyl or benzyl group,
preferably obtainable by etherifying the lated, saturated or unsaturated (C8-C20)'
fatty alcohols of type (i) and/or the lated and propoxylated saturated or
unsaturated (Cg-Cgo)-fatty alcohols of type (ii) with -(Cl~C6)-alky| halide or benzyl halide,
preferably n-butyl halide or benzyl halide, in presence of a base; examples of this type
include the surfactants known and commercially available under the trade name
"Dehypon® LT" and the end-capped surfactants known and commercially available under
the trade name "Plurafac®'.
ethoxylated and propoxylated s, preferably obtainable by etherifying a glycol,
preferably selected from the group consisting of ne glycol, propylene glycol,
trimethylene glycol, neopentyl glycol, diethylene glycol and triethylene glycol with
ethylene oxide and ene oxide so that a kylene glycol moiety is linked to at
least one hydroxyl group of the glycol via an ether bond; n the reaction product
preferably comprises 1 to 130 ethylene oxide units (-CHQCHQO-) and 1 to 60 propylene
oxide units (-CHZCH(CH3)O-); wherein the units (—CHQCHQO-) and (-CHZCH(CH3)O-) can
be present in any order, preferably in form of two or more separate blocks; examples of
this type include the surfactants known and commercially available under the trade name
nic®"; and
esters of saturated or unsaturated o)'fatty acids and the non-ionic surfactants of
type (I) or (ii) and/or mono- or rs of ted or unsaturated (Ca-Czo)-fatty acids
and the non-ionic surfactants of type (lV), preferably able by
esterifying a non-ionic surfactant of type (I) or (II) or (IV) with a saturated or
unsaturated (Cg-Cgo)-fatty acid; or
lating saturated or unsaturated (Ce—Cgo)-fatty acids with ethylene oxide so that
a polyethylene glycol moiety is linked to the hydroxyl group of the saturated or
unsaturated (Cg-C18)-fatty acids via an ester bond; wherein the polyethylene glycol
moiety preferably comprises 2 to 25 ethylene oxide units
(-CH20H20~), more preferably 2 to 20 ne oxide units; or
alkoxylating saturated or unsaturated (Cs‘C20)*fatty acids with ethylene oxide and
propylene oxide, sequentially or simultaneously, so that a polyalkylene glycol moiety
is linked to the hydroxyl group of the saturated or unsaturated (Cs-C20)'fatty acids via
an ester bond; wherein the polyalkylene glycol moiety preferably comprises 2 to 130
ethylene oxide units (-CHZCHZO-) and 1 to 60 propylene oxide units
(-CH20H(CH3)O-); wherein the units (—CHZCHQO-) and (-CHZCH(CH3)O-) can be
present in any order, preferably in form of two or more separate blocks.
Preferred ted (Ce-Cgo)-fatty alcohols are selected from the group consisting of 1~
octanol (capryl alcohol), 2—ethyl hexanol, 1-nonanol, 1-dodecanol c alcohol), 1-
undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, adecanol (myristyl
alcohol), 1~pentadecano| decyl alcohol), 1-hexadecanol (cetyl alcohol), heptadecyl
alcohol, 1-octadecanol (stearyl alcohol), isostearyl alcohol, nonadecyl l, dyl
alcohol and mixtures thereof.
Preferred unsaturated (Cs'Cgo)'fatty alcohols are selected from the group consisting of
palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, elaidolinoleyl alcohol,
linolenyl alcohol, elaidolinolenyl alcohol, ricinoleyl alcohol, and mixtures f.
Preferred saturated (Cg'C2o)'fafiy acids are selected from the group consisting of octanoic
acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), dodecanoic acid (lauric acid),
tetradecanoic acid (myristic acid), pentadecanoic acid, canoic acid (palmitic acid),
heptadecanoic acid ric acid), octadecanoic acid (stearic acid), nonadecanoic acid,
icosanoic acid (arachidic acid) and mixtures thereof.
2012/070786
Preferred unsaturated (Ca'Ceo)'fatty acids are selected from the group ting of
myristoleic acid, oleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic
acid, aidic acid, alpha~linolenic acid, eicosenoic acid, arachidonic acid,
eicosapentaenoic acid, and mixtures thereof.
According to the invention, Ft1 is ed from the group consisting of -H, -(Ce-Ceo)'alkyl,
-(Cs-Ceo)-alkenyl, -(C=O)—(Ca-Cgo)-alkyl and -(C=O)-(Cs-Cgo)-alkenyl, and R2 is selected from
the group consisting of —H, ~(Ci-Ce)—alkyl, ~benzyl, -(C=O)-(Cg—CQO)-alkyl and ‘(C=O)'(C8'C20)‘
alkenyl.
in a preferred ment, Fi1 is '(Ca'C20)'alky1 or ~(Ca-C20)-alkenyl and R2 is -H, i.e. the non-
ionic surfactant R1-O-A-O-R2 is preferably of type (i) or (ii).
in another preferred embodiment, R1 is -(C8~Cgo)-alkyl or -(Cg-Czo)-alkenyl and R2 is -(C1-CG)-
alkyl or -benzyl, i.e. the non—ionic tant R1-O-A—O-R2is preferably of type (iii).
In still another preferred embodiment, R1 is '(Cs'Czo)'C(=O)'alkyl or zo)-C(=O)-alkenyl
and R2 is selected from -H, -(Cg-Cgo)-C(=O)-alkyl and -(CB-Czo)-C(=O)-alkenyl, i.e. the non-
ionic surfactant R1-O-A-O-R2 is a (Ca'Czo)'fatty acid mono- or diester, preferably of type (v).
in yet another preferred embodiment, R1 and R2 stand for -H; i.e. the non-ionic surfactant
Fil-O-A-O—Fi2 is preferably of type (vi).
in a preferred ment, at least one of Ft1 and R2 stands for —H.
in a preferred embodiment, the surfactant Fi1-O-A-O—R2 can be represented by the general
formula(A
wwwmscnaq
wherein
R‘ is selected from the group consisting of -H, -(C8-Czo)-alkyl, -(C8-C20)'
alkenyl, '(C=O)-(Ce'C20)'alkyl and -(C=O)-(Cs-Cgo)-alkenyl,
Ft2 is selected from the group consisting of -H, -(Ci-C5)-alkyl, -benzyl,
'(C=O)'(Ca'020)'alky1 and -(C=O)~(C8-C20)-alkenyl,
o and p are integers of from 0 to 130, and the sum of o and p is within the
range of from 2 to 130;
q and r are integers of from 0 to 60; and the sum of q and r is within the range
of from O to 60;
preferably with the proviso that if R1 and R2 are both H, the sum of q and r may
not be 0.
Preferably, at least one of the integers o, p, q and r is 0; i.e. the polyalkylene glycol HO-A-OH
from which the residue -O-A-O- is derived from is preferably a homopolymer, a k
copoiymer or a triblock copoiymer.
In a preferred embodiment, q, p and r are 0; i.e. the polyalkylene glycol HO-A-OH from which
the residue - is derived from is a homopolymer.
In another preferred embodment, either q or p is 0; i.e. the polyalkylene glycol HO—A-OH from
which the e - is derived from is a diblock copoiymer.
In still another preferred embodiment, either 0 or r is 0; i.e. the polyalkylene glycol H
from which the residue -O-A-O- is derived from is a triblock copoiymer.
Preferably, the average moiecuiar weight of the surfactant is within the range of from 250 to
50.000 g/mol, more preferably within the range of from 500 to 25.000 g/mol, still more
preferably within the range of from 1.000 to 20.000 g/mol, and most preferably within the
range of from 2.000 g/mol to 10.000 g/mol.
Preferably, the surfactant has a HLB not exceeding 14, more preferably not exceeding 12
(for the definition of the HLB value, see W.C. Griffin, Journal of the Society of the ic
Chemist, 1 (1950), 311).
Preferably, the t of the tant is within the range of from 0.005 to 10.0 wt.—%, more
preferably 0.01 to 7.5 wt.—%, still more preferably 0.01 to 5 \Nt.'°/o, yet more preferabiy 0.02 to
3.0 wt.-%, most preferably 0.05 to 2.0 wt.-% and in particular 0.1 to 1.0 wt.-%, based on the
total weight of the composition.
The composition according to the invention comprises an ionic polymer.
2012/070786
In a preferred embodiment, the content of the ionic polymer is within the range of from 40 to
99.995 wt.-%, more preferably 50 to 99.99 wt.-%, still more preferably 60 to 99.99 wt.—%, yet
more preferably 75 to 99.99 wt.—%, most preferably 80 to 99.8 wt.-%, and in particular 85.0 to
99.7 wt.-%, based on the total weight of the composition.
Preferably, the ionic polymer can serve as coagulant and/or flocculating auxiliary. Chemical
coagulation, the alteration of suspended and colloidal particles so they adhere to each other,
is one type of al treatment process. Coagulation is a process that causes the
neutralization of charges or a reduction of the repulsion forces between particles.
Flocculation is the aggregation of particles into larger agglomerations ("flocs"). Coagulation is
virtually instantaneous, while flocculation requires some time for the flocs to develop.
Preferably, the ionic polymer is water-soluble or water-swellable.
For the purpose of the specification, the term "water~soluble", particularly when it relates to
the water-solubility of polymers, ably refers to a solubility in pure water at ambient
temperature of at least 1.0 g l", more preferably at least 2.5 g l", still more preferably at least
.0 g l", yet more preferably at least 10.0 g I“, most preferably at least 25.0 g l'1 and in
particular at least 50.0 g I“. For the purpose of the specification, the term "water-soluble",
particularly when it relates to the water-solubility of monomers, preferably refers to a
solubility in pure water at ambient ature of at least 10 9 l1, more preferably at least 25
g I", still more preferably at least 50 g l“, yet more ably at least 100 g I", most
preferably at least 250 g l'1 and in particular at least 500 g l".
For the purpose of the specification, the term "water—swellable" preferably means that the
polymer, while not water-soluble, absorbs an iable amount of water. Typically, the
weight of the polymer increases by at least 2 wt.-%, preferably at least 5 wt.-%, after being
immersed in water at room temperature, e.g., 25°C, for 1 hour, more preferably by about 60
to about 100 times its dry weight.
In a red embodiment, the relative weight ratio of the non-ionic surfactant -O-Ft2
to the ionic polymer is within the range of from 0.005 : 100 to 10 : 100, more ably within
the range of from 0.01 : 100 to 7.5 : 100, still more preferably within the range of from 0.01 :
100 to 5 : 100, yet more preferably within the range of from 0.02 : 100 to 3 : 100, most
preferably within the range of from 0.05 : 100 to 2 : 100, and in particular within the range of
from 0.1 : 100 to1 :100.
Preferably, the water-soluble ionic polymer is derived from a monomer composition
ning
a) one or more non-ionic ethylenically unsaturated monomers, and/or
b) one or more cationic ethylenically unsaturated monomers, and/or
0) one or more anionic ethylenically unsaturated monomers.
In this regard, "derived from" means that the polymer ne of the ionic polymer
comprises repetition units, i.e., tion units are incorporated in the polymer backbone of
the ionic polymer, which repetition units are formed from the corresponding monomers in the
course of the rization reaction. For e, when the ionic polymer is derived from
dimethylaminopropyl acrylamide quaternized with methylchloride (= DlMAPA quat.), the
following repetition unit is incorporated in the polymer backbone:
Suitable non-ionic ethylenically unsaturated monomers include non-ionic monomers
according to general formula (I)
i3 i R“
wherein
R3 means hydrogen or C1-Ca-alkyl, and
R4 and R5 mean, independently of each other, hydrogen, -(C1—Cs)—alkyl or ~(C1-C5)-
hydroxyalkyl.
es of non-ionic rs of general formula (l) include acrylamide, N-methyl-
(meth)acrylamide, N-isopropyl(meth)acrylamide and N,N-substituted (meth)acryl amides
such as methyl(meth)acry|amide, N,N-diethyl(meth)acrylamide, N-methyl-N-ethyl-
(meth)acrylamide and N-hydroxyethyl(meth)acrylamide. Especially preferred is acrylamide.
For the purpose of the specification, the term "(alk)acrylate" shall refer to alkacrylate as well
as acrylate. In analogy, the term "(meth)acrylate" shall refer to methacrylate as well as
acrylate.
Further suitable non-ionic ethylenically unsaturated monomers include non-ionic amphiphilic
monomers ing to general formula (ll)
RI 6
H 20—-—c—-—c——zverv—0%8 l”)
Z means 0, NH or NR9 with R9 being C1-CS-alkyl,
Ft6 means hydrogen or C1~Cs-alkyl,
R7 means Cg-CS-alkylene,
R8 means hydrogen, Cg-Cag-alkyl, 'arYI and/or Cg-ng-aralkyl, and
n means an integer between 1 and 50.
Examples of non-ionic amphiphilic monomers according to general formula (ll) include
reaction products of (meth)acrylic acid and polyethylene glycols (10 to 50 ethylene oxide
units), which are etherified with a fatty alcohol, or the ponding reaction products with
(meth)acrylamide.
Suitable cationic ethylenically unsaturated rs include cationic monomers according
to general formula (III)
[T10 fi Y1
H2C—C--C-—22—Y0-—l\ll@—Y2l__ (Ill)
Y3 Xe
wherein
Ft1O means hydrogen or C1-Ca—alkyl;
22 means 0, NH or NR11 with R11 being C1-Cs-alkyl; and
Y0 means Cg-Ce-alkylene, possibly substituted with one or more hydroxy groups,
Y1, Y2, Y3, independently of each other, mean C1-CS-alkyl, and
X' means halogen, pseudo-halogen, acetate or SO4CH3‘.
Preferably, Y1, Y2 and Y3 are identical, preferably methyl. In a preferred ment, 22 is O
or NH, Y0 is ethylene or ene, F?10 is en or methyl, and Y1, Y2 and Y3 are methyl.
The cationic ethylenically unsaturated monomer according to general formula (lll) may be an
amide (22 = NH), e.g., dimethylaminopropyl acrylamide quaternized with chloride
(DIMAPA quat). Preferably, however, the ic nically unsaturated monomer
according to general formula (H) is an ester (22 = O), particularly dimethylaminoethyl (meth)-
acrylate quaternized with methylchloride (ADAME quat.).
Preferred cationic ethylenically unsaturated monomers are cationic radically polymerizable
(alk)acrylic acid esters, (alk)acrylic acid ters and (alk)acrylic acid amides. Preferably,
the aforementioned cationic monomers comprise 6 to 25 carbon atoms, more ably 7 to
carbon atoms, most preferably 7 to 15 carbon atoms and in particular 8 to 12 carbon
atoms. Still more preferably, the cationic ethylenically unsaturated monomer according to
general a (lll) is selected from the group consisting of methyl de quaternized
ammonium salts of dimethylaminomethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,
dimethylaminopropyl(meth)acrylate, dimethylaminomethyl(meth)acrylamide, ylamino-
ethyl(meth)acrylamide and dimethylaminopropyl(meth)acrylamide.
Suitable anionic ethylenically unsaturated monomers are selected from the group consisting
(c1) ethylenically unsaturated carboxylic acids and carboxylic anhydrides, in particular
acrylic acid, rylic acid, itaconic acid, ic acid, glutaconic acid, maleic acid,
maleic anhydride, fumaric acid and the water-soluble alkali metal salts f, alkaline
earth metal salts therof, and ammonium salts thereof;
(c2) ethylenically unsaturated sulfonic acids, in particular aliphatic and/or aromatic
ulfonic acids, for example vinylsulfonic acid, allylsulfonic acid, styrenesulfonic
acid, acrylic and methacrylic sulfonic acids, in particular sulfoethyl acrylate, sulfoethyl
methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy
methacryloxypropylsulfonic acid and 2-acrylamido-2—methylpropanesulfonic acid, and
the water-soluble alkali metal salts thereof, alkaline earth metal salts thereof, and
ammonium salts thereof;
(c3) nically unsaturated onic acids, in particular, for example, vinyl- and allyl—
phosphonic acid, and the water-soluble alkali metal salts thereof, alkaline earth metal
salts thereof, and ammonium salts thereof; and
(c4) sulfomethylated and/or phosphonomethylated acrylamides and the water-soluble alkali
metal salts f, alkaline earth metal salts thereof, and ammonium salts thereof.
Preferred anionic ethylenically unsaturated monomers are ethylenically unsaturated
carboxylic acids and carboxylic acid anhydrides, in ular acrylic acid, methacrylic acid,
itaconic acid, crotonic acid, glutaconic acid, maleic acid, maleic anhydride, c acid, and
the water-soluble alkali metal salts thereof, alkaline earth metal salts thereof, and ammonium
salts thereof; the water~soluble alkali metal salts of acrylic acid, in ular its sodium and
potassium salts and its ammonium salts, being particularly preferred.
In a preferred embodiment the ionic polymer is a homopolymer or a mer.
For the purpose of the specification, the term "homopolymer" shall refer to a polymer
obtained by polymerization of ntially a single type of monomer, whereas the term
"copolymer" shall refer to a polymer obtained by polymerization of two, three, four or more
different types of monomers (co-monomers).
When the ionic r is a homopolymer, it is derived from a cationic ethylenically
unsaturated monomer or an anionic ethylenically unsaturated r. When the ionic
polymer is a copolymer, it can comprise anionic, non-ionic and cationic ethylenically
rated monomers. In this case, the concentration f is to be chosen such that the
total charge of the ionic polymer is either negative or positive. Water-insoluble monomers
may only be present to the extent that the water solubility or the water swellability of the
resulting polymer is not impaired.
When the ionic polymer is a copolymer, it is preferably derived from at least one cationic
ethylenically unsaturated monomer and at least one non-ionic ethylenically unsaturated co-
monomer, or from at least one anionic ethylenically unsaturated monomer and at least one
non—ionic ethylenically unsaturated omer.
In a red embodiment, the ionic polymer is a cationic polymer, i.e. the total charge of the
ionic polymer is positive.
The cationic polymer is preferably derived from a monomer composition comprising
— cationic monomers in an amount within the range of from 1 to 100 wt.-%, preferably of
from 1 to 99 wt.-% and more preferably from 5 to 95 wt.-% from 20 to 95
, most preferably
wt.-%, and in particular from 40 to 80 wt.—%;
— non-ionic monomers in an amount within the range of from 0 to 99 wt.-%, preferably of
from 1 to 99 wt.-%, more ably of from 5 to 95 wt.-%, most preferably from 5 to 80
wt.-%, and in particular from 20 to 60 wt.-%; and
WO 57267
— anionic monomers in an amount within the range of from O to 30 wt.-%, preferably within
the range of from 0 to 20 wt.-%, more preferably within the range of from O to 10 wt.-%,
and most preferably within the range of from O to 5 wt.-%, an in particular 0 wt.%,
in each case based on the total weight of monomers contained in the monomer composition.
Preferably, the cationic r is derived from a monomer ition sing cationic
monomers in an amount within the range of from 1 to 99 wt.-%, preferably from 5 to 90 wt.—
%, more preferably from 20 to 90 wt.-%, and in particular from 20 to 80 wt.-%, in each case
based on the total weight of monomers contained in the monomer composition.
Very preferably, the cationic polymer is derived from a mixture of nic monomers,
preferably acrylamide and cationic monomers of general formula (III), preferably quaternised
dialkylaminoalkyl (meth)acrylates and/or dialkylaminoalkyl(meth)acrylamides. Particularly
preferred is dimethylamminomethyl (meth)acrylate quaternised with methyl chloride.
In such monomer compositions, the amount of cationic monomers is preferably at least 20
wt.-%, in particular within the range of from 20 to 80 wt.-%.
In another preferred embodiment, the ionic polymer is an anionic polymer, i.e. the total
charge of the ionic polymer is negative.
The c polymer is preferably derived from a monomer composition comprising
— c monomers in an amount within the range of from 1 to 100 wt.-%, preferably of
from 5 to 70 wt.—% and more preferably from 5 to 40 wt.-% , and
-— non-ionic monomers in an amount within the range of from O to 99 wt.-%, preferably of
from 30 to 95 wt.-%, and more preferably from 60 to 95 wt.-%, and optionally
— cationic monomers in an amount within the range of from O to 30 wt.-%, preferably within
the range of from O to 20 wt.-%, more preferably within the range of from 0 to 10 wt.-%,
and most preferably within the range of from O to 5 wt.-%, and in particular 0 wt.%,
in each case based on the total weight of monomers contained in the monomer composition.
Very preferably, the anionic polymer is d from a mixture of non-ionic monomers,
preferably acrylamide and anionic monomers, in particular ethylenically unsaturated
carboxylic acids and carboxylic acid anhydrides, preferably c acid, rylic acid,
itaconic acid, crotonic acid, glutaconic acid, maleic acid, maleic anhydride, fumaric acid and
the water-soluble alkali metal salts thereof, alkaline earth metal salts thereof, and ammonium
salts thereof, acrylic acid being particularly preferred as the anionic monomer.
A mixture of acrylic acid with alkyl (meth)acrylates and/or alkyl (meth)acrylamides is also
preferred.
In such monomer compositions, the amount of anionic monomers is preferably at least 5 wt.-
Preferably, the ionic polymer is of high molecular weight, but is nevertheless a water-soluble
or water-swellable r. Preferably, the ionic polymer has an average molecular weight
MW, measured by the GPC method, of at least 1.0 x 106 g/mol, preferably of at least 1.5 x 106
g/mol. In a preferred embodiment, the ionic polymer has an average molecular weight MW,
measured by the GPC method, of at least 3 x 106g/mol.
When the water~so|uble ionic r contains acidic groups, the acidic groups are
preferably at least partly neutralized. ably, the degree neutralization of the acidic
groups is at least 50%, more preferably at least 60%, still more preferably at least 70%, yet
more preferably at least 80%, most preferably at least 90%, and in particular at least 95%,
ve to the total number of acidic groups ned in the ionic polymer.
In a preferred embodiment, the ition according to the invention further comprises an
ionic polymeric dispersant.
Preferably, the ionic polymeric dispersant can also serve as ant and/or flocculating
auxiliary.
Preferably, the ionic polymeric dispersant is water-soluble or swellable.
Preferably, the content of the ionic polymeric dispersant is at most 35 wt.-%, more preferably
at most 25 wt.-%, and most preferably at most 20 wt.-%, based on the total weight of the
composition.
In a preferred embodiment, the content of the ionic polymeric dispersant is within the range
of from 0.005 to 35 wt.-%, more preferably 0.01 to 25 wt.-%, still more preferably 0.1 to 20
wt.—%, yet more preferably 0.1 to 15 wt.—%, most preferably 0.15 to 12 wt.-% and in particular
0.2 to 10 wt.-%, based on the total weight of the composition.
ably, the combined content of the ionic polymer and the ionic polymeric dispersant is
within the range of from 40 to 99.995 wt.-%, more preferably 50 to 99.995 wt.-°/o, still more
ably 75 to 99.995 wt.-%, yet more preferably 90 to 99.99 wt.-%, most preferably 95 to
99.95 wt.-% and in particular 98.0 to 99.9 wt.-%, based on the total weight of the
composition.
Preferably, the ionic polymeric dispersant exhibits a degree of polymerization of at least 90%,
more preferably at least 95%, still more preferably at least 99%, yet more preferably at least
99.9%, most preferably at least 99.95% and in ular at least 99.99%.
Preferably, the weight average molecular weight of the ionic polymeric sant is lower
than that of the ionic polymer.
In a preferred embodiment, the ionic polymeric dispersant has a weight average molecular
weight Mw of at most 2.0><106 g/mol. Preferably, the weight average lar weight MW of
the ionic polymeric dispersant is within the range of from 50,000 to 1,500,000 g mol", more
preferably 75,000 to 1,250,000 g mol", still more preferably 100,000 to 1,000,000 9 moi", yet
more preferably 120,000 to 750,000 g mol", most preferably 140,000 to 400,000 g mol" and
in particular 0 to 0 g mol". In a preferred embodiment, the weight average
molecular weight MW of the ionic polymeric dispersant is within the range of from 75,000 to
350,000 g mol".
ably, the molecular weight sity Mw/Mn of the ionic polymeric dispersant is within
the range of from 1.0 to 4.0, more preferably 1.5 to 3.5 and in particular 1.8 to 3.2. in a
preferred embodiment, Mw/Mn is within the range of from 27:07, more preferably 2.7i0.5,
still more preferably 2.7i0.4, yet more ably 27:03, most preferably 27:02 and in
particular 2.7:0.1.
Preferably, the ionic ric dispersant has a product viscosity within the range of from
100 to 850 mPas, more preferably 150 to 800 mPas, still more preferably 200 to 750 mPas,
yet more preferably 250 to 700 mPas, most preferably 300 to 650 mPas and in particular 350
to 600 mPas.
In a preferred embodiment the ionic polymeric dispersant is a homopolymer or a copolymer.
When the ionic polymeric dispersant is a homopolymer, it is derived from a cationic
ethylenically unsaturated monomer or an anionic ethylenically unsaturated monomer. When
the ionic polymeric dispersant is a copolymer, it can comprise c, non-ionic and cationic
ethylenically unsaturated monomers. In this case, the concentration thereof is to be chosen
such that the total charge of the ionic polymeric dispersant is either negative or ve.
Water-insoluble monomers may only be present to the extent that the water solubility or the
water swellability of the ionic polymeric dispersant is not impaired.
When the ionic polymeric dispersant is a mer, it is preferably d from at least one
cationic ethylenically unsaturated monomer and at least one non—ionic ethylenically
unsaturated co-monomer, or from at least one anionic ethylenically unsaturated monomer
and at least one non-ionic ethylenically unsaturated co-monomer.
in a preferred ment, the ionic polymeric dispersant is a cationic polymeric sant,
is the total charge of the ionic polymeric dispersant is positive.
Preferably, the cationic polymeric dispersant is derived from one or more cationic monomers,
more preferably from a single cationic monomer.
In a preferred embodiment, the cationic ric dispersant is derived from one or more
radically polymerizable, ethylenically unsaturated cationic monomers. Preferably, the cationic
monomers are selected from the group consisting of (alk)acrylamidoalkyltrialkyl ammonium
s, (alk)acryloyloxyalkyl trialkyl ammonium halides, alkenyl trialkyl ammonium s
and nyl dialkyl ammonium halides. Preferably, the aforementioned cationic monomers
comprise 6 to 25 carbon atoms, more preferably 7 to 20 carbon atoms, most preferably 7 to
carbon atoms and in particular 8 to 12 carbon atoms.
Preferably, the ic polymeric dispersant is derived from
~ 30 to 100 wt.-%, more preferably 50 to 100 wt.-%, and most preferably 75 to 100 wt.—% of
(alk)acrylamidoalkyltrialkyl ammonium s, (alk)acryloyloxyalkyl trialkyl ammonium
halides, alkenyl trialkyl ammonium halides, and/or dialkenyl dialkyl ammonium halides,
- O to 70 wt.-%, more preferably 0 to 50 wt.-%, and most preferably 0 to 25 wt.-% of non-
ionic co-monomers.
In a preferred embodiment, the cationic polymeric dispersant is derived from a dialkenyl
dialkyl ammonium halide, preferably a diallyl dimethyl ammonium halide (DADMAC).
In another preferred ment, the cationic polymeric dispersant is a copolymerizate of
epichlorohydrin and dialkylamine, ably dimethylamine, i.e. poly-[N,N-dimethyl-Z—
hydroxy-propylen-(1,3)-ammonium chloride].
In still another preferred embodiment, the cationic polymeric dispersant is derived from a
cationic r according to general formula (lll) as defined supra.
The ic monomer according to general a (lll) may be an ester (Z = 0), such as
ylaminoethyl (meth)acrylate quaternized with methylchloride (ADAME quat.).
ably, however, the r according to general formula (Ill) is an amide (Z = NH),
particularly dimethylaminopropyl acrylamide quaternized with methylchloride (DIMAPA quat).
Preferably, quaternized dialkylaminoalkyl (meth)acrylates or dialkylaminoalkyl(meth)acryl~
amides with 1 to 3 C atoms in the alkyl or alkylene groups are employed as monomers
according to general a (ll), more preferably the methyl chloride-quaternized ammonium
salt of dimethylamino methyl(meth)acrylate, dimethylamino ethyl(meth)acrylate, yl-
amino propyl(meth)acrylate, diethylamino methyl(meth)acrylate, diethylamino ethyl(meth)-
acrylate, diethylamino propyl(meth)acrylate, dimethylamino methyl(meth)acrylamide,
dimethylamino ethyl(meth)acrylamide, dimethylamino propyl(meth)acrylamide, diethylamino
methyl(meth)acrylamide, diethylamino ethyl(meth)acrylamide, diethylamino propyl(meth)-
acrylamide.
Especially preferred monomers are dimethylaminoethyl te and dimethylaminopropyl—
acrylamide. Quaternization may be effected using dimethyl sulfate, diethyl sulfate, methyl
chloride or ethyl chloride. Monomers quaternized with methyl chloride are particularly
preferred.
When the cationic polymeric sant is a copolymer, it is preferably derived from at least
one cationic monomer in combination with at least one non-ionic monomer.
Suitable non-ionic monomers include nic monomers according to general a (I)
and amphiphilic, non-ionic monomers according to general formula (II).
Examples of non-ionic monomers of l formula (I) include (meth)acrylamide, N-methyl
(meth)acrylamide, N—isopropyl(meth)acrylamide or N,N-substituted (meth)acryl amides such
as N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl-N-ethyl(meth)—
acrylamide or N-hydroxyethyl(meth)acrylamide.
2012/070786
Examples of amphiphilic, non—ionic monomers of general formula (II) e reaction
products of acrylic acid and polyethylene glycols (10 to 50 ethylene oxide units), which
are etherified with a fatty alcohol, or the corresponding reaction products with
(meth)acrylamide.
ln another preferred embodiment, the ionic polymeric dispersant is an anionic polymeric
dispersant, i.e. the total charge of the ionic polymeric dispersant is negative.
ably, the c polymeric dispersant is derived from one or more anionic monomers,
more ably from a single anionic monomer.
ably, the anionic polymeric dispersant is derived from one or more radically
polymerizable, ethylenically unsaturated rs.
Preferably, the anionic polymeric dispersant contains at least one of the functional groups
selected from ether groups, carboxyl groups, sulfone groups, sulfate ester groups, amino
groups, amido groups, imido groups, ten-amino groups, and/or quaternary ammonium
groups.
As examples thereof mention may be made of cellulose derivatives, polyvinyl acetates,
, starch derivatives, dextrans, polyvinylpyrrolidones, polyvinylpyridines, polyethylen—
imines, polyamines, polyvinylimidazoles, polyvinylsuccinimides, polyvinylmethylsuccin-
imides, polyvinyl-i,3-oxazolidones, polyvinylmethylimidazolines and/or their respective
copolymers with maleic acid, maleic anhydride, fumaric acid, ic acid, itaconic
anhydride, (meth)acrylic acid, salts and/or esters of (meth)acrylic acid and/or
(meth)acrylamide compounds.
Preferably, the anionic polymeric dispersant is derived from at least 30 wt.—%, preferably at
least 50 wt.-%, more preferably 100 wt.-%, of anionic monomer units which are derived from
anionic rs, such as, for example,
- nically unsaturated carboxylic acids and carboxylic acid anhydrides, in particular
acrylic acid, methacrylic acid, itaconic acid, crotonic acid, glutaconic acid, maleic acid
and maleic ide, fumaric acid and the water-soluble alkali metal salts thereof,
alkaline earth metal salts thereof, and ammonium salts thereof;
- ethylenically unsaturated ic acids, in particular aliphatic and/or aromatic
ulfonic acids, for example vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid,
acrylic and methacrylic ic acids, in particular sulfoethyi acrylate, sulfoethyi
methacrylate, suifopropyl acrylate, sulfopropyi methacrylate, 2-hydroxymethacryloxy-
propylsulfonic acid and 2-acryiamido-2—methylpropanesulfonic acid, and the water-
soluble alkali metal salts thereof, alkaline earth metal salts thereof, and um salts
thereof;
- ethylenicaliy unsaturated phosphonic acids, in particular, for example, vinyl- and allyl-
phosphonic acid and the water-soluble alkali metal salts thereof, alkaline earth metal
salts thereof, and ammonium salts f;
- ethylated and/or phosphonomethylated mides and the water-soluble alkali
metal salts thereof, alkaline earth metal salts thereof, and ammonium salts thereof.
Preferred anionic monomers are water-soluble alkali metal salts of acrylic acid,
polypotassium te being particularly preferred according to the invention.
Preferred embodiments A to D of the composition according to the invention are summarized
in the table here below:
substantiail un-branched and un-crosslinked cationic oi mer derived from at least a + b :
8) nic monomer according to monomer according (alk)acryiamide acryiamide
ethylenicaily formula (i) or (II) to formula (l)
unsaturated
monomer
b) cationic monomer according to monomer according (alk)acryloyloxyalkyi ADAME quat.
ethylenicaliy formula (ill) to formula (iii) where trialkyl ammonium
unsaturated 22 means 0 halide
monomer
non-ionic non-ionic surfactant comprises monomer surfactant according to ing to
surfactant Rl-O-A-O-R2 units derived from type (i), (ii), (iii), (iv) or general
ethylene glycol or (V) formula
(A)1
ethylene glycol and and
propylene glycol. HLB s 14
ionic polymeric monomer according to r according (alk)acryiamidoalkyl DIMAPA quat.
sant formula (ii) to formula (ll) where trialkyl ammonium
derived from
red variants ‘l to 6 of the embodiments A to D are summarized in the table here below:
-————_1
water s 65 wt.-% 5 12wt.-% s
% %
non-ionic surfactant 0.005-10 0.01-7.5
wt.—% wt.-% % wt.-%
S 35 wt-% 5 25 wt% 0.15 to 12 0.2 to 10
——__.wt.-%
cationic polymer derived from 40 to 50 to 99.99 75 to 999 75 to 99. 9 80 to 998 85 to 99.7
a) + b) + c) 99.995 wt.-% wt.-% o wt.-% .-°/o
wt.-%
a) non-ionic ethylenically 0 to 99 95 5 to 95 5 to 80
unsaturated monomer(s) wt.-% °/o wt wt.-% .- .-
b) cationic ethylenically 1 to 100 HO 99 wt.- 95 5 to 95 20 to 95 20 to 95
rated monomer(s) wt.-% % wt.-% .-
c) anionic ethylenically 0 to 30 20 0 to 10 0t05wt.-
unsaturated monomers wt.-% wt.-%
Preferred embodiments E to H of the composition according to the invention are summarized
in the table here below:
A ' fl 7—HWWWVVW
-com—onent—_G
ntiall un-b-ranched and un--crosslinked anionic ooi merderived from at least a + c:
a) non-ionic monomer according to monomer according to (alk)acrylamide acrylamide
ethylenically formula (I) or (ii) formula (i)
unsaturated
monomer
c) anionic ethylenically unsaturated ethylenically water-soluble salt sodium,
monomer carboxylic,sulfonic or unsaturated carboxylic of acrylic acid potassium or
phosphonic acid acid, carboxylic ammonium
derivative, anhydride or a water- acrylate
sulfomethylated or soluble salt thereof
phosphonomethylated
acrylamide, or a water-
e salt thereof
non—ionic non-ionic surfactant comprises monomer surfactant ing to
tant R1-O-A-O-R2 units derived from according to type general
ethylene glycol or (i), (ii), (iii), (iv) or formula (A),
ethylene glycol and (V) and
propylene . HLB .<. 14
ionic polymeric nically rated ethylenically water-soluble salt .
dispersant carboxylic, sulfonic or rated carboxylic of acrylic acid potassium or
derived from phosphonic acid acid, carboxylic ammonium
tive, anhydride or a water- acrylate
sulfomethylated or soluble salt thereof
phosphonomethylated
acrylamide, or a water-
solubie salt thereof
Preferred variants 7 to 12 of the embodiments E to H are summarized in the table here
below:
___I=__—__ater<65wt%<12wt.-% <12wt.-_—%-<10wt% <10wt.%
non-ionic surfactant 0005-10 5 0/001-5 Wt.- 0.02-3.0 0.05-2.0 011.0
wt-.% wt-.% wt.-% Wt-°/o Wt.-°/o
ionic polymeric dispersant(s) <25 wt.% <20 wt.-% 0.1 to 15 015 to 12 0.2 to 10
.-°/o Wt-%
anionicol merderivedfrom 50 to 9999 75 to 99.9 75 to 99.9 _0to_8599.8 99_7°/o_Wt.-to
W0 20131057267
—wt.-%))+b +0)
rated monomers mole.-% mole.-% mole.-% mole.-% mole.-% mole.-%
unsaturated monomers wt.-%
unsaturated monomers wt.-% % %
In the above tables, in case of the water, non—ionic surfactant, ionic polymeric dispersant and
cationic or anionic polymer all percentages by weight ) are based on the total weight of
the composition. In case of the monomers all percentages by weight (wt.-%) are based on
the total molar amount of monomers forming the cationic or anionic polymer.
Preferred components of the water-in-water polymer dispersion and their tive content
result from the following combinations of embodiments A to D with variants 1 to 6: A‘, A2, A3,
A4, A5, A6, B1, 82, B3, B4, B5, BS, C1, 02’ Ca, C4, CS, CG, D1, D2, D3, D4, D5, D6, E7, E8, E9, E10,
E11, E12, F7, F8, F93 F10, F11, F12, G7, G8, G9, G7, G8, G9, H7, H8, H9, H10, H11 and H12. For
example, "0“" means a combination of ment C with variant 4, Le, a ition
containing s wt.-% water; 0.02—3.0 wt.—% of at least one non-ionic surfactant Fil-O-A-O-Fi2
according to type (i), (ii), (iii), (iv) or (v); 0.1 to 15 wt.-% of at least one cationic polymer
dispersant derived from (alk)acrylamidoalkyl trialkyl ammonium halide; 75 to 99.9 wt.-% of at
least one cationic copolymer derived from a) 5-95 wt.-% of at least one (alk)acrylamide, b) 5-
95 wt.-% of at least one (alk)acryloyloxyalkyl yl um halide and c) at most 10 wt.-
% of an anionic monomer.
Preferably, the composition according to the invention is solid. in comparison to liquids, solid
compositions exhibit higher storage stability and allow an easier transportation.
Preferably the composition according to the ion is obtainable by a process comprising
the method of adiabatic gel polymerization, wherein the ionic polymer is formed by radical
rization of its monomer constituents in aqueous solution, optionally in presence of the
non-ionic surfactant R1-O-A-O-R2 and optionally in presence of the ionic polymeric
dispersant.
Preferably, the process ses the step of
(i) ting an aqueous reaction mixture comprising
a) one or more non-ionic ethylenically rated monomers, and/or
b) one or more cationic ethylenically unsaturated monomers, and/or
W0 5726’7
c) one or more anionic ethylenically unsaturated monomers,
d) optionally the ionic polymeric sant, and
e) optionally the non-ionic tant R1-O-A-O-R2,
to a radical polymerization by adiabatic gel polymerization, wherein the ionic polymeric
dispersant, the non-ionic surfactant R1-O-A-O~R2 and the non-ionic, anionic and cationic
ethylenically unsaturated monomers are defined as bed above.
Preferably, the content of the ionic polymeric dispersant, if present, is within the range of
from 0.1 to 40 wt.-%, more preferably 0.5 to 35 wt.-%, still more preferably 1.0 to 30 wt.-%,
yet more preferably 5.0 to 25 wt.-%, most preferably 10 to 20 wt.-% and in particular 12 to 16
wt.—%, based on the total weight of the aqueous reaction mixture.
In a preferred embodiment, the reaction mixture of step (i) comprises the non-ionic surfactant
R1-O-A-O-R2. In another preferred embodiment, the non-ionic surfactant R1-O-A-O-R2 is
added at a later stage of the process.
The aqueous reaction mixture comprises water, preferably deionized water. The water
content may vary from 0.01 to 99.99 wt.—%. In a preferred embodiment, the water content is
within the range of from 10 to 90 wt.-%, more preferably 15 to 85 wt.-%, still more preferably
to 80 wt.—%, yet more preferably 25 to 75 wt.—%, most preferably 30 to 70 wt.-% and in
particular 35 to 65 wt.-%, based on the total weight of the s reaction mixture. in
another preferred embodiment, the water content is within the range of from 35 to 90 wt.—%,
more preferably 40 to 85 wt.-%, still more preferably 45 to 80 wt.-%, yet more preferably 50
to 75 wt.-%, most preferably 55 to 70 wt.-% and in particular 60 to 66 wt.-%, based on the
total weight of the aqueous reaction mixture.
Preferably, the aqueous reaction e does not contain branching agents and cross—
linkers (particularly monomers having more than one radically rizable ethylenically
unsaturated moiety) such that the resulting cationic copolymer is substantially free of
branching. For e, the aqueous reaction mixture preferably does not contain any
monomers having more than one radically rizable nically unsaturated moiety.
Therefore, the ionic copolymer that is polymerized from the monomer composition, optionally
in the presence of the ionic polymeric dispersant, is preferably ntially un-branched and
substantially un-crosslinked.
If the water-soluble ionic polymer is derived from a monomer composition sing minor
amounts of cross-linking monomers, a preferred cross-linking monomer is allylacrylamide.
According to the invention, the complete absence of cross-linking monomers is principally
desirable, as cross-linking of the polymers tends to deteriorate the overall performance of the
composition according to the invention. r, mainly due to side reactions in the course
of monomer sis, in the production of cal grade monomer products the formation
of minor amounts of cross—linking monomers cannot always be completely suppressed.
However, this does not mean that branching reactions that might take place e.g. due to
radical ation reactions are completely excluded from the ion. Rather, as such
branching reactions always take place to a certain extent, they are generally tolerable. For
example, when the propagating radical chain abstracts a proton from a polymer backbone,
rization of this chain is terminated but a new radical is generated which in turn might
originate a new propagating radical, thereby leading to a branching point. However,
branching and cross-linking to an extent that can be observed in the course of (thermal)
azeotropic dewatering of c polymers in the presence of polyethylene glycol should
avoided.
The degree of branching and cross-linking, respectively, can be routinely determined by
measuring the gel content of a standardized aqueous solution of the water-soluble ionic
polymer. For the purpose of the specification, the gel content is preferably determined
according to the following procedure: 0,8 g of the sample is weighed to an accuracy of 0.01 g
into a 1000 ml . 800 ml of tap water (19—25 °C) is added in such a way that no lumps
are formed. Then, the solution is stirred for 30, 60, or 90 minutes, depending on the formula
instruction, with a finger r at 300 rpm. (dimensions of the finger stirrer: material:
ess steel, er: 8 mm, offset: 15 mm (measured from center to center), length of
the lower part of the shank: 65 mm, length of the section that provides the offset when
measured in parallel to said lower part of the shank: 25 mm, overall length: 240 mm. When
stirring is finished, the solution is placed on a standard sieve (315 4m O 3310/1-
200x50mm) and once it has passed through the sieve, this is rinsed through five times with
one liter of fresh water from the beaker. After the rinsing water has passed through the sieve
any residual water under the sieve is wiped off with the rubber policeman. Using the rubber
policeman and the powder funnel the residue is erred to a 100 ml measuring er
and the volume determined ing to the following formula: ml/L (undissolved gel
component) = Volume (residue) x 1,25.
2012/070786
Preferably, the water-soluble ionic polymer that is optionally d with an ionic polymeric
dispersion has a gel content (undissolved gel ent) of at most 50 ml/L, more
preferably at most 45 mI/L, still more preferably at most 40 ml/L, yet more preferably at most
mI/L, even more preferably at most 30 ml/L, most preferably at most 25 ml/L, and in
particular at most 20 mI/L, according to the above procedure.
Usually, before the free radical polymerization is initiated, the s on mixture is
prepared from its components. The preparation of aqueous reaction mixtures is known to the
skilled person. The components may be added simultaneously or consecutively.
The components may be added by conventional means, e.g. by pouring or dropping liquids,
by dosing powders, and the like.
Preferably, an aqueous dispersion is prepared comprising the ionic ethylenically unsaturated
monomer, the non-ionic ethylenically unsaturated monomer and optionally the ionic
polymeric dispersant, preferably in homogeneous aqueous solution. Further ents
may be added to the aqueous sion, such as chelating agents, buffers (acids and/or
bases), branching agents, cross-linkers, chain transfer agents, and the like.
le branching agents, cross-linkers and chain transfer agents are known to the skilled
person. Preferably, however, no branching agents, cross—linkers or chain transfer agents are
added.
in a preferred embodiment, the pH of the aqueous dispersion is adjusted to a value within the
range of from 1.0 to 5.0, more preferably 1.5 to 4.5, still more preferably 2.0 to 4.0, and most
preferably 2.5 to 3.5. In another preferred embodiment, the pH is adjusted to a value within
the range of from 2.0 to 6.0, more preferably 2.5 to 5.5, and most preferably 3.0 to 5.0. The
pH value may be adjusted by means of suitable acids and bases, respectively. Preferred
acids are organic acids and mineral acids, such as formic acid, acetic acid, hydrochloric acid
and sulfuric acid.
Preferably, the aqueous dispersion is vigorously stirred by means of, e.g., a conventional
spiral-stirrer, high-speed mixer, homogenizer, and the like.
In principle, it is not ary that the entire amount of each component is lly present
when the aqueous reaction mixture is ed. Alternatively, l dispersion of the
monomers can be effected at the beginning of the polymerization, the remainder of the
W0 20131‘057267
monomers being added as metered portions or as a continuous feed distributed over the
entire course of polymerization. For example, only a certain portion of a particular
component, e.g., only 70 wt.-% of the non-ionic ethylenically unsaturated monomer may be
lly employed, and thereafter, possibly in the course of the polymerization reaction, the
remainder of said particular component, e.g., the residual 30 wt.-% of the non-ionic
ethylenically unsaturated monomer, is employed.
In a preferred ment of the method according to the invention, before the aqueous
reaction mixture is subjected to a radical polymerization, a water-soluble salt is added in
quantities of 0.1 to 5.0 wt.~%, based on the total weight of the aqueous reaction mixture.
Ammonium, alkali metal and/or alkaline earth metal salts, preferably ammonium, sodium,
potassium, calcium and/or ium salts, can be used as water-soluble salts. Such salts
can be salts of an inorganic acid or of an organic acid, preferably of an organic carboxylic
acid, sulfonic acid, onic acid, or of a mineral acid. The water-soluble salts are
ably salts of an aliphatic or aromatic mono-, di-, polycarboxylic acid, of a
hydroxycarboxylic acid, ably of acetic acid, propionic acid, citric acid, oxalic acid,
succinic acid, malonic acid, adipic acid, fumaric acid, maleic acid or c acid, or ic
acid, hloric acid or phosphoric acid. Very particularly preferably, sodium chloride,
ammonium e and/or sodium sulfate are used as water-soluble salts.
The salts can be added before, during or after polymerization, polymerization ably
being carried out in the presence of a water—soluble salt.
After the aqueous reaction mixture has been prepared, it is subjected to a radical
polymerization by tic gel polymerization reaction, i.e., polymerization of the monomer
composition containing the non—ionic ethylenically unsaturated monomers and/or the cationic
ethylenically unsaturated monomers, and/or the non-ionic ethylenically rated
monomers, optionally in the presence of the ionic polymeric dispersant and optionally in
presence of the non-ionic surfactant ~A-O-R2 is initiated, thereby yielding a solid gel
comprising the ionic polymer, the ionic polymeric dispersant, if present during the
polymerization process, and the non-ionic surfactant R1-O-A-O-R2, if present during the
polymerization process.
The d person knows how to radically polymerize monomers in an aqueous reaction
mixture.
Preferably, the start temperature for the polymerization is adjusted to a range of from —10 to
°C, more preferably a range of from 0 °C to 15 °C. Higher start temperatures lead to
polymer gels which are too soft to be further processed in uent eduction and
drying processes.
Preferably, oxygen is purged from the aqueous reaction mixture by an inert gas, such as
nitrogen. The polymerization is preferably carried out under an inert gas atmosphere, e.g.
under a nitrogen atmosphere.
Typically, the exothermic polymerization on of the monomers is started by addition of a
polymerization initiator.
ls may be formed, e.g., upon thermally induced or photochemically induced homolysis
of single bonds or redox ons.
es of suitable water-soluble tors include, e.g., 2,2'-azobis-(2—amidinopropane)
dihydrochloride, 4,4'-azobis-(4-cyanopentanoic acid), 2,2‘-azobis(2-(-imidazolinyl)propane
dihydrochloride or redox s such as ammonium persulfate/ferric sulfate. Oil-soluble
initiators include, e.g., dibenzoyl peroxide, dilauryl peroxide or tert-butyl de, or azo
compounds such as 2,2‘-azobisisobutyronitrile, dimethyl 2,2'-azobisisobutyrate and 2,2”-
azobis-(4-methoxy—2, 4—dimethylvaleronitrile). The initiators may be used either individually or
in combinations and generally in an amount of about 0.015 to O.5wt.-% of the total weight of
the aqueous reaction mixture. The skilled person principally knows how to modify the amount
and type of the initiator in order to modify the properties of the resultant polymer product,
e.g., its average molecular weight.
Preferably, azo compounds such as 2,2‘-azobisisobutyronitrile, 2,2'-azobis(2-(-imidazolin-2—
yl)propane dihydrochloride, 2,2’-azobis(2-aminopropane) dihydrochloride or preferably
potassium persulfate, ammonium persulfate, hydrogen de, optionally in ation
with a reducing agent, e.g. an amine or sodium sulfite, are used as radical initiators. The
amount of tor, relative to the monomers to be polymerized, generally ranges from 10‘3 to
1.0 wt.-%, preferably from 10‘2 to 0.1 wt.-%. The initiators can be added completely or also
only in part at the beginning of the polymerization, with subsequent apportioning of the
residual amount over the entire course of polymerization. in a preferred ment, the
polymerization is initiated by means of a sodiumperoxodisulfate and, after reaching the
maximum temperature, continued with an azo initiator, such as 2,2'-azobis(2-(-imidazolin-2—
yl)propane dihydrochloride. At the end of the polymerization, a redox initiator system is
ably added in order to reduce the content of residual monomers.
In a preferred embodiment, once the exothermic polymerization reaction is complete, i.e.
lly after the temperature maximum, the content of residual monomers is further
d by uent addition of redox initiator.
in another red embodiment, the monomer composition and optionally the ionic
polymeric dispersant is apportioned into the polymerization reactor during polymerization. in
general, a portion, e.g. 10 to 20% of the monomers and optionally the ionic polymeric
dispersant, is initially introduced. Following initiation of rization, the above-mentioned
apportioning is ed, optionally accompanied by further apportioning of polymerization
initiator.
In addition, it is also possible to remove water during polymerization and optionally to add
further cationic polymeric dispersant.
The polymerization may be carried out in aqueous solution, in batches in a polymerization
vessel or continuously on an endless belt, as is described, for example, in DE 3544770.
Preferably, the polymerization reaction is d out at atmospheric re t a
supply of external heat. Through the exothermal reaction, heating of the polymerization
mixture takes place with formation of a polymer gel.
Preferably, the reaction mixture reaches a maximal end temperature within the range of from
50 to 150 °C, depending on the content of polymerisable material and on the decomposition
kinetics of the initiator used.
Polymerization times are the same as those conventionally used in the art, generally 1.5 to
18 hours and preferably 2 to 6 hours, although as little as one-half hour could be used.
However, ting more rapid polymerization over a shorter period of time creates
problems with removing heat. In this regard it is greatly preferred that the polymerization
medium be stirred well or otherwise agitated during the polymerization.
Polymerization conversion or the end of polymerization can easily be detected by
determining the t of residual monomers. Methods for this purpose are familiar to those
skilled in the art (e.g. HPLC).
After the temperature maximum has been reached, the solid polymer gel being formed can
be further processed immediately or else after a holding time. Preferably the polymer gel will
be further processed ately after the maximum temperature has been reached.
Following polymerization, it also can be advantageous to cool down the aqueous reaction
mixture before optionally adding further additives, such as salts or acids, to the dispersion,
preferably with stirring.
To reduce the residual monomer content, it is also possible to increase the temperature
during the course of the polymerization. Alternatively, it is also possible to use onal
initiators during and at the end of the polymerization and/or residual monomer destructors.
al monomer destructors within the meaning of the invention are substances that
modify polymerizable rs by means of a Chemical reaction in such a way that they are
no longer polymerizable, such that within the meaning of the invention they are no longer
monomers. Substances that react with the double bond t in the monomers and/or
substances that can initiate a more extensive polymerization can be used for this purpose.
As residual monomer destructors that react with the double bond, reducing agents can for
example be used, preferably nces from the group of acids and neutral salts of acids
derived from sulfur having an oxidation number lower than Vl, preferably sodium dithionite,
sodium thiosulfate, sodium sulfite or sodium disulfite, and/or substances having a hydrogen
sulfide group, preferably sodium hydrogen sulfide or compounds from the group of thiols,
preferably mercaptoethanol, dodecyl tan, thiopropionic acid or salts of thiopropionic
acid or thiopropanesulphonic acid or salts of opanesulphonic acid, and/or substances
from the group of amines, preferably from the group of amines with low volatility, preferably
ropanolamine or thyl ethanolamine, and/or nces from the group
comprising Bunte salts, formamidine sulfinic acid, sulfur dioxide, aqueous and organic
solutions of sulfur e or thio urea.
Preferably, at the end of the polymerization the remaining aqueous ition has a
residual t of cationic ethylenically unsaturated monomers of at most 5,000 ppm, more
preferably at most 2,500 ppm, still more preferably at most 1,000 ppm, yet more preferably at
most 800 ppm, most preferably at most 600 ppm an in particular at most 400 ppm.
Preferably, at the end of the polymerization the remaining aqueous composition has a
residual content of anionic ethylenically unsaturated monomers of at most 5,000 ppm, more
WO 57267
preferably at most 2,500 ppm, still more preferably at most 1,000 ppm, yet more preferably at
most 800 ppm, most ably at most 600 ppm an in particular at most 400 ppm.
Preferably, at the end of the polymerization the remaining aqueous composition has a
residual content of non-ionic ethylenically unsaturated monomers of at most 5,000 ppm,
more ably at most 2,500 ppm, still more preferably at most 1,000 ppm, yet more
preferably at most 800 ppm, most preferably at most 600 ppm an in particular at most 400
ppm.
Preferably, the composition according to the invention contains no substantial amounts of
organic solvents and volatile organic constituents (VOC). ably, the composition does
not contain any organic solvents or volatile c constituents (VOC), or at most 50 ppm,
preferably at most 45 ppm, more preferably at most 40 ppm, still more preferably 35 ppm, yet
more preferably at most 30 ppm, even more preferably at most 25 ppm, most preferably at
most 20 ppm, and in particular at most 15 ppm. The content of c solvents and volatile
organic constituents (VOC) can be measured by routine procedures.
ably, the composition according to the invention contains no substantial amounts of oil.
ably, the composition does not contain any oil, or at most 50 ppm, preferably at most
45 ppm, more preferably at most 40 ppm, still more ably 35 ppm, yet more preferably
at most 30 ppm, even more preferably at most 25 ppm, most preferably at most 20 ppm, and
in particular at most 15 ppm. The content of oil can be measured by routine procedures.
Preferably, the process according to which the composition according to the invention is
obtainable further comprises the step of
(ii) crushing or chopping the gel obtained from step (i);
Step (ii) may be carried out in standard industrial apparatus.
If the polymerization is carried out in presence of an ionic polymeric dispersant as d
supra, the weight ratio of the ionic polymeric dispersant to the ionic polymer is decisive for
further sing of the polymer gel. if the ratio exceeds the value of 0.01 :10 to 1:4, there
are formed very soft gels, which immediately coalesce once again after size reduction and
make drying on the industrial scale almost impossible.
2012/070786
lonic polymers with ionic monomer proportions of greater than 60 wt % are particularly critical
as regards further processing. In those cases, it has often proved effective to adjust the
weight ratio of the ionic polymeric dispersant to the ionic polymer to 02:10 to <1 :10.
in a preferred embodiment, in step (ii) a separating and/or ticking agent is added to the
gel obtained from step (i).
The separating and/or anti-sticking agent can be any surfactant with separating and/or anti-
sticking properties. Preferably, the separating and/or anti-sticking agent is selected from the
group consisting of fatty acid dialcohol amides, quaternized reaction products of fatty acids
and alcohol amines and fatty acid amidoalkyl betaines.
Typically, for the size-reduction of a gel formed by a gel polymerization process the addition
of such ting and/or anti-sticking agent is required.
It has been surprisingly found that by the presence of the nic surfactant R1-O-A-O-R2,
the amount of separating and/or anti-sticking agent can be reduced or completely omitted.
If a separating and/or anti-sticking agent is used, it is added in such an amount that the
flowability of the final composition obtained after step (iv) is not impaired and the foaming
behavior of the final composition when used as a flocculant in solid-liquid tion is not
negatively affected.
Preferably, the separating and/or anti-sticking agent does not have any defoaming or anti—
foaming properties.
In another red embodiment, step (ii) is performed without the addition of a separating
and/or anti-sticking agent.
After size reduction, the gel is preferably dried at a temperature within the range of from 70°C
to 150°C, i.e. the process preferably further ses the step of
(iii) drying the product obtained from step (ii) at a temperature within the range of from 70
to 150 °C.
More ably, step (iii) is performed at a temperature within the range of from 80 °C to 120
°C, in particularly within the range of from 90 °C to 110 °C.
Preferably, the drying is performed in batches in a circulating-air drying oven. In the
continuous version, drying takes place in the same temperature ranges, for example on a
belt dryer or in a fluidized-bed dryer. After drying, the product preferably has a moisture
content of less than or equal to 12 wt.-%, and particularly preferably of less than or equal to
wt.-%.
After drying, the product is preferably ground to the desired particle-size fraction, i.e. the
process preferably r comprises the step of
(iv) grinding the product obtained from step (iii).
Preferably, at least 90 wt % of the ground product should have a size not exceeding 2.0 mm,
more preferably a size not exceeding 1.5 mm, in order to achieve rapid dissolution of the
product. Preferably, fine fractions smaller than 0.1 mm should amount to less than 10 wt %,
preferably less than 5 wt %.
Preferably, the particles after drying have a form factor of at most 50%, more preferably at
most 45%, still more preferably at most 40%, yet more ably at most 35%, even more
preferably at most 30%, most preferably at most 35%, and in particular at most 30%. The
form factor can be routinely determined according to the following procedure:
Preferably, when the composition according to the invention is provided in particulate form,
the polymer particles are characterized by a specific particle shape and spherical particle
content. The non-spherical parameter (NSP) is a measure of the degree of deviation from a
spherical shape. When determining the non-spherical parameter (NSP) of the les
ing to the invention, 9.9. by means of a PartAn 2001 L (photo-optical image analyzing
system), the non-spherical ter (NSP) is preferably at least 20%, more ably at
least 30%, still more preferably at least 40%, yet more preferably at least 50%, even more
preferably at least 60%, most preferably at least 70%, and in particular at least 75%.
ably, the process further comprises the step of
(v) adding the nic tant R1-O-A-O-R2.
Step (v) may be performed at any time during the process according which the composition
according to the invention can be obtained, i.e. before step (i), after step (iv) or at any time in
between.
In a preferred embodiment, step (v) is performed before step (i), i.e. the non-ionic surfactant
Ft1-O-A-O-Ft2 is added to the aqueous reaction mixture comprising the monomer composition
and is t during the polymerization reaction.
in another preferred embodiment, step (v) performed after step (iv), i.e. the non-ionic
surfactant Ft1-O-A-O-R2 is added to the ground product obtained from step (iv).
In still another preferred embodiment, step (v) is performed between steps (i) and (iv), i.e. the
non—ionic surfactant Ft1-O—A—O-R2 is added to the gel obtained from step (i), to the crushed or
d gel ed from step (ii) or to the dried product obtained from step (iii).
in yet another preferred embodiment, the amount of non-ionic tant divided into at least
two ns, which independently of one r may be added at any time of the process.
For example, one portion is added before step (i) and the other portion is added to the
ground product obtained from step (iv).
A further aspect of the invention relates to a process for manufacturing the composition
according to the invention comprising steps (i), optionally (if), optionally (iii), optionally (iv)
and (v) as defined supra. Preferably, the process comprises all of the steps (i)-(v).
The composition according to the invention is useful as additive in solid/liquid separation
processes, e.g., as flocculating auxiliary in the sedimentation, ion or filtration of solids;
as thickener; or as a ion agent or drainage aid, e.g., in papermaking/ retention in paper;
or in sludge dewatering in sewage plants.
A further aspect of the ion relates to the use of the composition according to the
invention as flocculating auxiliary for purifying waste water or conditioning potable water.
A further aspect of the invention relates to a process for treating waste water, drinking water
or process water, the process comprising the steps of
(a) optionally, especially when the composition according to the invention is provided in
solid form, preparing a water-in-water polymer sion by mixing the ition
according to the invention with water, and
(b) flocculating an aqueous suspension or slurry, ably sewage sludge, by introducing
the water-in-water polymer dispersion, and
(c) dewatering the aqueous suspension or slurry, preferably by using a decanter, chamber
filter press or belt filter press.
Preferably, the composition according to the invention is used in a dosage within the range of
from 20 g/m3 to 1000 g/ms, more ably within the range of from 60 g/m3 to 500 g/m3, still
most preferably within the range of from 80 g/m3 to 450 g/m3, most preferably within the
range of from 100 g/mato 400 g/m3, and in ular within the range of from 120 g/m3 to 350
g/m3, based on the amount of the s suspension or slurry.
A further aspect of the invention relates to the use of the composition according to the
invention as additive, preferably as retention agent or drainage aid, in the cture of
paper, paperboard or cardboard.
A further aspect of the invention relates to a process for the manufacture of paper,
paperboard or cardboard, the process comprising the steps of
(a) optionally, ally when the ition according to the invention is provided in
solid form, preparing a water—in-water polymer dispersion by mixing the composition
according to the invention with water, and
(b) adding the water-in-water polymer dispersion to an aqueous cellulosic suspension.
Preferably, the composition according to the invention is employed in a dosage within the
range of from 20 g/m3 to 1000 g/ms, more preferably within the range of from 60 g/m3 to 500
g/m3, still most ably within the range of from 80 g/m3 to 450 g/m3, most preferably within
the range of from 100 g/m3 to 400 g/m3, and in particular within the range of from 120 g/m3 to
350 g/m3, based on the amount of the aqueous cellulosic suspension.
As all preferred embodiments of the composition ing to the invention also apply to the
uses according to the invention as well as to the ses according to the invention, these
preferred embodiments are not mentioned again.
EXAMPLES
The following examples further illustrate the invention but are not to be construed as limiting
its scope.
EXAMPLE 1
WO 2013057267
Lab tests were performed by dewatering sludge s (obtained from central wastewater
treatment plant in DiJsseldorf-llverich) by the sieve method bed here below.
Two flocculation auxiliaries were tested:
Comparative flocculation auxiliary: copolymer of acrylamide with cationic acrylic acid
derivative
Inventive lation auxiliary: copolymer of acrylamide with cationic acrylic acid
derivative and 0.5% non-ionic tant (reaction product
of a 012-C18 fatty alcohol, ethylene oxide and propylene
oxide) applied in the preparation process of the copolymer
before the drying process.
In a 600 ml beaker, a 0.1 wt.-% aqueous solution of the tive flocculating auxiliary (500
:r 10 ml) was prepared and sheared by means of a dispersing device "Ultra Turrax T 25 N"
with sing tool "8 25 N — 18 G" (Janke & Kunkel) at a rotation speed of 24,000 min'i.
Then, a sample of sludge (500 i 10 ml) was conditioned with a portion of the sheared
flocculating auxiliary solution (flocculating auxiliary dose: 200 g(weight solids)/m3) using a
four—blade ess stirrer (RW 20 DZM Janke & Kunkel) at 1000 i 20 min'1 for 10 i 0.5
seconds and dewatered by a drainage screen (stainless steel, 150 x 50 mm; 200 um mesh).
The resulting filtrate (centrate) was subjected to a foaming test.
Foam test conditions: 300 ml filtrate, 100 | air/hour, foam height in mm
The ing foam heights over time periods are depicted in the table here below and in
Figure l:
foam height (mm)
comp.
time (min.) Example Examplei
A clearly reduced foaming tendency could be seen in the lab trial.
EXAMPLES 2-4
The inventive flocculation auxiliary of e 1 was tested at three ent wastewater
treatment plants (\MNTP). Two plants are purely pal sewage treatment plants, each
with a design capacity of 137,000 and 120,000 population equivalents. The third treatment
plant has a design capacity of 1,200 000 population lent.
All water treatment plants bed here set to a degradation of organic constituents in the
sludge digestion tanks. Then the sludge is drained with the addition of powdered flocculating
auxiliaries using modern high performance decanters.
EXAMPLE 2
Design capacity 1.2 million inhabitants.
In this new ty the inflowing water consists of 75% from industry and 25% from municipal
s. The biological process is d here into high-and low-load range. The resulting
excess sludge is thickened using a decanter and then fed to the digester.
The sludge is dewatered by a total of three Sharpless decanters at a rotation speed of 2700
min“. During the operational testing centrifuge 1 was charged with 40 mm sludge. The
dosing of the flocculating auxiliary was 265 g/m3. The resulting te was fed into a
process water tank and after nitrogen elimination and neutralization re-added to the inflow of
sewage. Since development of foam would be disruptive approximately 16 l/day of defoamer
(suspension of polyethylene wax in mineral oil) are dosed into the te, normally.
Comparative operational tests were conducted with the comparative flocculation auxiliary
and the inventive flocculation auxiliary according to Example 1. By adding an additional
defoamer (suspension of polyethylene wax in mineral oil), the foam height was kept constant.
W0 2013(057267
1) Pump for defoamer when using the comparative flocculation auxiliary: 50 strokes / minute
2) Pump for defoamer when using the inventive flocculation auxiliary: 25 strokes / minute
in summary, the dosage of additional er could be cut by half.
EXAMPLE 3
Design capacity 137 000 inhabitants.
Mainly municipal wastewater is processed in this treatment plant. The biological return
sludge is thickened using a decanter and then fed to the digester. After a digestion period of
days 220 g/m3 lating auxiliary are dosed and dehydrated with a modern high
performance decanter of the company KHD.
As no antifoam agent is used in this application the formation of foam in the centrate limits
the volume flow of the machine. Foam formation is a massive handicap. With no or less foam
pment, the flow rate and, therefore, productivity can be increased.
1) Maximum throughput when using the comparative flocculation auxiliary: 27 WM
2) Maximum hput when using the inventive flocculation auxiliaryExample 1: 32 m3/ h.
Le. 19% performance se.
The higher mud flow shortens the run time of the er and, thus, saves energy and
costs.
EXAMPLE 4
Design capacity 120 000 inhabitants
This sewage plant is processing almost exclusively domestic sewage. The sludge is
processed in a biology stage, thickened with a flotation and fed to the digester. After an
appropriate residence time, the sludge is dewatered. Then 163 g / m3 flocculating auxiliaries
is added and the dewatering is med by using a modern high performance decanter with
a hput of 43 m3/h. Since there is a great tendency to foam a defoamer from Ashland
nsion of a polyethylene wax in l oil) is dosed.
1) Output power for the pump for defoaming agent when using the comparative flocculation
auxiliary: 120%
2) Output power for the pump for defoaming agent when using the inventive flocculation
auxiliary: 20%
ln es 24, no negative effect could be observed on the drainage behavior in the
decanter such as lower separation rate or dry solids.
EXAMPLES 5 TO 11
In a series of experiments (polymerization reactions of acrylamide and various ionic
comonomers) the influence of cross—linkers (contained in the starting material and/or
specifically added in predetermined amounts) on undesirable gel formation was studied.
In Examples 5, 8, 10 and 11, a technical grade of cationic monomer was employed that
already contained about 30 ppm cross-linking monomer (N-allylacrylamide, NAA). In
Example 9, an analytical grade of the same cationic monomer was employed that did not
contain any detectable amount of cross—linker.
ln Examples 5, 6 and 7, N,N'-methylenebisacrylamide (MBA) was separately added as cross-
linker in various predetermined amounts. ln Examples 8 and 9, lacrylamid (NAA) was
separately added as cross-linker in various predetermined s.
The composition of the reaction mixtures, the experimental conditions as well as the
measured salt viscosities and gel amounts are summarized in the table here below. The gel
s ed for Examples 5 to 9 are additionally depicted in Figure 2:
batch cross-linking ionic monomer time sis results
monomer degassing
] temp in ppm] viscosity
in °C mL mPas 7
Exam-le 5 catal sis: ABAH 500 um;TBHPlNads 10/15 um;ful| lioohtexosure //1 % Al
m—m_'-’-_——
I}---_—-_--
_--'--—--
E--_—-_-
W0 20131057267
___—___-
|Example 6 (catalysis ABAH 500 ppm; full light exposure // 1 % Al)
m—“——-_--
___-___-
“___—___
___—___-
Example 7 (catalysis ABAH 500 ppm, TBHP/Nads 1/3 ppm; full light exposure // 1 % Al)
___-
___——-3 0 38 _-
3 0 100
“___-__-
Example 8 (catalysis: ABAH 500 ppm; TBHP/ Nads 10/15 ppm; full light exposure // 1 % AI)
m—u————-
[___—___-
I--——0 150 300 _-
E--———--
___—___-
Example 9 (catalysis: ABAH 500 ppm; TBHP/ Nads 10/15 ppm; full light exposure // 1 % Al)
___-3 100 34 2
[___-—-3 100 105
-3 100 300
___ _-
Example 10 (catalysis: ABAH 500 ppm; TBHP/ Nads 10/15 ppm; full light exposure // 1 % Al)
_—_—0 200 4 _-
I-—-__-—--
m—u__-_—
m—“—_-—--
--___-_—-
Examnle 11 catal sis: ABAH 500 o m; TBHP/ Nads 10/15 um; full liht exosure // 1 % Al
m_-_DIMAPAQuattechnicaH nd 100 22 _—
_-—DlMAPAQuattechnical‘i nd 100 150 _-
DlMAPA chnical‘i nd 100 160 _-
nd = not determined
DlMAPA Quat = N,N,N-trimethylammoniumpropylacrylamide chloride
ADAME Quat = N,N,N-trimethylammoniumethyl(meth)acrylate chloride
NAA = N-allylacrylamid
MBA = ethyleneblsacrylamide
ABAH = 2,2'-azo-bis(2-amidinopropane)dihydrochloride
TBHP = tertbutylhydroperoxide
Nads = sodium disulfite
AI = defoamer
1 completely cross-linked, only swells. measuring viscosity not possible
2 starting material not containing detectable s of cross-linker
3 conclusions can hardly be drawn from viscosity, as liquid is very diluted and swollen particles disturb
measurement by sing viscosity
Noam:- starting material contains about 30 ppm cross-linker (and varying amounts of tor)
starting material not containing detectable amounts of cross-linker
relative to total amount of active substance
at velocity 10
Additional differences between the polymers contained in the composition according to the
invention and the r of Example 5 have been demonstrated by measuring the particle
shape and spherical particle content. By using a PartAn 2001 L, a photo-optical image
analyzing system, the non-spherical parameter (NSP), a shape factor of these polymer
particles was ed. These ements showed for the particles of the polymer of
Example 5 a deviation of the NSP from an ideal spherical shape of approx. 14% and for the
polymers of Example 7 and 9 a deviation of approximately 76%.
When comparing the above experimental data with the teaching of US 5,684,107, the
following can be concluded:
When ing the r compositions according to the invention in the intended
application, products having an excellent water-solubility are , as insoluble parts do
not provide any functional properties or even cause problems in these ations. In nearly
all intended applications some kind of flocculation or ation mechanism is the key to
product performance. Only water-soluble polyelectrolytes possess the ability to interact with
material in the intended way. Further, ble parts (gel particles) may lead to clogging of
protective filters or, e.g. in paper production, may lead to holes or even breaks of the paper
sheets which is a very cost intensive problem for paper manufacturers. Therefore, for the
purposes of the polymer dispersions ing to the invention, it is always desirable to
produce polymer products (e.g. s) that easily dissolve and form smooth solutions
without or only with a very low formation of insoluble parts.
To prove the good solubility of the products according to the invention, solubility tests and
gelling tests have been conducted. Based upon long application experience, in standard
applications the gel/insoluble limit should certainly not exceed 30 ml/L (cf. values in the 3rd
column in above table). For other applications like e.g. paper production, even more
demanding limits are set, e.g. below 10 ml/L, below 5 ml/L or even below 1 ml/L. As
evidenced by the above experimental data, gel contents below these limits can only be
achieved at very low contents or in absence of linkers.
At contents of cross-linker amounting to 50 ppm or more according to US 5,684,107, the
resultant products are wide out of specification. The exemplified itions of US
,684,107 contain such inacceptable high quantities of cross-linkers. Further, if no cross-
linkers would be added to the reaction mixtures according to US 5,684,107, the subsequent
azeotropic (in general thermal) dewatering step in presence of polyalkylene glycol would lead
to crosslinking/gel formation with acid groups connected to the polymer backbone.
W0 2013[057267
Furthermore, the polymer compositions according to the invention are ably only water-
based in contrast to the products in US 5,684,107 which are water-in-oil based polymers.
Further, the polymer compositions according to the invention do not need to be dewatered
and other solvents or oils do not need to be removed. Thus, the polymer compositions
according to the ion are easier to manufacture and have a better ecological profile.
Claims (15)
1. A ition comprising (i) a non-ionic surfactant R1-O-A~O-R2, wherein — the residue -O—A-O— is derived from a polyalkylene glycol HO-A-OH that comprises monomer units derived from an (Cg-Ce)-alkylene glycol or a mixture of at least two different (Cg-C6)-alkylene glycols; and — R1 is ed from the group consisting of -H, -(C3—Czo)-a|ky|, '(Cs'C20)'aIKGHYI, '(C=O)-(C3'CZO)'aIKYI and ~(C=O)—(Cg-Czo)-alkenyl, and — R2 is selected from the group consisting of -H, -(C1-Cs)-alkyl, -benzyl, ~(C=O)~ (C8-C20)-alkyl and -(C=O)—(Cs-Cgo)-alkenyl; and (ii) a soluble ionic r; wherein the water-soluble ionic polymer is derived from a monomer ition (i) not comprising any cross—linking monomers, or (ii) containing not more than 50 ppm cross-linking monomers, relative to the total content of monomers in the monomer ition.
The composition according to claim 1, which is a solid.
The composition according to claim 1 or 2, wherein the residue -O-A—O— is derived from a polyalkylene glycol HO-A-OH that comprises monomer units derived from ethylene glycol or a mixture of ethylene glycol and propylene glycol.
The composition according to any one of the preceding claims, wherein the residue -0— A—O- is derived from a polyalkylene glycol HO-A-OH that comprises 2-130 monomer units derived from ethylene glycol and 0-60 monomer units derived from propylene glycol.
The composition according to claim 3 or 4, wherein the monomer units derived from the ne glycol and the monomer units derived from the propylene glycol are present in any order or form two or more separate blocks.
The composition according to any one of the preceding , wherein the surfactant R1—O-A—O—R2 can be represented by the general formula (A) R10 0 0 CH3 q P . r wherein R1 is selected from the group consisting of —H, zo)-alkyl, {Cg-Cm)- alkenyl, -(C=O)-(Cg-C20)-alkyl and -(C=O)—(Ca-Czo)-alkenyl, R2 is selected from the group consisting of —H, —(C1-C6)-a|kyl, —benzyl, -(C=O)-(C8-C20)-alkyl and -(C=O)—(Cg-C20)—alkenyl, o and p are integers of from 0 to 130, and the sum of o and p is within the range of from 2 to 130; q and r are integers of from 0 to 60; and the sum of q and r is within the range of from 0 to 60; with the proviso that if R1 and R2 are both H, the sum of q and r may not be 0.
The composition according to any one of the preceding claims, wherein the non-ionic surfactant R1-O-A-O—R2 has a HLB not ing 14 and/or the ionic polymer is water- soluble or water-swellable.
The composition ing to any one of the ing claims, n the non-ionic surfactant R1—O-A-O-R2 is present in an amount of from 0.05 wt.-% to 2.0 wt.—%, based on the total weight of the composition.
The composition according to any one of the preceding claims, wherein the relative weight ratio of the non-ionic surfactant R‘—O-A-O-R2 to the ionic polymer is within the range of from 0.05 : 100 to 2 : 100.
10. The composition according to any one of the preceding claims, wherein the water- soluble ionic polymer is derived from a monomer composition ning a) one or more non-ionic ethylenically unsaturated monomers, and/or b) one or more cationic ethylenically unsaturated monomers, and/or 0) one or more anionic ethylenically unsaturated monomers; n the non-ionic ethylenically unsaturated monomer is selected from the group consisting of (a1) non-ionic rs according to general formula (I) Hzcwclt—j—N/R3 R4 R3 is hydrogen or Ci-C3-alkyl, and R4 and R5 are, independently of each other, hydrogen, C1-C5—alkyl or C1-C5- hydroxyalkyl; and (a2) non-ionic amphiphilic monomers according to general a (ll) H zCZC—Icl—z-<R7—O>-R8 U" wherein z1 is 0, NH or NR9 with R9 being C1—Cg—alkyl, R6 is hydrogen or alkyl, R7 is Cz-Ce-alkylene, R8 is hydrogen, Cg-ng-alkyl, C8-C32-aryl and/or C8-C32-aralkyl, and n is an integer between 1 and 50; the cationic ethylenically unsaturated monomer is a monomer according to general formula (lll) R10 0 Y1 H202(1)—lC|——ZZ—-YO—i\|1@—Y2 (Ill) is X6 wherein R10 is hydrogen or C1-C3'aIKYI; z2 is 0, NH or NR“ with R" being C1—Cg—alkyl; and Y0 is C2-Ce-alkylene, tuted with one or more hydroxy groups, Y1, Y2, Y3, independently of each other, are C1-C5—alkyl, and X' is a halogen, pseudo-halogen, acetate or SO4CH3'; and the anionic nically unsaturated monomer is ed from the group consisting of (c1) ethylenically unsaturated carboxylic acids, carboxylic anhydrides, and water- soluble alkali metal salts, alkaline earth metal salts, and ammonium salts thereof, (c2) ethylenically unsaturated sulfonic acids and water-soluble alkali metal salts, alkaline earth metal salts, and ammonium salts thereof, (03) ethylenically unsaturated onic acids and water-soluble alkali metal salts, alkaline earth metal salts, and ammonium salts thereof, and (c4) sulfomethylated and/or phosphonomethylated acrylamides and water—soluble alkali metal salts, alkaline earth metal salts, and ammonium salts thereof.
11. The composition according to any one of the preceding claims further ning an ionic polymeric dispersant.
12. The composition according to any one of the preceding claims, which is obtained by a process comprising the steps (i) subjecting an aqueous reaction mixture comprising a) one or more non—ionic nically unsaturated monomers, and/or b) one or more cationic ethylenically unsaturated monomers, and/or c) one or more anionic ethylenically unsaturated monomers, d) optionally the ionic ric dispersant, and e) ally the non-ionic surfactant, to radical polymerization by adiabatic gel polymerization; (ii) optionally crushing or chopping the gel ed from step (i); (iii) drying the material obtained from step (i) or (ii) at a temperature of 70 to 150 °C; (iv) optionally grinding the material obtained from step (iii); and (v) adding the non-ionic surfactant R1-O-A-O-R2; wherein step (v) is performed before step (i), after step (iv) andfor at any time in between.
13. Use of the composition according to any one of the ing claims — as a flocculating auxiliary in the sedimentation, flotation or filtration of , — as a thickener, or — as additive in papermaking.
14. Use of the composition according to any one of claims 1 to 12 as a flocculating auxiliary for purifying waste water or conditioning potable water.
15. The composition according to claim 1, substantially as herein bed with reference to any one of the Examples and/or
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11008418.3 | 2011-10-19 | ||
EP11008418 | 2011-10-19 | ||
PCT/EP2012/070786 WO2013057267A1 (en) | 2011-10-19 | 2012-10-19 | Composition comprising a non-ionic surfactant and an ionic polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ622068A NZ622068A (en) | 2016-07-29 |
NZ622068B2 true NZ622068B2 (en) | 2016-11-01 |
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