AU2006248161B2 - Process for preparing a polymer dispersion and a polymer dispersion - Google Patents
Process for preparing a polymer dispersion and a polymer dispersion Download PDFInfo
- Publication number
- AU2006248161B2 AU2006248161B2 AU2006248161A AU2006248161A AU2006248161B2 AU 2006248161 B2 AU2006248161 B2 AU 2006248161B2 AU 2006248161 A AU2006248161 A AU 2006248161A AU 2006248161 A AU2006248161 A AU 2006248161A AU 2006248161 B2 AU2006248161 B2 AU 2006248161B2
- Authority
- AU
- Australia
- Prior art keywords
- acid
- sulphonic acid
- polymer dispersion
- stabiliser
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 239000004815 dispersion polymer Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 49
- 239000000178 monomer Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- 125000000129 anionic group Chemical group 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000123 paper Substances 0.000 claims description 12
- 230000014759 maintenance of location Effects 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 claims description 8
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 8
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 8
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- -1 methallyl sulphonic acid Chemical compound 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 6
- SYPKYPCQNDILJH-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)butane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(CC)NC(=O)C=C SYPKYPCQNDILJH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 229920003169 water-soluble polymer Polymers 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- FTVFDANWRINFJW-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)butane-1-sulfonic acid Chemical compound CCC(C)C(S(O)(=O)=O)NC(=O)C=C FTVFDANWRINFJW-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 claims description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 2
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 2
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 claims description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 2
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 claims description 2
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 claims description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- QQZXAODFGRZKJT-UHFFFAOYSA-N n-tert-butyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC(C)(C)C QQZXAODFGRZKJT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- GASMGDMKGYYAHY-UHFFFAOYSA-N 2-methylidenehexanamide Chemical compound CCCCC(=C)C(N)=O GASMGDMKGYYAHY-UHFFFAOYSA-N 0.000 claims 1
- MVBJSQCJPSRKSW-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]prop-2-enamide Chemical compound OCC(CO)(CO)NC(=O)C=C MVBJSQCJPSRKSW-UHFFFAOYSA-N 0.000 claims 1
- 229920002125 Sokalan® Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920006318 anionic polymer Polymers 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-(1-amino-1-imino-2-methylpropan-2-yl)azo-2-methylpropanimidamide Chemical compound NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 description 1
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Paper (AREA)
- Polymerisation Methods In General (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
WO 2006/123993 PCT/SE2006/050112 1 PROCESS FOR PREPARING A POLYMER DISPERSION AND A POLYMER DISPERSION 5 The present invention relates to a process for preparing a polymer dispersion. It also relates to a polymer dispersion, the use of the polymer dispersion and a process for producing paper. Background of the invention An important use of aqueous dispersions of anionic charged polymers is 10 retention and dewatering aid in paper manufacturing industry. Further uses of such polymer dispersions are as aids in various processes where they act as, for example, flocculants when treating wastewater or aids in other solid-liquid separation processes in, for example, the metal-, ceramic-, printing-, biotechnological-, and pharmaceutical industries. They can also be used as thickeners in, e.g., chemical- biotechnological-, 15 pharmaceutical-, and cosmetic industries and soil improving agents. Generally, these polymer dispersions comprise a dispersed polymer and a dispersant in which the dispersant usually is a polymeric dispersant. Anionic polymer dispersions are generally prepared by polymerising a reaction mixture of water-soluble anionic and non-ionic monomers in the presence of a salt. 20 Finished polymer will precipitate from the aqueous salt solution and, by using a suitable dispersant, form a stable polymer dispersion. WO 01/18063, US 5,837,776 and US 5,605,970 disclose processes for preparing a dispersion of a water-soluble polymer comprising polymerising water-soluble monomers in an aqueous reaction mixture containing a salt. 25 Factors to consider are, for example, the process viscosity, active content, stability, good retention properties, and easiness of preparing the polymer dispersion sometimes including preparing the stabiliser. Also, criteria such as environmental and safety aspects are of importance. There are a number of criteria that the polymer dispersion should fulfil to give good 30 results in the final application and be of commercial interest. Such criteria are for example low-cost production, rapid performance, effective flocculation or dewatering, and long shelf life. Prior art anionic polymer dispersions described contain significant amounts of salt which makes up a great part of the weight of the polymer dispersion. There is 35 presently a desire to reduce, or completely avoid, the use of salt in polymer dispersions due to environmental and economical reasons.
WO 2006/123993 PCT/SE2006/050112 2 The viscosity of the reaction mixture when producing the polymer dispersion, "the process viscosity", should be kept low and viscosity peaks should be avoided, or at least reduced as much as possible, during the production of the polymer dispersion. The shelf life of the dispersion, i.e., the stability of the polymer dispersion over 5 time, is an important property. An efficient dispersant is needed for keeping the polymer particles stable in dispersion without settling as sediment. A further factor to consider is the active content, i.e., the amount of dispersed polymer in the polymer dispersion. A high active content minimises transportation costs and gives easier handling at the end-application. By using an efficient dispersant, 10 dispersions with a high active content can be obtained at the same time the viscosity can be kept low. However, an increase of the active content above a certain level may not always give improved performance in retention and dewatering in a papermaking process. During preparation of a polymer dispersion, deposits of polymer may form and 15 stick to the reaction vessel and stirrer. This leads to time consuming cleaning procedures of the reaction equipment. It is an object of the present invention to provide a, preferably salt-free, water soluble anionic polymer dispersion having high stability and high active content. The polymer dispersion should also give good retention and dewatering results when used in 20 papermaking processes, act as a good flocculant in other processes such as waste water treatment, act as a good thickener in various applications such as cosmetic formulations and also be possible to use in soil improvement processes. It is further an object of the present invention to provide a process for preparing a, preferably salt-free, water soluble anionic polymer dispersion in which the process viscosity is kept low and smooth during 25 preparation without any large viscosity peaks, and which gives no deposits. Finally, it is an object of the present invention to provide a process for producing paper in which the polymer dispersion is used. The invention 30 By "stabiliser" is herein meant a polymer which function is to keep dispersed polymer particles/droplets in dispersion. By "co-stabiliser" is herein meant a polymer which function is to make a polymer formed from polymerisation of one or more monomers to precipitate out from solution into solid particles or liquid droplets. 35 According to the invention it has surprisingly been found that a highly stable polymer dispersion having high active content of a dispersed polymer and low process viscosity can be achieved by a process for preparing a polymer dispersion comprising WO 2006/123993 PCT/SE2006/050112 3 polymerising one or more anionic monomers (m 1 ) and one or more non-ionic vinyl monomers (M 2 ) present in a reaction mixture further comprising a polymeric stabiliser (B) and a polymeric co-stabilisers (C). The invention further comprises a polymer dispersion comprising a dispersed 5 polymer (A) of one or more anionic monomers (m 1 ) and one or more non-ionic vinyl monomers (m 2 ), a polymeric stabiliser (B), and a polymeric co-stabiliser (C). The reaction medium is suitably an aqueous medium. The polymer dispersion is suitably an aqueous polymer dispersion. The polymer dispersion is suitably water soluble. The polymer particles/droplets suitably has an average size (thickness) of up to 10 about 25 pm, also suitably from about 0.01 to about 25 pm, preferably from about 0.05 to about 15 pm, most preferably from about 0.2 to about 10 pm. The polymeric stabiliser (B) is suitably an organic polymer. Preferably the polymeric stabiliser (B) is a polymer of one or more monomers belonging to the group of acrylic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-methyl-1-propane sulphonic 15 acid (AMPS), 2-acrylamido-2-methyl-1-butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, methacryloyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, methacryloyloxypropyl sulphonic acid, vinyl sulphonic acid, allyl sulphonic acid, methallyl sulphonic acid, styrene sulphonic acid, maleic acid, maleamidic acid, and/or vinyl phosphonic acid. Other suitable polymeric stabilizers are copolymers of maleic acid or 20 maleamidic acid, respectively, with styrene or vinyl ethers, or alpha-olefins which may contain additional comonomers. Preferably, the polymeric stabiliser (B) is a copolymer of acrylic acid or methacrylic acid with a further of the listed monomers, preferably 2 acrylamido-2-methyl-1 -propane sulphonic acid (AMPS). The weight average molecular weight of the polymeric stabiliser (B) is suitably 25 from about 5.000 to about 5.000.000 g/mole, preferably from about 10.000 to about 1.000.000 g/mole, more preferably from about 20.000 to about 1000.000 g/mole, most preferably from about 35.000 to about 500.000 g/mole. The polymer dispersion suitably comprises from about 0.2 to about 5 weight % of the polymeric stabiliser (B) based on the total weight of the dispersion or reaction mixture, 30 preferably from about 0.5 to about 3 weight %, most preferably from about 0.8 to about 1.5 weight %. The polymeric co-stabiliser (C) is suitably an organic polymer. Preferably, the polymeric co-stabiliser (C) is a polymer of one or more monomers belonging to the group of acrylic acid, methacrylic acid, vinyl sulphonate, styrene sulphonic acid, itaconic acid, 35 vinylphosphonic acid, 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS), 2 acrylamido-2-methyl-1-butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, WO 2006/123993 PCT/SE2006/050112 4 methacryloyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, and methacryloyloxypropyl sulphonic acid. Preferably, two or more co-stabilisers (C) are present in the reaction mixture and polymer dispersion. 5 The weight average molecular weight of the polymeric co-stabiliser (C) is suitably from about 100 to about 50.000 g/mol, preferably from about 500 to about 30.000 g/mol, more preferably from about 1.000 to about 20.000 g/mol, even more preferably from about 1.000 to about 15.000 g/mol, most preferably from about 1.000 to about 10.000 g/mol. 10 The polymer dispersion suitably comprises from about 2 to about 50 weight % of one or more polymeric co-stabilisers (C) based on the total weight of the dispersion or reaction mixture, preferably from about 3 to about 25 weight %, most preferably from about 5 to about 15 weight %. The polymeric stabiliser (B) and the polymeric co-stabiliser (C) in the reaction 15 mixture or polymer dispersion are preferably made up from different monomers or, if they are made up from the same monomers, contain different monomer ratios. The polymeric stabiliser (B) or polymeric co-stabiliser (C) is suitably not a dextrin or dextrin derivative. The one or more anionic monomers (m 1 ) suitably belong to the group of acrylic 20 acid, methacrylic acid, (styrene sulphonic acid), 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS), 2-acrylamido-2-methyl-1-butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, methacryloyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, methacryloyloxypropyl sulphonic acid, vinyl sulphonic acid, and their alkali, earth alkali or ammonium salts. 25 The one or more non-ionic monomers (M 2 ) suitably belong to the group of acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N ethylacrylamide, N-ethylmethacrylamide, N-isopropylacrylamide, N isopropylmethacrylamide, N,N-dimethylacrylamide, N-t-butylacrylamide, N-t butylmethacrylamide, N-hydroxyethylacrylamide, N-(tris-(hydroxymethyl)-methyl) 30 acrylamide, N-vinyl formamide, N-vinyl acetamide, hydroxyalkylacrylate or hydroxyalkylmethacrylate with C2-C4 alkyl, alkylacrylate or alkylmethacrylate with Cl-C4 alkyl, benzylacrylate or benzylmethacrylate, esters of acrylic or methacrylic acid with dihydroxy-(polyethylene oxide) having 1-20 ethylene oxide units, or esters of acrylic or methacrylic acid with monomethoxyhydroxy-(polyethylene oxide) having 1-20 ethylene 35 oxide units. Preferably, the one or more non-ionic monomers (M 2 ) belong to the group of acrylamide, acrylate or methacrylate esters.
WO 2006/123993 PCT/SE2006/050112 5 The molar ratio between the anionic monomer (m 1 ) and the non-ionic monomer
(M
2 ) is suitably from about 1:99 to about 25:75, preferably from about 3:97 to about 20:80, most preferably from about 5:95 to about 15:85. The weight average molecular weight of the dispersed polymer (A) is suitably 5 from about 1.000.000 to about 15.000.000 g/mole, preferably from about 1.500.000 to about 10.000.000 g/mole, most preferably from about 2.000.000 to about 8.000.000 g/mole. The polymerisation is suitably a free-radical polymerisation. The initiator is suitably a radical former, preferably a water-soluble azo-initiator, a water-soluble 10 peroxide, or a water-soluble redox initiator. Preferred initiators include 2,2'-azobis (amidinpropane) hydrochloride, 2,2'-azobis-(2-methyl-N-(2-hydroxyethyl)-propionamide, 4,4'-azobis-(4-cyanovaleric acid) and its alkali and ammonium salts, t-butylhydroperoxide, perhydrol, peroxydisulphate, or the before mentioned peroxides in combination with a reducing agent such as sodium metabisulphite or ferrous salts. 15 The polymer dispersion suitably comprises from about 5 to about 40 weight % of the dispersed polymer (A) based on the total weight of the dispersion, preferably from about 10 to about 30 weight %, most preferably from about 12 to about 25 weight %. The amount of one or more inorganic salts in the polymer dispersion is suitably from 0 to about 1.9 weight % based on the total weight of the dispersion or reaction 20 mixture, preferably from 0 to about 1 weight %, more preferably from 0 to about 0.5 weight %, most preferably from 0 to about 0.1 weight %, or substantially salt-free. By "inorganic salts" is herein suitably meant any inorganic salt, preferably salts belonging to the group of inorganic alkali metal, alkali earth metal or ammonium halides, sulphates and phosphates. 25 The polymer dispersion may also comprise additional substances, such as cross-linkers and branching agents. The polymerisation temperature when may vary depending on, e.g., which monomers and polymerisation initiator are being used. Suitably, the polymerisation temperature is from about 30 to about 90*C, preferably from about 35 to about 70*C. The 30 process is suitably a semi-batch process, i.e., the monomers m 1 and m 2 are both present at the beginning of the polymerisation process and further added at a later stage, either in one or more portions or continuously over a period of time during the reaction. The reaction mixture is suitably stirred during the polymerisation process at a stirring rate suitable for the process. Suitably, the stirring rate is from about 100 to about 1000 rpm. 35 The invention further comprises use of a polymer dispersion as retention and dewatering aid for paper manufacturing, as thickening agent, as soil improvement agent and/or as an additive for increasing the dry strength of paper. The polymer dispersion of WO 2006/123993 PCT/SE2006/050112 6 the present invention can more specifically be used as aid in various processes as, for example, flocculants when treating wastewater or aids in other solid-liquid separation processes in, for example, the metal-, ceramic-, printing-, biotechnological-, and pharmaceutical industries. The polymer dispersion can also be used as thickener in, e.g., 5 chemical- biotechnological-, pharmaceutical-, and cosmetic industries. Finally, the present invention comprises a process for the production of paper from an aqueous suspension containing cellulosic fibres, and optional fillers, which comprises adding to the suspension an aqueous polymer dispersion according to the invention, forming and draining the suspension on a wire. 10 When using the polymer dispersion, according to the invention, in papermaking processes, the dispersion is added to the suspension of cellulosic fibres, and optional fillers, to be dewatered in amounts which can vary within wide limits depending on, inter alia, type and number of components, type of furnish, filler content, type of filler, point of addition, etc. The dispersed polymer is usually added in an amount of at least 0.001%, often at least 15 0.005% by weight, based on dry substance in the stock to be dewatered, and the upper limit is usually 3% and suitably 1.5% by weight. The polymer dispersion according to the invention is suitably diluted before adding it to the cellulosic suspension. Further additives which are conventional in papermaking can of course be used in combination with the polymer dispersion according to the invention, such as, for example, silica-based sols, dry 20 strength agents, wet strength agents, optical brightening agents, dyes, sizing agents like rosin-based sizing agents and cellulose-reactive sizing agents, e.g. alkyl and alkenyl ketene dimers, alkyl and alkenyl ketene multimers, and succinic anhydrides, etc. The cellulosic suspension, or stock, can also contain mineral fillers of conventional types such as, for example, kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium 25 carbonates such as chalk, ground marble and precipitated calcium carbonate. The term "paper", as used herein, include not only paper and the production thereof, but also other cellulosic fibre-containing sheet or web-like products, such as for example board and paperboard, and the production thereof. The process can be used in the production of paper from different types of suspensions of cellulose-containing fibres and the suspensions 30 should suitably contain at least 25 % by weight and preferably at least 50 % by weight of such fibres, based on dry substance. The suspension can be based on fibres from chemical pulp such as sulphate, sulphite and organosolv pulps, mechanical pulp such as thermome chanical pulp, chemo-thermomechanical pulp, refiner pulp and groundwood pulp, from both hardwood and softwood, and can also be based on recycled fibres, optionally from de-inked 35 pulps, and mixtures thereof.
WO 2006/123993 PCT/SE2006/050112 7 The invention will now further be described in connection with the following examples which, however, not should be interpreted as limiting the scope of the invention. 5 Examples Example 1: A stabiliser made of methacrylic acid (MAA) and 2-acrylamido-2-methyl-1 propane sulphonic acid (AMPS) in a mole ratio of 80:20 was prepared: A mixture of 85g ultra-pure water, 8.24g AMPS (solid), 16.62g MAA and 11.5g NaOH (50%) was adjusted 10 to pH 7 by means of NaOH (50%). 0.02g EDTA (solid) was given into the mixture. Further ultra-pure water was added to reach a total mass of 127g. This was filled into a double wall 150ml glass reactor with anchor stirrer, nitrogen inlet, reflux condenser and bottom valve. The mixture was stirred with 150/min and purged with nitrogen. The reactor content was heated up to 45*C. 0.05g V-50 (2,2'-Azobis-(2-amidinopropane) dihydrochloride) 15 were added. After 60min, temperature was increased up to 50*C. The mixture was polymerised over 72 h at 50*C and 150/min. The stabiliser was purified and isolated by ultrafiltration and freeze-drying. The weight average molecular weight was about 15.000 g/mole. 20 Examples 2-7: A polymer dispersion was prepared by polymerising a monomer mixture comprising acrylamide and acrylic acid in the presence of a polymeric stabiliser and a polymeric co-stabiliser. A mixture of 30 g water, 24.3 g co-stabiliser polyacrylic acid (45%, Sigma 25 Aldrich, Mw 1.200), 1.2 g stabiliser poly (MAA-co-AMPS) (80:20) copolymer (according to example 1, Mw 15.000), 28.1 g acrylamide (50 wt%), 1.07 g acrylic acid, 0.04 g sodium formiate, 0.03 g EDTA, and 1.17 g NaOH (50 wt%) was stirred and the pH was adjusted to 7. Water was added up to 100 g and during 8 hours azo-initiator VA-044 (4%) (2,2' azobis-(N,N'-dimethyleneisobutyramidine) dihydrochloride, Wako) was added (0.5 g in 30 steps). The temperature was kept at 35*C. After 16 hours, the stirring was stopped. Five further polymer dispersions were prepared using the same procedure as described above but changing the ratio non-ionic monomer and anionic monomer, using a second non-ionic monomer in the dispersed polymer, and also using as co-stabiliser in some cases a combination of polyacrylic acid and polymethacrylic acid. As stabiliser 1.2 35 weight % poly-(MMA-co-AMPS) in a mole ratio of 80:20 was used. The active contents (polymer content) in the stabiliser was around 15 weight%. 11 weight % of co-stabiliser was used.
WO 2006/123993 PCT/SE2006/050112 8 In Table 1, the following abbreviations are used: AAm = acrylamide AA = acrylic acid MMA = methylmethacrylate 5 t-BuA = t-butyl acrylate n-BuA = n-butyl acrylate PAA = polyacrylic acid PMAA = polymethacrylic acid 10 Table 1. Dispersion anionic monomer non-ionic co-stabiliser stabiliser monomer Example 2 AA (10 mol-%) AAm PAA (Mw 1.200) poly-(MMA-co-AMPS) (90 mol-%) (Mw 15.000) Example 3 AA (15 mole-%) AAm PAA (Mw 1.200) poly-(MMA-co-AMPS) (85 mole-%) (Mw 20.000) Example 4 AA (15 mole-%) AAm PAA (Mw 1.200) poly- (MMA-co-AMPS) (85 mole-%) PMAA (Mw 9.500) (Mw 20.000) (1:1 ratio) Example 5 MMA (10 mole-%) AAm PAA poly-(MMA-co-AMPS) AA (10 mole-%) (80 mole-%) (Mw 1.200) (Mw 20.000) Example 6 MMA (10 mole-%) AAm PAA poly-(MMA-co-AMPS) t-BuA (10 mole-%) (80 mole-%) (Mw 1.200) (Mw 20.000) Example 7 MMA (10 mole-%) AAm PAA (Mw 1.200) poly-(MMA-co-AMPS) n-BuA (10 mole-%) (80 mole-%) PMAA (Mw 9.500) (Mw 20.000) (1:1 ratio) The process viscosity was low (lower than -2000 mPas) for all dispersions. Example 8: 15 The polymer dispersions prepared in Examples 2-4 were tested for retention and dewatering performance in papermaking processes by means of a Dynamic Drainage Analyser (DDA) available from Akribi, Sweden. The furnish used was based on 60 % by weight of bleached 80/20 birch-pine pulp and 40 % by weight of calcium carbonate. The WO 2006/123993 PCT/SE2006/050112 9 stock volume was 800 ml, the pulp concentration 5 g/L and the conductivity 1.5 mS/cm. The stock was stirred at a speed of 1500 rpm while the following was added to the stock: an anionic trash catcher (0.5 kg/t), polymer dispersion (1.0 kg/t) and finally anionic inorganic particles (0.5 kg/t). The temperature was 22.5*C. A vacuum of 0.35 bar was 5 used for the analysis. The retention time (s) and turbidity (NTU) was measured. Table 2. Polymer dispersions and application tests Polymer Application tests dispersion Polymer load Retention time Turbidity (kg/t) (s) (NTU) Example 2 1.0 15.2 198 Example 3 1.0 14.6 220 Example 4 1.0 13.2 214 It is concluded that the dispersions according to the invention function well in 10 retention and dewatering aids. Example 9: The shelf life, measured as sedimentation stability, was tested for the dispersions according to Examples 2-7. A 10 g sample of each dispersion was 15 centrifuged for 30 minutes at 3000 rpm. The amount of polymer sediment was determined for each sample. No sample gave any polymer sediment Thus, it is concluded that polymer dispersions with long shelf life can be obtained by the present invention, also at high active contents.
Claims (21)
1. Process for preparing a water-soluble polymer dispersion comprising polymerising one or more water soluble anionic monomers (mi) and one or more non ionic vinyl monomers (m 2 ) present in a reaction mixture further comprising 5 - a polymeric stabiliser (B) being a polymer of one or more monomers belonging to the group of acrylic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS), 2-acrylamido-2-methyl-1-butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, methacryloyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, methacryloyloxypropyl sulphonic acid, vinyl sulphonic acid, allyl sulphonic 10 acid, methallyl sulphonic acid, styrene sulphonic acid, maleic acid, maleamidic acid, and/or vinyl phosphonic acid, or a copolymer of maleic acid or maleamidic acid, respectively, with styrene, vinyl ethers or alpha-olefins, and - a polymeric co-stabiliser (C) being a polymer of one or more monomers belonging to the group of acrylic acid, methacrylic acid, vinyl sulphonate, styrene sulphonic acid, itaconic 15 acid, vinylphosphonic acid, 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS), 2 acrylamido-2-methyl-1-butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, methacryloyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, and methacryloyloxypropyl sulphonic acid, the weight average molecular weight of the polymeric stabiliser (B) is from about 20.000 20 to about 1.000.000 g/mole and the weight average molecular weight of the polymeric co stabiliser (C) is from about 1.000 to about 15.000 g/mole.
2. Water-soluble polymer dispersion comprising - a dispersed polymer (A) of one or more water soluble anionic monomers (m 1 ) and one or more non-ionic vinyl monomers (m 2 ), 25 - a polymeric stabiliser (B) being a polymer of one or more monomers belonging to the group of acrylic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS), 2-acrylamido-2-methyl-1 -butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, methacryloyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, methacryloyloxypropyl sulphonic acid, vinyl sulphonic acid, allyl sulphonic 30 acid, methallyl sulphonic acid, styrene sulphonic acid, maleic acid, maleamidic acid, and/or vinyl phosphonic acid, or a copolymer of maleic acid or maleamidic acid, respectively, with styrene, vinyl ethers or alpha-olefins, and - a polymeric co-stabiliser (C) being a polymer of one or more monomers belonging to the group of acrylic acid, methacrylic acid, vinyl sulphonate, styrene sulphonic acid, itaconic 35 acid, vinylphosphonic acid, 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS), 2 acrylamido-2-methyl-1-butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, C3181PcTk
2007-s-24 AMED S&LHEET %#I- "LUUUO IV - 16 1124-08-207 methacryloyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, and methacryloyloxypropyl sulphonic acid, the weight average molecular weight of the polymeric stabiliser (B) is from about 20.000 to about 1.000.000 g/mole and the weight average molecular weight of the polymeric co 5 stabiliser (C) is from about 1.000 to about 15.000 g/mole.
3. Process according to claim 1, or polymer dispersion according to claim 2, wherein the reaction mixture is an aqueous medium and the polymer dispersion is an aqueous polymer dispersion.
4. Process according to any one of claims 1 or 3, or polymer dispersion 10 according to any one of claims 2-3, wherein the polymer particles/droplets have an average size of up to about 25 pm.
5. Process according to any one of claims I or 3-4, or polymer dispersion according to any one of claims 2-4, wherein two or more co-stabilisers (C) are present in the reaction mixture and the polymer dispersion. 15
6. Process according to any one of claims I or 3-5, or polymer dispersion according to any one of claims 2-5, wherein the polymeric stabiliser (B) and the polymeric co-stabiliser (C) are made up from different monomers.
7. Process according to any one of claims I or 3-6, or polymer dispersion according to any one of claims 2-6, wherein the anionic monomer (m 1 ) suitably belongs to 20 the group of acrylic acid, methacrylic acid, (styrene sulphonic acid), 2-acrylamido-2 methyl-1 -propane sulphonic acid (AMPS), 2-acrylamido-2-methyl-l-butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, methacryloyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, methacryloyloxypropyl sulphonic acid, vinyl sulphonic acid, and their alkali, earth alkali or ammonium salts. 25
8. Process according to any one of claims 1 or 3-7, or polymer dispersion according to any one of claims 2-7, wherein the one or more non-ionic monomers (m 2 ) belong to the group of acrylamide, methacrylamide, N-methylacrylamide, N methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N isopropylacrylamide, N-isopropylmethacrylamide, N,N-dimethylacrylamide, N-t 30 butylacrylamide, N-t-butylmethacrylamide, N-hydroxyethylacrylamide, N-(tris (hydroxymethyl)-methyl)-acrylamide, N-vinyl formamide, N-vinyl acetamide, hydroxyalkylacrylate or hydroxyalkylmethacrylate with C2-C4 alkyl, alkylacrylate or alkylmethacrylate with C1-C4 alkyl, benzylacrylate or benzylmethacrylate, esters of acrylic or methacrylic acid with dihydroxy-(polyethylene oxide) having 1-20 ethylene oxide 35 units, or esters of acrylic or methacrylic acid with monomethoxyhydroxy-(polyethylene oxide) having 1-20 ethylene oxide units. C3181PCTk 2007-08-24 AMENDED SHEET 14 UU~ LUW 12
9. Process according to any one of claims I or 3-8, or polymer dispersion according to any one of claims 2-8, wherein the one or more monomers (M 2 ) belong to the group of acrylamide, acrylate or methacrylate esters.
10. Process according to any one of claims I or 3-9, or polymer dispersion 5 according to any one of claims 2-9, wherein the amount of inorganic salt is from 0 to about 1.9 weight % based on the total weight of the dispersion or reaction mixture.
11. Process according to any one of claims I or 3-10, or polymer dispersion according to any one of claims 2-10, wherein the amount of one or more inorganic salts is from 0 to about 0.5 weight % based on the total weight of the dispersion or reaction 10 mixture.
12. Process according to any one of claims I or 3-11, wherein the reaction mixture comprises from about 3 to about 20 mol % of the one or more water soluble anionic monomers (m 1 ).
13. Process according to any one of claims I or 3-12, wherein the reaction 15 mixture comprises from about 80 to about 97 mol % of the one or more non-ionic vinyl monomers (m 2 ).
14. Process according to any one of claims 1 or 3-13, wherein the reaction mixture comprises from about 0.5 to about 3 weight % of the polymeric stabiliser (B).
15. Process according to any one of claims I or 3-14, wherein the reaction 20 mixture comprises from about 3 to about 25 weight % of the polymeric co-stabiliser (C).
16. Polymer dispersion according to any one of claims 2-11, comprising from about 10 to about 30 weight % of the dispersed polymer (A).
17. Polymer dispersion according to any one of claims 2-11 or 16, comprising from about 0.5 to about 3 weight % of the polymeric stabiliser (B). 25
18. Polymer dispersion according to any one of claims 2-11 or 16-17, comprising from about 3 to about 25 weight % of the polymeric co-stabiliser (C).
19. Use of a polymer dispersion according to any of claims 2-11 or 16-18 as retention and dewatering aid for paper manufacturing, as additive for increasing the dry strength of paper, as thickening agent, and/or as soil improvement agent. 30
20. Process for the production of paper from an aqueous suspension containing cellulosic fibres, and optional fillers, which comprises adding to the suspension a polymer dispersion according to any of claims 2-11 or 16-18, forming and draining the suspension on a wire. C3181PCTk 2007-08-24 AMENDED SHEET 13
21. Process for preparing a water-soluble polymer dispersion according to claim 1, or a water-soluble polymer dispersion according to claim 2, and substantially as herein described with reference to any one of Examples 2 to 7. Dated 21 December, 2009 5 Akzo Nobel N.V. Fraunhofer-Gesellschaft zur Forderung der angewandten Forschung e.V. Patent Attorneys for the Applicant/Nominated Person SPRUSON & FERGUSON
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| PT2315785E (en) * | 2008-08-22 | 2014-10-01 | Fraunhofer Ges Forschung | Polymer dispersion |
| PL2470603T3 (en) * | 2009-08-24 | 2017-04-28 | Solenis Technologies Cayman, L.P. | Cationic cross-linked polymers in water-in-water polymer dispersions |
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2006
- 2006-05-09 MX MX2007013907A patent/MX276303B/en active IP Right Grant
- 2006-05-09 AU AU2006248161A patent/AU2006248161C1/en not_active Ceased
- 2006-05-09 JP JP2008512247A patent/JP4799611B2/en not_active Expired - Fee Related
- 2006-05-09 CN CNB2006800175052A patent/CN100558751C/en not_active Expired - Fee Related
- 2006-05-09 WO PCT/SE2006/050112 patent/WO2006123993A2/en active Application Filing
- 2006-05-09 EP EP06733482A patent/EP1881997A2/en not_active Withdrawn
- 2006-05-09 RU RU2007147474/02A patent/RU2394841C2/en not_active IP Right Cessation
- 2006-05-09 BR BRPI0610071-6A patent/BRPI0610071A2/en not_active IP Right Cessation
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- 2006-05-09 ZA ZA200709250A patent/ZA200709250B/en unknown
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- 2007-11-20 KR KR1020077026940A patent/KR100923849B1/en not_active Expired - Fee Related
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| US6245838B1 (en) * | 1998-02-03 | 2001-06-12 | 3M Innovative Properties Company | Method of suspension polymerization of (meth)acrylic monomers using dextrin, and polymer beads resulting from that method |
| US6265477B1 (en) * | 1999-09-08 | 2001-07-24 | Nalco Chemical Company | Aqueous dispersion of a particulate high molecular weight anionic or nonionic polymer |
| WO2003097703A1 (en) * | 2002-05-15 | 2003-11-27 | Akzo Nobel N.V. | A water-soluble polymer dispersion and a method of producing a water-soluble polymer dispersion |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006123993A2 (en) | 2006-11-23 |
| CN101180321A (en) | 2008-05-14 |
| CN100558751C (en) | 2009-11-11 |
| WO2006123993A3 (en) | 2007-08-16 |
| MX2007013907A (en) | 2008-03-25 |
| NO20076511L (en) | 2008-02-20 |
| AU2006248161A1 (en) | 2006-11-23 |
| KR20080012301A (en) | 2008-02-11 |
| BRPI0610071A2 (en) | 2010-05-25 |
| EP1881997A2 (en) | 2008-01-30 |
| ZA200709250B (en) | 2009-02-25 |
| JP2008540796A (en) | 2008-11-20 |
| CA2608408C (en) | 2011-07-19 |
| JP4799611B2 (en) | 2011-10-26 |
| RU2394841C2 (en) | 2010-07-20 |
| AU2006248161C1 (en) | 2010-07-29 |
| RU2007147474A (en) | 2009-06-27 |
| MX276303B (en) | 2010-06-02 |
| KR100923849B1 (en) | 2009-11-04 |
| CA2608408A1 (en) | 2006-11-23 |
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