EP2870287A1 - Improved method for manufacturing paper using a cationic polymer obtained by hofmann degradation - Google Patents
Improved method for manufacturing paper using a cationic polymer obtained by hofmann degradationInfo
- Publication number
- EP2870287A1 EP2870287A1 EP13737326.2A EP13737326A EP2870287A1 EP 2870287 A1 EP2870287 A1 EP 2870287A1 EP 13737326 A EP13737326 A EP 13737326A EP 2870287 A1 EP2870287 A1 EP 2870287A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- thick paste
- charges
- polymer
- white water
- cationic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229920006317 cationic polymer Polymers 0.000 title claims description 21
- 230000015556 catabolic process Effects 0.000 title description 25
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000010790 dilution Methods 0.000 claims abstract description 17
- 239000012895 dilution Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 229920003118 cationic copolymer Polymers 0.000 claims abstract description 7
- 239000011111 cardboard Substances 0.000 claims abstract description 6
- 238000000265 homogenisation Methods 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 35
- 229920001577 copolymer Polymers 0.000 claims description 22
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 17
- 229920002873 Polyethylenimine Polymers 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 11
- 150000001408 amides Chemical class 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011087 paperboard Substances 0.000 claims description 6
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 6
- 239000006085 branching agent Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229920000083 poly(allylamine) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920006295 polythiol Polymers 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000000123 paper Substances 0.000 abstract description 23
- 229920002678 cellulose Polymers 0.000 abstract 1
- 239000001913 cellulose Substances 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 description 19
- 239000002585 base Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 9
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 4
- 229920005601 base polymer Polymers 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- -1 clays Substances 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 230000036314 physical performance Effects 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000006105 Hofmann reaction Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229920006322 acrylamide copolymer Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 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
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 2
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 2
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- CUGZWHZWSVUSBE-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)ethanol Chemical compound OCCOCC1CO1 CUGZWHZWSVUSBE-UHFFFAOYSA-N 0.000 description 1
- NBTXFNJPFOORGI-UHFFFAOYSA-N 2-ethenoxyethyl prop-2-enoate Chemical compound C=COCCOC(=O)C=C NBTXFNJPFOORGI-UHFFFAOYSA-N 0.000 description 1
- ZKYCLDTVJCJYIB-UHFFFAOYSA-N 2-methylidenedecanamide Chemical compound CCCCCCCCC(=C)C(N)=O ZKYCLDTVJCJYIB-UHFFFAOYSA-N 0.000 description 1
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Chemical class 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 229940059260 amidate Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WJMQFZCWOFLFCI-UHFFFAOYSA-N cyanomethyl prop-2-enoate Chemical compound C=CC(=O)OCC#N WJMQFZCWOFLFCI-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZLSJVVLETDAEQY-UHFFFAOYSA-N n,n-dihexylprop-2-enamide Chemical compound CCCCCCN(C(=O)C=C)CCCCCC ZLSJVVLETDAEQY-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- CHDKQNHKDMEASZ-UHFFFAOYSA-N n-prop-2-enoylprop-2-enamide Chemical compound C=CC(=O)NC(=O)C=C CHDKQNHKDMEASZ-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
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011780 sodium chloride 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
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/66—Pulp catching, de-watering, or recovering; Re-use of pulp-water
- D21F1/82—Pulp catching, de-watering, or recovering; Re-use of pulp-water adding fibre agglomeration compositions
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Definitions
- the invention relates to an improved process for the production of paper, cardboard or the like using at least one cationic polymer obtained by Hofmann degradation and making it possible to increase the level of filler in said paper and paperboard, while retaining properties of interesting physical resistance. It also relates to paper or paperboard obtained by this method.
- Hofmann degradation polymers are chemical compounds commonly used in the papermaking industry.
- the document WO2011 / 015783 describes, in particular, cationic (co) polymers derived from acrylamide obtained by Hofmann degradation. These compounds are added as dripping agents in so-called diluted pastes, or to improve dry strength performance, also in diluted pastes.
- composition of most fibrous suspensions used in the manufacture of paper contains, following a direct or indirect addition (using recycled paper), inorganic fillers such as clays, kaolin, calcium carbonate, or titanium dioxide.
- inorganic fillers such as clays, kaolin, calcium carbonate, or titanium dioxide.
- the most used fillers are calcium carbonates, either in ground form (we speak of GCC for "Ground Calcium Carbonate”), or in precipitated form (it is called PCC for "Precipitated Calcium Carbonate") .
- GCC Ground Calcium Carbonate
- PCC Precipitated Calcium Carbonate
- retention agents are used to increase the overall retention in the sheet (RPF: “First Pass Retention”), and in particular the retention of charges (FPAR: “First Pass Ash Retention”).
- these retention agents are generally polymers of high molecular weight (i.e. greater than 1 million g / mol), such as acrylamide copolymers. These polymers can be combined with inorganic microparticulate compounds (bentonite, colloidal silica).
- the retention agents conventionally used are added to the diluted dough, ie a fibrous suspension containing from 0.1 to 1.5% of dry matter. They make it possible to improve the charge retention, ie to optimize the quantity of charge used. Their role consists in particular to retain the charges in the paper and thus reduce the amount of charges discharged into the white water from the drainage of the sheet during its formation on the canvas.
- WO2009 / 036271 discloses a process for increasing the filler content in the paper by pre-flocculation of the "slurry" of fillers (liquid paste) in the presence of two flocculants injected successively, and combined with an added global retention agent near the headbox.
- this technique is difficult to implement because of the multitude of compounds added in a well-defined sequence.
- the documents US2006 / 0024262 and US2009 / 0272506 describe a treatment using an amphoteric PolyVinylAmine (PVA) resulting from the hydrolysis of an N-vinylformamide base copolymer (NVF).
- PVA amphoteric PolyVinylAmine
- US2012073774A1 discloses a process involving the addition of a cationic polymer and an aqueous suspension of tackifier.
- the cationic polymer is preferably a polyvinylamine obtainable in particular by hydrolysis or by the Hofmann degradation reaction. These two compounds are typically integrated into the diluted dough. They make it possible to reduce the adhesion of the sheet of paper to the fabric during drying.
- the problem to be solved by the invention concerns, in particular, the optimum increase in the quantity of charges, or charge rates, in the sheets of paper or cardboards, while maintaining satisfactory physical performances.
- the present invention provides an improved process for producing paper, board and the like comprising adding to a fibrous suspension at least one polymer obtained by Hofmann degradation characterized in that the polymer obtained by Hofmann degradation is cationic, and added before the dilution pump ("fan pump") of the thick stock (thick stock) with white water.
- the present invention relates to a method of manufacturing a sheet of paper and / or cardboard and the like, according to which, in an installation comprising a dilution pump and a headbox:
- a cellulosic fibrous suspension is prepared in which charges are advantageously introduced, referred to as thick stock;
- the mixture thus obtained is homogenized in the dilution pump (fan pump); the thin stock is transferred from the homogenization to the headbox;
- the sheet is dried.
- This process is characterized in that before homogenization of the mixture in the dilution pump, that is to say before the dilution pump, a cationic copolymer obtained by Hofmann degradation reaction is introduced into the white water and / or the thick paste, and / or the mixture formed by the white waters and the thick paste.
- the present invention also relates to the paper or paperboard obtained that can be obtained by this method.
- the Applicant considers that the cationic polymer obtained by Hofmann degradation can play the role of affinity activator between charges and fibers, which allows the charges to be retained quantitatively. in the sheet of paper at the time of formation of the paper network. Moreover, this very good affinity seems to reinforce the cohesion of the structure of the sheet of paper, thus conferring on it an unequaled physical resistance relative to the percentage of load present in the sheet.
- the white water is added to the thick stock before the fan pump.
- the dough forms a diluted paste (dilute suspension, "thin stock") which at the output of the dilution pump goes to the head box where the wet sheet is formed before to be dried.
- a shearing step is provided between the dilution pump and the headbox: it is the "pressure screen”.
- the fillers are generally added in the form of slurry in the thick paste. However, these fillers may come from a raw material containing fillers, for example deinked pastes, broken / glued pasta, etc.
- the thick paste, or thick fibrous suspension generally contains between 2 and 5% of dry matter.
- the cationic polymer obtained by Hofmann degradation can be introduced into the process in the thick paste and / or in the white waters and / or in the mixture of the two before the dilution pump.
- fillers are added, especially in the form of slurry, before the dilution pump. They are in the thick paste and / or the white waters and / or the mixture of the two, and this, in one or in several times. The fillers are nevertheless most often advantageously added to the thick paste.
- the polymer is added in the immediate vicinity of the point or points of introduction of the charges.
- the cationic polymer is introduced at the same time as the charges.
- it is introduced in this case in the "slurry" of charges or during its preparation.
- Slurry filler is an aqueous dispersion containing fillers. Generally a “slurry” contains more than 10% by weight.
- the improved process according to the invention may further comprise the addition in the paper sequence of any other mineral compound or natural or synthetic polymer well known to those skilled in the art.
- the process according to the invention comprises the addition of at least one cationic polymer obtained by Hofmann degradation before the dilution pump, and at least one cationic polymer based on acrylamide in the diluted dough, that is to say after the dilution pump.
- this cationic polymer based on acrylamide has a molecular weight greater than 1 million g / mol.
- the amount of cationic polymer obtained by Hofmann degradation introduced according to the process of the invention is between 50 and 4000 grams of active polymer per tonne of dry pulp (g / t).
- the amount introduced is between 100 g / t and 1000 g / t.
- Hofmann's degradation is a reaction discovered by Hofmann at the end of the nineteenth century, which makes it possible to convert an amide into a primary amine by eliminating carbon dioxide.
- the reaction mechanism is detailed below. In the presence of a base (soda), a proton is torn from the amide.
- the amidate ion formed then reacts with the active chlorine (Cl 2 ) of the hypochlorite (eg: NaClO which is in equilibrium: 2 NaOH + Cl 2 NaClO + NaCl + H 2 O) to give an N-chloramide.
- the base (NaOH) removes a proton from chloramide to form an anion.
- the anion loses a chloride ion to form a nitrene which is transposed to isocyanate.
- a carbamate is formed.
- - Alpha (alkaline and / or alkaline earth / acrylamide hypohalide)
- - Beta (alkali and / or alkaline earth hydroxide / alkaline and / or alkaline earth hypohalide).
- the cationic polymers obtained by Hofmann degradation implemented in the process according to the invention are advantageously chosen from the polymers described in document WO2011 / 015783.
- the heteroatoms can be: N, S, O, P
- the polyfunctional compounds may in particular be oligomers, polymers, or carbon chains containing at least three carbon atoms.
- the polyfunctional compound may be chosen from the group comprising polyethyleneimines (PEI), polyamines (primary or secondary), polyallylamines, polyamines amides (PAA), polythiols, polyalcohols, polyamides epichloridrine (PAE) and their mixtures.
- PEI polyethyleneimines
- PAA polyamines amides
- PAE polythiols
- PAE polyalcohols
- PAE polyamides epichloridrine
- the polyfunctional compound incorporated may be polyethyleneimine (PEI) or a polyamine amide (PAA).
- PEI polyethyleneimine
- PAA polyamine amide
- the polymer obtained at the end of the Hofmann reaction may be branched, due to a branching of the base polymer. In other words, it is the branched nature of the base copolymer which will confer its branched state on the final polymer.
- the polymer is obtained by Hofmann degradation reaction in the presence, as hypohalogenide, of an alkaline hypochlorite, preferably sodium hypochlorite.
- the alpha hypohalide / nonionic monomer coefficient (expressed in molar ratios) used for the preparation of the polymers of the invention is greater than 0.3 or even 0.5, advantageously between 0.8 and 1. included.
- the Hofmann degradation product is produced at a concentration greater than 4% by weight, preferably greater than 5%, advantageously greater than 7%.
- the copolymer of the invention may have a cationic charge density of preferably greater than 2 meq / g and advantageously greater than 5 meq / g.
- a nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide and / or acrylonitrile, preferably acrylamide,
- polyethyleneimine polyamine (primary or secondary), polyallylamine, preferably polyethyleneimine polythiols, optionally at least:
- an unsaturated cationic ethylenic monomer preferably chosen from the group comprising dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acidic salt monomers.
- DMAC dimethyldiallylammonium chloride
- APITAC acrylamidopropyltrimethylammonium chloride
- MATAC methacrylamidopropyltrimethylammonium chloride
- / or a nonionic monomer preferably chosen from the group comprising N-vinylacetamide.
- N-vinyl formamide, N-vinylpyrrolidone and / or vinyl acetate is branched and preferably consists of three types of compounds:
- At least one unsaturated cationic ethylenic comonomer selected from the group comprising dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine and their quaternary ammonium or acid salts, preferably dimethyldiallylammonium chloride. It is important to note that, in combination with these monomers, it is also possible to use water-insoluble monomers such as acrylic, allylic or vinyl monomers having a hydrophobic group. In use, these monomers are employed in amounts generally less than 20 mol%, preferably less than 10 mol%.
- N-alkylacrylamide for example N-tert-butylacrylamide, octylacrylamide and ⁇ , ⁇ -dialkylacrylamides, such as N, N-dihexylacrylamide, etc.
- the precursor based on acrylamide or derivatives incorporates, within itself, at least polyethyleneimine (PEI);
- PEI polyethyleneimine
- the alpha hypohalide / nonionic monomer coefficient used for the preparation of the polymers of the invention is between 0.8 and 1 inclusive;
- the base copolymer is branched.
- the branching may preferably be carried out during (or possibly after) the polymerization of the "base” copolymer, in the presence of a polyfunctional branching agent and optionally of a transfer agent.
- a polyfunctional branching agent and optionally of a transfer agent.
- the following is a non-limiting list of branching agents: methylene bisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate or methacrylate, triallylamine, formaldehyde, glyoxal, glycidyl ether compounds such as ethylene glycol glycidyl ether, or epoxy or any other means well known to those skilled in the art for crosslinking.
- MBA methylene bisacrylamide
- ethylene glycol di-acrylate polyethylene glycol dimethacrylate
- diacrylamide diacrylamide
- cyanomethylacrylate vinyloxyethylacrylate or meth
- the branching agent is advantageously introduced at a rate of from five to fifty thousand (5 to 50,000) parts per million by weight relative to the active ingredient, preferably from 5 to 10,000, advantageously from 5 to 5,000.
- the branching agent is methylenebisacrylamide (MBA).
- MBA methylenebisacrylamide
- the additional polyfunctional compound is mixed with a comonomer before polymerization.
- the transfer agent may in particular be chosen in a non-limiting manner from the group comprising isopropyl alcohol, sodium hypophosphite, and mercaptoethanol.
- the copolymer serving as a basis for the Hofmann degradation reaction does not require the development of a particular polymerization process.
- the main polymerization techniques well known to those skilled in the art and which can be used are: precipitation polymerization, emulsion polymerization (aqueous or inverse) followed or not by a distillation step and / or “spray drying” “(Spray drying), and suspension polymerization or solution polymerization, both of which are preferred.
- Beta (alkali and / or alkaline-earth hydroxide / alkaline and / or alkaline-earth hypochlorite) From a previously described "base" copolymer solution of concentration of between 10 and 40% by weight, preferably between 15 and 25%, the molar amount of total amide function is determined. The level of degradation Alpha is then chosen, which makes it possible to determine the dry quantity of alkaline and / or alkaline earth hypohalide and then the beta coefficient, which makes it possible to determine the dry quantity of alkaline hydroxide and / or alkaline-earthy.
- hypohalide and alkali and / or alkaline earth hydroxide are then prepared from the alpha and beta ratios.
- the reagents preferably used are sodium hypochlorite (bleach) and sodium hydroxide (sodium hydroxide).
- amine functions that will be produced, it may optionally be added to the reactor containing the base polymer, one (or possibly more) quaternary ammonium derivative as described in JP 57077398 and well known by the US Pat. one skilled in the art, it is indeed intended to avoid the reaction between the amine functions and residual amide functions. It will be noted, moreover, that the addition of these agents can be carried out separately, simultaneously, mixed or not, in any order of introduction and at one or more injection points.
- the increase in cationicity of the base copolymer takes place during the so-called Hofmann degradation, by the use of an alkaline or alkaline-earth hypohalide.
- the polymers of the invention may also be provided in solid form.
- the solid form contains not only the copolymer, but also a proportion of salt obtained at the end of the Hofmann degradation reaction.
- they are obtained inter alia by methods of drying the aforementioned solution.
- the main insulation techniques then used are those of spray drying (which consists of creating a cloud of fine droplets in a hot gas stream for a controlled period of time), drum drying, fluidized bed dryers, etc.
- the process according to the invention can be used with all types of pulp: virgin fiber pulps (kraft, bisulfite, etc.), recycled fibers, deinked pastes, mechanical and thermomechanical pulps, etc.
- fillers it may be all types of fillers that may be selected from the group consisting of clays, kaolin, ground calcium carbonate (GCC), precipitated calcium carbonate (PCC), titanium dioxide, and mixtures thereof.
- GCC ground calcium carbonate
- PCC precipitated calcium carbonate
- titanium dioxide titanium dioxide
- the charges can be added in different forms, the shape "slurry" being the most encountered. They can be prepared with or without dispersant, out of or on paper manufacturing site.
- the cationic polymer obtained by Hofmann degradation may be prepared near the paper machine.
- DMDMAC dimethyldiallyl ammonium chloride
- the polyethyleneimine is mixed with the DADMAC monomer and the MBA in the reactor.
- the acrylamide will be incorporated in continuous casting for 2 hours, in a reaction medium maintained at 85 ° C.
- the polymerization is catalyzed in the presence of SPS (sodium persulfate) and MBS (sodium metabisulfite), catalysts well known to those skilled in the art.
- the precursor polymer thus obtained has a viscosity of 5500 cps (25 ° C, Brookfield LV3, 12 rpm).
- the Hofmann degradation itself is carried out in the same manner as in Example 1 of the Applicant's document WO2010061082, by performing a complete Hofmann degradation.
- the acrylamide-derived cationic copolymer thus prepared has a bulk viscosity of 35 cps (25 ° C, Brookfield LV1, 60 rpm) and a concentration of 8.5% active material.
- Polymer B Polymer B:
- DMDMAC dimethyldiallyl ammonium chloride
- the polyethyleneimine is mixed with the DADMAC monomer and the MBA in the reactor.
- Acrylamide and acrylic acid will be incorporated in continuous casting for 2 hours, in a reaction medium maintained at 85 ° C.
- the polymerization is catalyzed in the presence of SPS and MBS, catalysts well known to those skilled in the art.
- the precursor polymer thus obtained has a viscosity of 4500 cps (25 ° C, Brookfield LV3, 12 rpm).
- the Hofmann degradation itself is carried out in the same manner as in Example 1 of the Applicant's document WO2010061082, by performing a complete Hofmann degradation.
- the resulting acrylamide-derived cationic copolymer has a bulk viscosity of 55 cps (25 ° C, Brookfield LV1, 60 rpm) and a concentration of 9%.
- polymers will be compared to (1) a high molecular weight acrylamide / ADAME MeCl powder copolymer (FO 4190 PG1, SNF Floerger), standard retention agent, and (2) Luredur PR 8351 from BASF, an amphoteric copolymer based on PVA (from the hydrolysis of NVF), current reference as a charge retention agent and DSR performance maintainer.
- a high molecular weight acrylamide / ADAME MeCl powder copolymer (FO 4190 PG1, SNF Floerger), standard retention agent
- Luredur PR 8351 from BASF
- an amphoteric copolymer based on PVA from the hydrolysis of NVF
- current reference as a charge retention agent and DSR performance maintainer.
- the "slurry" of the dough is made by disintegrating dry pulp in order to obtain a final concentration of 3%.
- the necessary amount of pulp is removed so as to finally obtain a sheet having a basis weight of 60 g / m 2 .
- the concentrated paste is introduced into the vat of the dynamic form and stirred there.
- a "slurry" of fillers injected simultaneously (but separately) to the polymer A, B or Luredur PR 8351 from BASF. This paste is then diluted to a concentration of 0.32%.
- the dough In manual mode, the dough is pumped to the nozzle level to prime the circuit.
- a blotter and training cloth are placed in the bowl of the dynamic formette before starting the rotation of the bowl at 900m / min and constructing the water wall. Potentially, a retention agent will be injected 10 seconds before the start of the production cycle of the sheet.
- the sheet is then made (in automatic mode) by 22 round trips of the nozzle projecting the paste into the wall of water. Once the water is drained and the automatic sequence is complete, the forming web with the formed fiber network is removed from the dynamically shaped bowl and placed on a table.
- a dry blotter is deposited on the side of the wet fiber mat and is pressed once with a roll. The whole is returned and the fabric is delicately separated from the fibrous mat.
- a second dry blotter is deposited and the sheet (between the two blotters) is pressed once under a press delivering 4 bars and is then dried on a dryer stretched for 9 min at 107 ° C.
- the two blotters are then removed and the sheet is stored overnight in a room with controlled humidity and temperature (50% relative humidity and 23 ° C). The dry strength properties of all the sheets obtained by this procedure are then evaluated.
- the burst index is measured with a Messmer Buchel M 405 (average of 14 measurements).
- Dry traction is measured in the machine direction with a Testometric AX tensile tester (average of 5 samples).
- the rate of fillers in the sheet is measured using a muffle furnace according to a standard non-organic material measurement procedure (570 ° C for 5 hours)
- polymer A provides more charge retention but also more DSR performance than Luredur PR 8351.
- the polymer B amphoteric, gives performance equivalent to Luredur PR 8351 but lower than the polymer A.
- the polymer A In combination with a retention agent, the polymer A provides the highest amount of fillers in the paper sheet while maintaining good physical strength properties of the sheet.
Abstract
Description
Claims
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FR1256575A FR2992981B1 (en) | 2012-07-09 | 2012-07-09 | IMPROVED PAPER MANUFACTURING METHOD USING POLYMER OBTAINED BY HOFMANN DEGRADATION |
PCT/FR2013/051406 WO2014009621A1 (en) | 2012-07-09 | 2013-06-17 | Improved method for manufacturing paper using a cationic polymer obtained by hofmann degradation |
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EP2870287A1 true EP2870287A1 (en) | 2015-05-13 |
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US (1) | US9303359B2 (en) |
EP (1) | EP2870287B1 (en) |
KR (1) | KR102123132B1 (en) |
CN (1) | CN104395525A (en) |
BR (1) | BR112014031379A2 (en) |
CA (1) | CA2876609C (en) |
ES (1) | ES2590528T3 (en) |
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WO (1) | WO2014009621A1 (en) |
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FR3016363B1 (en) * | 2014-01-15 | 2017-05-26 | Snf Sas | AQUEOUS SOLUTION OF ACRYLAMIDE-DERIVED CATIONIC COPOLYMERS, PROCESS FOR PREPARATION AND USE |
CN105754022B (en) * | 2016-03-15 | 2018-07-17 | 福州大学 | 3- ethylene amido -2- hydroxypropyl-trimethyl ammonium chlorides copolymers and its preparation and application |
WO2018049537A1 (en) * | 2016-09-19 | 2018-03-22 | Fpinnovations | In-plane isotropic, binderless products of cellulosic filament based compositions by compression molding |
CN110653913A (en) * | 2019-08-26 | 2020-01-07 | 江苏中联路基工程有限公司 | Degradable plant drainage plate core and preparation method thereof |
CN112194743B (en) * | 2020-10-09 | 2022-12-09 | 安徽天润化学工业股份有限公司 | Preparation method and application of modified polyacrylamide based on Hofmann degradation reaction |
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JPS5777398A (en) | 1980-10-27 | 1982-05-14 | Seiko Kagaku Kogyo Co Ltd | Papermaking method due to paper making stock material containing water glass |
DE3445932A1 (en) * | 1984-12-17 | 1986-06-26 | Boehringer Ingelheim KG, 6507 Ingelheim | PHARMACEUTICAL COMPOSITIONS |
US5126014A (en) * | 1991-07-16 | 1992-06-30 | Nalco Chemical Company | Retention and drainage aid for alkaline fine papermaking process |
DE10334133A1 (en) | 2003-07-25 | 2005-02-24 | Basf Ag | Aqueous composition and its use for papermaking |
DE102004013007A1 (en) * | 2004-03-16 | 2005-10-06 | Basf Ag | Process for the production of paper, cardboard and cardboard |
SE0402178D0 (en) * | 2004-09-10 | 2004-09-10 | Swedish Bioclean Engineering A | Device and method related process industry |
EP1828481B1 (en) | 2004-12-17 | 2015-09-23 | Basf Se | Papers with a high filler material content and high dry strength |
DE102005025374A1 (en) * | 2005-05-31 | 2006-12-07 | Basf Ag | Polymer-pigment hybrids for papermaking |
GB0702249D0 (en) * | 2007-02-05 | 2007-03-14 | Ciba Sc Holding Ag | Manufacture of paper or paperboard |
FR2912749B1 (en) * | 2007-02-19 | 2009-04-24 | Snf Soc Par Actions Simplifiee | CATIONIC COPOLYMERS DERIVED FROM ACRYLAMIDE AND THEIR USES |
FR2918989B1 (en) * | 2007-07-18 | 2010-08-27 | Snf Sas | WATER-SOLUBLE, WATER-SOLUBLE CATIONIC ACRYLAMIDE POLYMERS AND THEIR ACHIEVEMENTS |
US8172983B2 (en) | 2007-09-12 | 2012-05-08 | Nalco Company | Controllable filler prefloculation using a dual polymer system |
FR2938842B1 (en) * | 2008-11-27 | 2012-09-21 | Snf Sas | NOVEL PROCESS FOR THE PREPARATION OF ACRYLAMIDE COPOLYMERS BY HOFMANN DEGRADATION REACTION |
WO2010145990A1 (en) * | 2009-06-16 | 2010-12-23 | Basf Se | Method for reducing deposits in the drying section in the manufacture of paper, paperboard, and cardboard |
FR2948941B1 (en) | 2009-08-04 | 2011-10-28 | Snf Sas | CATIONIC COPOLYMERS DERIVED FROM ACRYLAMIDE AND USES THEREOF |
FR2963364B1 (en) * | 2010-08-02 | 2014-12-26 | Snf Sas | METHOD FOR MANUFACTURING PAPER AND CARDBOARD HAVING IMPROVED RETENTION AND DRIPPING PROPERTIES |
JP5777398B2 (en) | 2011-05-13 | 2015-09-09 | キヤノン株式会社 | Image processing apparatus, image processing method and program for image processing apparatus |
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- 2013-06-17 WO PCT/FR2013/051406 patent/WO2014009621A1/en active Application Filing
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- 2013-06-17 BR BR112014031379A patent/BR112014031379A2/en not_active Application Discontinuation
- 2013-06-17 ES ES13737326.2T patent/ES2590528T3/en active Active
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WO2014009621A1 (en) | 2014-01-16 |
FR2992981B1 (en) | 2014-07-04 |
BR112014031379A2 (en) | 2017-06-27 |
US20150176208A1 (en) | 2015-06-25 |
CA2876609C (en) | 2020-02-11 |
KR102123132B1 (en) | 2020-06-15 |
EP2870287B1 (en) | 2016-08-17 |
CA2876609A1 (en) | 2014-01-16 |
FR2992981A1 (en) | 2014-01-10 |
KR20150035723A (en) | 2015-04-07 |
US9303359B2 (en) | 2016-04-05 |
ES2590528T3 (en) | 2016-11-22 |
CN104395525A (en) | 2015-03-04 |
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