EP2870287B1 - 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 degradation Download PDFInfo
- Publication number
- EP2870287B1 EP2870287B1 EP13737326.2A EP13737326A EP2870287B1 EP 2870287 B1 EP2870287 B1 EP 2870287B1 EP 13737326 A EP13737326 A EP 13737326A EP 2870287 B1 EP2870287 B1 EP 2870287B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- process according
- fillers
- sheet
- thick stock
- 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.)
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- 238000000034 method Methods 0.000 title claims description 36
- 238000006731 degradation reaction Methods 0.000 title claims description 35
- 229920006317 cationic polymer Polymers 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 230000015556 catabolic process Effects 0.000 title description 24
- 229920000642 polymer Polymers 0.000 claims description 47
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 26
- 229920001577 copolymer Polymers 0.000 claims description 22
- 239000000945 filler Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 229920002873 Polyethylenimine Polymers 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 11
- 150000001408 amides Chemical class 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- 239000003643 water by type Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003118 cationic copolymer Polymers 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
- 238000000265 homogenisation Methods 0.000 claims description 4
- 229920000083 poly(allylamine) Polymers 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 125000005842 heteroatom Chemical group 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
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 229920003043 Cellulose fiber Polymers 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 description 21
- 239000000123 paper Substances 0.000 description 21
- 239000002585 base Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000010790 dilution Methods 0.000 description 12
- 239000012895 dilution Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 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 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 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
- -1 clays Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000001412 amines Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000002655 kraft paper Substances 0.000 description 5
- 239000011087 paperboard Substances 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- 229920005601 base polymer Polymers 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 239000011111 cardboard Substances 0.000 description 4
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 4
- 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 4
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 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
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 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
- 239000007787 solid Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 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 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 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
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 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
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-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
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229920002554 vinyl polymer Polymers 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
- 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
- 241000447437 Gerreidae Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 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
- 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
- 238000009434 installation Methods 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
- 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
- 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 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
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material 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
- VZTGWJFIMGVKSN-UHFFFAOYSA-O trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium Chemical compound CC(=C)C(=O)NCCC[N+](C)(C)C VZTGWJFIMGVKSN-UHFFFAOYSA-O 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
- 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
- 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
- D21H17/34—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
- 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
-
- 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
Definitions
- the invention relates to an improved process for producing paper, cardboard or the like using at least one cationic polymer obtained by Hofmann degradation and making it possible to increase the rate of charge in said paper and paperboard, while maintaining 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 especially 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”), including retention of charges (FPAR: “First Pass Ash Retention”).
- 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).
- Conventionally used retention agents are added to the diluted dough, i.e. a fibrous suspension containing 0.1 to 1.5% solids. They allow to improve the charge retention, i.e. to optimize the amount 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.
- the document WO2009 / 036271 describes 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 body of head.
- this technique is difficult to implement because of the multitude of compounds added in a well-defined sequence.
- the document 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.
- 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.
- PAC coagulation agents
- DDR dry-strength resins
- DSR native starch, cationic starch, polyvinylamine
- drainage agents polyethyleneimine
- 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 Hofinann 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.
- 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.
- - Alpha (alkaline and / or alkaline earth / acrylamide hypohalide)
- - Beta (alkali and / or alkaline earth hydroxide / alkaline and / or alkaline earth hypohalide).
- 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.
- 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 hypohalide, of an alkaline hypochlorite, advantageously 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.
- water-insoluble monomers such as acrylic, allylic or vinyl monomers having a hydrophobic group.
- these monomers are employed in amounts generally less than 20 mol%, preferably less than 10 mol%. They may be chosen preferentially from the group comprising acrylamide derivatives such as N-alkylacrylamide, for example N-tert-butylacrylamide, octylacrylamide and N, N-dialkylacrylamides, such as N, N-dihexylacrylamide, etc.
- 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).
- the incorporation of the additional polyfunctional compound into the base copolymer can be carried out in the reaction medium, before or during the polymerization of the monomers constituting the (co) polymer base, or by any other grafting method on the finished base copolymer.
- 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.
- 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 earth.
- 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 the document JP 57077398 and well known by those skilled in the art, it is indeed intended to avoid the reaction between 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 cationicity increase 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
- Ti 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.
- SPS sodium persulfate
- MBS sodium metabisulfite
- the Hofmann degradation in itself takes place in the same way as in Example 1 of the Applicant's document WO2010061082 , by performing a complete Hofmann degradation.
- the cationic copolymer derived from acrylamide thus prepared has a bulk viscosity of 35 cps (25 ° C., Brookfield LV1, 60 rpm) and a concentration of 8.5% of active material.
- DADMAC dimethyldiallyl ammonium chloride
- 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 in itself takes place in the same way 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.
- Paper forms are made with an automatic dynamic form.
- 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.
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Description
L'invention concerne un procédé amélioré de fabrication de papier, de carton ou analogues mettant en oeuvre au moins un polymère cationique obtenu par dégradation d'Hofmann et permettant d'augmenter le taux de charges dans lesdits papier et cartons, tout en conservant des propriétés de résistance physique intéressantes. Elle a également pour objet les papiers ou cartons obtenus par ce procédé.The invention relates to an improved process for producing paper, cardboard or the like using at least one cationic polymer obtained by Hofmann degradation and making it possible to increase the rate of charge in said paper and paperboard, while maintaining properties of interesting physical resistance. It also relates to paper or paperboard obtained by this method.
Les polymères obtenus par dégradation d'Hofmann sont des composés chimiques couramment utilisés dans l'industrie de fabrication du papier. Par exemple, le document
La composition de la plupart des suspensions fibreuses utilisées lors de la fabrication du papier contient, suite à un ajout direct ou indirect (par utilisation de papiers recyclés), des charges inorganiques telles que des argiles, des kaolins, du carbonate de calcium, ou encore du dioxyde de titane. Industriellement, les charges les plus utilisées sont les carbonates de calcium, que ce soit sous forme broyée (on parle de de GCC pour « Ground Calcium Carbonate »), ou encore sous forme précipitée (on parle de PCC pour « Precipitated Calcium Carbonate »). A l'heure actuelle, eu égard à l'augmentation importante du prix des fibres papetières, il existe un intérêt croissant pour substituer, dans la feuille, une partie de la fibre par des charges minérales moins onéreuses.The 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. Industrially, 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") . At present, in view of the significant increase in the price of paper fibers, there is an increasing interest in substituting some of the fiber for the sheet with less expensive mineral fillers.
Classiquement, des agents de rétention sont utilisés afin d'augmenter la rétention globale dans la feuille (FPR : « First Pass Retention »), et notamment la rétention de charges (FPAR : « First Pass Ash Retention»). Chimiquement, ces agents de rétention sont, généralement, des polymères de hauts poids moléculaires (i.e. supérieur à 1 million de g/mol), tels que les copolymères d'acrylamide. Ces polymères peuvent être combinés avec des composés inorganiques microparticulaires (bentonite, silice colloïdale).Conventionally, retention agents are used to increase the overall retention in the sheet (RPF: "First Pass Retention"), including retention of charges (FPAR: "First Pass Ash Retention"). Chemically, 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).
Or, l'augmentation du taux de charges, au détriment des fibres, avec cette technologie très répandue, a tendance à détériorer les propriétés physiques du papier. La quantité de charges incorporées dans la feuille est donc limitée en raison des contraintes de résistance.However, the increase in the charge rate, to the detriment of fibers, with this widespread technology, tends to deteriorate the physical properties of the paper. The amount of charges incorporated in the sheet is therefore limited because of the strength constraints.
Les agents de rétention classiquement utilisés sont ajoutés dans la pâte diluée, i.e. une suspension fibreuse contenant de 0,1 à 1,5% de matière sèche. Ils permettent d'améliorer la rétention de charge, i.e. d'optimiser la quantité de charge utilisée. Leur rôle consiste notamment à retenir les charges dans le papier et ainsi à diminuer la quantité de charges évacuées dans les eaux blanches issues du drainage de la feuille lors de sa formation sur la toile.Conventionally used retention agents are added to the diluted dough, i.e. a fibrous suspension containing 0.1 to 1.5% solids. They allow to improve the charge retention, i.e. to optimize the amount 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.
Le document
Les documents
Le document
Bien que ces procédés permettent d'introduire dans la feuille un taux de charge avantageux tout en maintenant des propriétés physiques acceptables, ils présentent néanmoins des limites. Il existe donc un besoin d'augmenter encore la quantité de charges sans pour autant détériorer les performances physiques du papier.Although these methods make it possible to introduce into the sheet an advantageous loading rate while maintaining acceptable physical properties, they nevertheless have limits. There is therefore a need to further increase the amount of charges without deteriorating the physical performance of the paper.
Le problème que se propose de résoudre l'invention concerne notamment l'augmentation optimale de la quantité de charges, ou taux de charges, dans les feuilles de papier ou les cartons, tout en conservant des performances physiques satisfaisantes.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.
La présente invention propose un procédé amélioré de fabrication du papier, du carton et analogues comprenant l'ajout, dans une suspension fibreuse, d'au moins un polymère obtenu par dégradation d'Hofmann caractérisé en ce que le polymère obtenu par dégradation d'Hofmann est cationique, et ajouté avant la pompe de dilution (« fan pump ») de la pâte épaisse (thick stock ») avec les eaux blanches.
Plus précisément, la présente invention concerne un procédé de fabrication d'une feuille de papier et/ou de carton et analogues, selon lequel, dans une installation comprenant une pompe de dilution et une caisse de tête :
- on prépare une suspension fibreuse cellulosique, dans laquelle on introduit avantageusement des charges, désignée pâte épaisse (thick stock) ;
- on introduit dans la pâte épaisse les eaux blanches issues du drainage de la feuille ;
- on homogénéise le mélange ainsi obtenu dans la pompe de dilution (fan pump) ;
- on transfert la pâte diluée (thin stock) issue de l'homogénéisation jusqu'à la caisse de tête ;
- on forme la feuille ;
- on sèche la feuille.
More specifically, 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 white water coming from the drainage of the leaf is introduced into the thick paste;
- 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 formed;
- the sheet is dried.
Ce procédé est caractérisé en ce que, avant homogénéisation du mélange dans la pompe de dilution, c'est-à-dire avant la pompe de dilution, on introduit un copolymère cationique obtenu par réaction de dégradation dite d'Hofmann dans les eaux blanches et/ou la pâte épaisse, et/ou le mélange formé par les eaux blanches et la pâte épaisse.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.
Au regard de l'art antérieur, il est tout à fait surprenant de constater qu'une version cationique du polymère obtenue par dégradation d'Hofmann, lorsqu'elle est introduite dans le procédé comme ci-avant mentionné, puisse apporter de meilleures performances que les versions amphotères en termes de rétention de charge tout en conservant de très bonnes propriétés de résistance physique.In view of the prior art, it is quite surprising to find that a cationic version of the polymer obtained by Hofmann degradation, when introduced into the process as mentioned above, can provide better performance than the amphoteric versions in terms of charge retention while maintaining very good properties of physical resistance.
La présente invention a également pour objet les papiers ou cartons obtenus susceptibles d'être obtenus selon ce procédé.The present invention also relates to the paper or paperboard obtained that can be obtained by this method.
Sans être lié à une quelconque théorie, la Demanderesse considère que le polymère cationique obtenu par dégradation d'Hofmann peut jouer le rôle d'activateur d'affinités entre les charges et les fibres, ce qui permet aux charges d'être retenues de façon quantitative dans la feuille de papier au moment de la formation du réseau papetier. Par ailleurs, cette très bonne affinité semble renforcer la cohésion de la structure de la feuille de papier, lui conférant ainsi une résistance physique inégalée rapporté au pourcentage de charge présent dans la feuille.Without being bound to any theory, 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.
Comme précédemment mentionné, dans un processus de fabrication du papier, cartons ou analogues, les eaux blanches (« white water ») sont ajoutées dans la pâte épaisse (« thick stock ») avant la pompe de dilution (« fan pump »). Une fois mélangée, la pâte forme une pâte diluée (suspension diluée, « thin stock ») qui à la sortie de la pompe de dilution va jusqu'à la caisse de tête (« head box ») où la feuille humide est formée avant d'être séchée. Généralement une étape de cisaillement est prévue entre la pompe de dilution et la caisse de tête : il s'agit du « pressure screen » (épurateur à panier). Les charges sont ajoutées généralement sous forme de pâte liquide (« slurry ») dans la pâte épaisse. Cependant ces charges peuvent provenir d'une matière première contenant des charges, par exemple des pâtes désencrées, des pâtes cassées / collées etc....As previously mentioned, in a paper making process, cardboard or the like, the white water is added to the thick stock before the fan pump. Once mixed, 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. Generally 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.
La pâte épaisse, ou suspension fibreuse épaisse contient généralement entre 2 et 5% de matière sèche.The thick paste, or thick fibrous suspension generally contains between 2 and 5% of dry matter.
Comme déjà indiqué, le polymère cationique obtenu par dégradation d'Hofmann, peut être introduit dans le procédé dans la pâte épaisse et/ou dans les eaux blanches et/ou dans le mélange des deux avant la pompe de dilution.As already indicated, 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.
De manière conventionnelle, des charges sont ajoutées, notamment sous la forme de slurry, avant la pompe de dilution. Elles le sont dans la pâte épaisse et/ou les eaux blanches et/ou le mélange des deux, et ce, en une ou en plusieurs fois. Les charges sont néanmoins le plus souvent ajoutées avantageusement dans la pâte épaisse.Conventionally, 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.
Dans un premier mode de réalisation, le polymère est ajouté à proximité immédiate du ou des points d'introduction des charges.In a first embodiment, the polymer is added in the immediate vicinity of the point or points of introduction of the charges.
Dans un second mode de réalisation, le polymère cationique est introduit en même temps que les charges. Avantageusement, il est introduit dans ce cas dans le « slurry » de charges ou pendant sa préparation.In a second embodiment, the cationic polymer is introduced at the same time as the charges. Advantageously, it is introduced in this case in the "slurry" of charges or during its preparation.
Lorsque le polymère est introduit dans les eaux blanches, il l'est avantageusement juste avant leur mélange avec la pâte épaisse.When the polymer is introduced into the white water, it is advantageously just before mixing with the thick paste.
Par « slurry » de charge, on désigne une dispersion aqueuse contenant des charges. Généralement un « slurry » contient plus de 10% de charges en poids."Slurry" filler is an aqueous dispersion containing fillers. Generally a "slurry" contains more than 10% by weight.
Le procédé amélioré selon l'invention peut comprendre en outre l'addition dans la séquence papetière de tout autre composé minéral ou polymère naturel ou synthétique bien connu de l'homme de métier. On citera de manière non limitative l'addition d'au moins un additif choisi dans le groupe comprenant les agents de coagulation (PAC (polyaluminium chloride), polyDADMAC, polyamine), les agents de rétention (polymères anioniques, cationiques ou amphotères , bentonites, matériaux siliceux), les agents de résistance à sec (DSR) (« Dry-Strength Resins ») (amidon natif, amidon cationique, polyvinylamine) ou encore les agents de drainage (polyethyleneimine).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 addition of at least one additive chosen from the group comprising coagulation agents (PAC (polyaluminium chloride), polyDADMAC, polyamine), retention agents (anionic, cationic or amphoteric polymers, bentonites, siliceous materials), dry-strength resins (DSR) (native starch, cationic starch, polyvinylamine) or drainage agents (polyethyleneimine).
Dans un mode de réalisation particulier, le procédé selon l'invention comprend l'ajout d'au moins un polymère cationique obtenu par dégradation d'Hofmann avant la pompe de dilution, et d'au moins un polymère cationique à base d'acrylamide dans la pâte diluée, c'est-à-dire après la pompe de dilution. Préférentiellement ce polymère cationique à base d'acrylamide présente un poids moléculaire supérieur à 1 million de g/mol.In a particular embodiment, 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. Preferably, this cationic polymer based on acrylamide has a molecular weight greater than 1 million g / mol.
La quantité de polymère cationique obtenu par dégradation d'Hofmann introduite selon le procédé de l'invention est comprise entre 50 et 4000 grammes de polymère actif par tonne de pâte sèche (g/t). De préférence, la quantité introduite est comprise entre 100 g/t et 1000 g/t.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). Preferably, the amount introduced is between 100 g / t and 1000 g / t.
La dégradation d'Hofmann est une réaction découverte par Hofinann à la fin du dix-neuvième siècle, qui permet de convertir une amide en amine primaire par élimination de dioxyde de carbone. Le mécanisme réactionnel est détaillé ci-dessous.Hofmann's degradation is a reaction discovered by Hofinann 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.
En présence d'une base (soude), un proton est arraché à l'amide.
L'ion amidate formé réagit alors avec le chlore actif (Cl2) de l'hypochlorite (e.g. : NaClO qui est en équilibre : 2 NaOH + Cl2 ⇔ NaClO + NaCl + H2O) pour donner un N-chloramide. La base (NaOH) arrache un proton du chloramide pour former un anion. L'anion perd un ion chlorure pour former un nitrène qui subit une transposition en isocyanate.
Par réaction entre l'ion hydroxyde et l'isocyanate, un carbamate est formé.
Après décarboxylation (élimination de CO2) à partir du carbamate, on obtient une amine primaire
Pour la conversion de tout ou partie des fonctions amide d'un (co)polymère d'acrylamide en fonction amine, 2 facteurs principaux interviennent (exprimés en rapports molaires). Il s'agit de : - Alpha = (hypohalogénure d'alcalin et/ou alcalino terreux / acrylamide) et - Beta = (hydroxyde d'alcalin et/ou alcalino terreux / hypohalogénure d'alcalin et/ou alcalino terreux).
Les polymères cationiques obtenus par dégradation Hofmann mis en oeuvre dans le procédé selon l'invention sont avantageusement choisis parmi les polymères décrits dans le document
The cationic polymers obtained by Hofmann degradation used in the process according to the invention are advantageously chosen from the polymers described in the document
Ils sont obtenus par dégradation d'Hofmann sur un précurseur à base acrylamide ou dérivés, autrement appelé (co)polymère base, préalablement modifié avec au moins un composé polyfonctionnel contenant au moins 3 hétéroatomes identiques ou différents et présentant chacun au moins un hydrogène mobile.They are obtained by Hofmann degradation on a precursor based on acrylamide or derivatives, otherwise called (co) polymer base, previously modified with at least one polyfunctional compound containing at least 3 identical or different heteroatoms and each having at least one mobile hydrogen.
Les hétéroatomes peuvent être : N, S, O, PThe heteroatoms can be: N, S, O, P
Les composés polyfonctionnels peuvent notamment être des oligomères, des polymères, ou des chaînes carbonées comportant au moins trois atomes de carbone.The polyfunctional compounds may in particular be oligomers, polymers, or carbon chains containing at least three carbon atoms.
Dans un mode de réalisation avantageux, le composé polyfonctionnel peut être choisi dans le groupe comprenant les polyéthylèneimines (PEI), les polyamines (primaires ou secondaires), les polyallylamines, les polyamines amides (PAA), les polythiols, les polyalcools, les polyamides epichloridrine (PAE) et leurs mélanges.In an advantageous embodiment, 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.
Dans un mode préférentiel, le composé polyfonctionnel incorporé peut être la polyéthylèneimine (PEI) ou une polyamine amide (PAA).In a preferred embodiment, the polyfunctional compound incorporated may be polyethyleneimine (PEI) or a polyamine amide (PAA).
En pratique, le polymère obtenu à l'issue de la réaction d'Hofmann pourra être ramifié, du fait d'une ramification du polymère base. En d'autres termes, c'est le caractère ramifié du copolymère base qui conférera son état ramifié au polymère final.In practice, 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.
Dans un mode de réalisation préféré, le polymère est obtenu par réaction de dégradation dite d'Hofmann en présence, en tant qu'hypohalogénure, d'un hypochlorite d'alcalin, avantageusement l'hypochlorite de sodium.In a preferred embodiment, the polymer is obtained by Hofmann degradation reaction in the presence, as hypohalide, of an alkaline hypochlorite, advantageously sodium hypochlorite.
Selon une autre caractéristique, le coefficient Alpha hypohalogénure/monomère non ionique (exprimés en rapports molaire) utilisé pour la préparation des polymères de l'invention est supérieur à 0,3, voire à 0,5, avantageusement compris entre 0,8 et 1 inclus.According to another characteristic, 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.
Selon une autre caractéristique, le produit de dégradation d'Hofmann est produit à une concentration supérieure à 4% en poids, de préférence supérieure à 5%, avantageusement supérieure à 7%.According to another characteristic, the Hofmann degradation product is produced at a concentration greater than 4% by weight, preferably greater than 5%, advantageously greater than 7%.
En outre, le copolymère de l'invention peut présenter une densité de charge cationique de préférence supérieure à 2 meq/g et avantageusement supérieure à 5 meq/g.In addition, 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.
Le polymère mis en oeuvre dans le procédé selon l'invention est avantageusement obtenu par réaction de dégradation d'Hofmann sur un copolymère base comprenant :
- au moins 5 moles % d'un monomère non ionique choisi dans le groupe comprenant l'acrylamide (et/ou le méthacrylamide), le N, N diméthylacrylamide et/ou l'acrylonitrile, préférentiellement l'acrylamide,
- au moins 0,001 moles % d'au moins un composé polyfonctionnel additionnel choisi dans le groupe comprenant polyéthylèneimine, polyamine (primaire ou secondaire), polyallylamine, polythiols avantageusement polyethylèneimine,
- optionnellement au moins :
- o un monomère éthylénique cationique non saturé, choisi préférentiellement dans le groupe comprenant les monomères de type dialkylaminoalkyl (meth)acrylamide, diallylamine, methyldiallylamine et leurs sel d'ammonium quaternaire ou d'acides. On citera en particulier le chlorure de dimethyldiallylammonium (DADMAC), le chlorure d'acrylamidopropyltrimethylammonium (APTAC) et/ou le chlorure de methacrylamidopropyltrimethylammonium (MAPTAC),
- o et/ou un monomère non ionique choisi préférentiellement dans le groupe comprenant le N-vinyl acetamide, N-vinyl formamide, la N-vinylpyrrolidone et/ou le vinyl acétate.
- at least 5 mole% of a nonionic monomer chosen from the group comprising acrylamide (and / or methacrylamide), N, N-dimethylacrylamide and / or acrylonitrile, preferably acrylamide,
- at least 0.001 mol% of at least one additional polyfunctional compound selected from the group consisting of polyethyleneimine, polyamine (primary or secondary), polyallylamine, preferably polyethylene polyethiols,
- 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. In particular, mention may be made of dimethyldiallylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC) and / or methacrylamidopropyltrimethylammonium chloride (MAPTAC),
- and / or a nonionic monomer preferably chosen from the group comprising N-vinyl acetamide, N-vinyl formamide, N-vinylpyrrolidone and / or vinyl acetate.
Avantageusement, le polymère base est ramifié et constitué de préférence des trois types de composés suivants :
- acrylamide,
- polyéthylèneimine, et
- au moins un co-monomère éthylénique cationique non saturé, choisi dans le groupe comprenant les monomères de type dialkylaminoalkyl (meth)acrylamide, diallylamine, methyldiallylamine et leurs sel d'ammonium quaternaire ou d'acides, de préférence le chlorure de dimethyldiallylammonium.
- acrylamide,
- polyethyleneimine, and
- at least one unsaturated cationic ethylenic comonomer selected from the group consisting of dialkylaminoalkyl (meth) acrylamide, diallylamine, methyldiallylamine monomers and their quaternary ammonium or acid salts, preferably dimethyldiallylammonium chloride.
II est important de noter que, en association avec ces monomères, il est également possible d'utiliser des monomères insolubles dans l'eau tels que les monomères acryliques, allyliques ou vinyliques comportant un groupement hydrophobe. Lors de leur utilisation, ces monomères sont employés dans des quantités généralement inférieures à 20 moles%, de préférence inférieures à 10 moles%. Ils peuvent être choisis préférentiellement dans le groupe comprenant les dérivés de l'acrylamide comme les N-alkylacrylamide par exemple le N-tert-butylacrylamide, l'octylacrylamide ainsi que les N,N-dialkylacrylamides comme le N,N-dihexylacrylamide...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%. They may be chosen preferentially from the group comprising acrylamide derivatives such as N-alkylacrylamide, for example N-tert-butylacrylamide, octylacrylamide and N, N-dialkylacrylamides, such as N, N-dihexylacrylamide, etc.
Dans un mode de réalisation préféré, le précurseur à base acrylamide ou dérivés (autrement appelé polymère base sur lequel la dégradation d'Hofmann est effectuée) incorpore, en son sein même, au moins de la polyéthylèneimine (PEI) ;
- le coefficient alpha hypohalogénure/monomère non ionique utilisé pour la préparation des polymères de l'invention est compris entre 0,8 et 1 inclus ;
- le copolymère base est ramifié.
- 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.
On pourra effectuer la ramification de préférence durant (ou éventuellement après) la polymérisation du copolymère " base ", en présence d'un agent ramifiant polyfonctionnel et éventuellement d'un agent de transfert. On trouvera ci-dessous une liste non limitative d'agents ramifiant : méthylène bisacrylamide (MBA), l'ethylene glycol di-acrylate, le polyethylene glycol dimethacrylate, le diacrylamide, le cyanomethylacrylate, le vinyloxyethylacrylate ou methacrylate, la triallylamine, le formaldehyde, le glyoxal, les composés de type glycidyléther comme l'éthylèneglycol di glycidyléther, ou des époxy ou tout autre moyen bien connu de l'homme de métier permettant la réticulation.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. 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.
En pratique, l'agent de ramification est introduit avantageusement à raison de cinq à cinquante milles (5 à 50000) parties par million en poids par rapport à la matière active, de préférence 5 à 10000, avantageusement de 5 à 5000. Avantageusement, l'agent de ramification est le méthylène bis acrylamide (MBA).In practice, 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. Advantageously, the branching agent is methylenebisacrylamide (MBA).
L'incorporation du composé polyfonctionnel additionnel au sein du copolymère base peut être réalisée dans le milieu réactionnel, avant ou pendant la polymérisation des monomères constituant le (co)polymère base, ou par tout autre méthode de greffage sur le copolymère base fini.The incorporation of the additional polyfunctional compound into the base copolymer can be carried out in the reaction medium, before or during the polymerization of the monomers constituting the (co) polymer base, or by any other grafting method on the finished base copolymer.
De façon préférentielle, le composé polyfonctionnel additionnel est mélangé à un co-monomère avant polymérisation.Preferably, the additional polyfunctional compound is mixed with a comonomer before polymerization.
L'agent de transfert peut notamment être choisi de manière non limitative dans le groupe comprenant l'alcool isopropylique, l'hypophosphite de sodium, et le mercaptoethanol.
Le copolymère servant de base à la réaction de dégradation d'Hofmann ne nécessite pas le développement de procédé de polymérisation particulier. Les principales techniques de polymérisation, bien connues par l'homme de métier et pouvant être utilisées sont : la polymérisation par précipitation, la polymérisation en émulsion (aqueuse ou inverse) suivie ou non d'une étape de distillation et/ou de « spray drying » (séchage par pulvérisation), et la polymérisation en suspension ou la polymérisation en solution, ces deux techniques étant préférées.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.
Il est également possible d'ajouter dans la solution de copolymère base, avant ou pendant la réaction de dégradation d'Hofmann certains composés qui sont susceptibles de réagir sur les fonctions isocyanates du polymère générées en cours de dégradation. De manière générale, il s'agit de molécules portant des fonctions chimiques nucléophiles telles que des fonctions hydroxyle, ou amine. A titre d'exemples, les composés en question peuvent donc être de la famille : des alcools, des polyols, des polyamines, des polyéthylèneimines.It is also possible to add in the base copolymer solution, before or during the Hofmann degradation reaction, certain compounds which are capable of reacting with the isocyanate functions of the polymer generated during degradation. In general, they are molecules carrying nucleophilic chemical functions such as hydroxyl or amine functions. As examples, the compounds in question can therefore be of the family: alcohols, polyols, polyamines, polyethyleneimines.
L'incorporation de sels d'ions cationiques polyvalents, comme mentionnée dans le document de la Demanderesse
Comme déjà précisé, la réaction d'Hofmann nécessite la conversion des fonctions amide en fonctions amines en faisant intervenir 2 facteurs principaux (exprimés en rapports molaires) :
- Alpha = (hypochlorite d'alcalin et/ou d'alcalino-terreux/ (meth)acrylamide)
- Beta = (hydroxyde d'alcalin et/ou alcalino-terreux / hypochlorite d'alcalin et/ou d'alcalino-terreux)
- Alpha = (alkaline and / or alkaline earth hypochlorite / (meth) acrylamide)
- Beta = (alkali and / or alkaline earth hydroxide / alkaline and / or alkaline earth hypochlorite)
A partir d'une solution de copolymère " base " précédemment décrit de concentration comprise entre 10 et 40% en poids, de préférence entre 15 et 25%, on détermine la quantité molaire de fonction amide totale. On choisit alors le niveau de dégradation Alpha, qui permet de déterminer la quantité sèche d'hypohalogénure d'alcalin et/ou d'alcalino-terreux et ensuite le coefficient béta, qui permet de déterminer la quantité sèche d'hydroxyde d'alcalin et/ou alcalino-terreux.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 earth.
On prépare alors une solution d'hypohalogénure et d'hydroxyde d'alcalin et/ou alcalino-terreux à partir des rapports alpha et béta. Selon l'invention, les réactifs préférablement utilisés sont l'hypochlorite de sodium (eau de javel) et la soude (hydroxyde de sodium).A solution of hypohalide and alkali and / or alkaline earth hydroxide is then prepared from the alpha and beta ratios. According to the invention, the reagents preferably used are sodium hypochlorite (bleach) and sodium hydroxide (sodium hydroxide).
Afin de stabiliser les fonctions aminées qui vont être produites, on peut éventuellement rajouter, dans le réacteur contenant le polymère base, un (ou éventuellement plusieurs) dérivé d'ammonium quaternaire tel que cela est décrit dans le document
L'augmentation en cationicité du copolymère base s'effectue lors de la dégradation dite d'Hofmann, par l'utilisation d'un hypohalogénure d'alcalin ou d'alcalino-terreux.In order to stabilize the 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 the document
The cationicity increase of the base copolymer takes place during the so-called Hofmann degradation, by the use of an alkaline or alkaline earth hypohalide.
De même, bien que préparés en solution, les polymères de l'invention peuvent également être proposés sous forme solide. Dans ces conditions, la forme solide contient non seulement le copolymère, mais également une proportion de sel obtenue à l'issue de la réaction de dégradation d'Hofmann. En pratique, ils sont obtenus entre autres par des procédés consistant à sécher la solution précédemment citée. Les principales techniques d'isolation alors utilisées sont celles du séchage par atomisation ou pulvérisation (qui consiste à créer un nuage de fines gouttelettes dans un courant gazeux chaud pendant une durée contrôlée), du séchage à tambour, des sécheurs à lit fluidisé...Similarly, although prepared in solution, the polymers of the invention may also be provided in solid form. Under these conditions, the solid form contains not only the copolymer, but also a proportion of salt obtained at the end of the Hofmann degradation reaction. In practice, 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.
L'incorporation du polymère cationique obtenu par dégradation d'Hofmann se fera avec les moyens conventionnels connus de l'homme de l'art.The incorporation of the cationic polymer obtained by Hofmann degradation will be done with the conventional means known to those skilled in the art.
Le procédé selon l'invention pourra être utilisé avec tous types de pâte : des pâtes de fibres vierges (Kraft, Bisulfite...), de fibres recyclées, des pâtes désencrées, des pâtes mécaniques et thermomécaniques, 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.
En ce qui concerne les charges, il peut s'agir de tous les types de charges pouvant être choisies dans le groupe comprenant les argiles, les kaolins, le carbonate de calcium broyé (GCC), le carbonate de calcium précipité (PCC), le dioxyde de titane, et leurs mélanges. Les charges pourront être ajoutées sous différentes formes, la forme « slurry » étant la plus rencontrée. Elles pourront être préparées avec ou sans dispersant, hors ou sur site de fabrication du papier.With respect to 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. 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.
Le polymère cationique obtenu par dégradation d'Hofmann pourra être préparé à proximité de la machine à papier.The cationic polymer obtained by Hofmann degradation may be prepared near the paper machine.
Les exemples ci-après permettent d'illustrer l'invention, mais n'ont aucun caractère limitatif.The following examples illustrate the invention, but are not limiting in nature.
Le polymère cationique A est obtenu par une réaction de dégradation d'Hofmann (alpha = 1) sur un copolymère base (solution à 20% de copolymère base), d'acrylamide (70% molaire) et de chlorure de dimethyldiallyl ammonium (DADMAC) (30% molaire) ramifié (MBA : 600 ppm / matière active) modifié avec un polymère de polyéthylèneimine (de type Polymin HM de BASF), à hauteur de 5% en matière active.The cationic polymer A is obtained by a Hofmann degradation reaction (alpha = 1) on a base copolymer (20% solution of base copolymer), of acrylamide (70 mol%) and of dimethyldiallyl ammonium chloride (DADMAC). (30% molar) branched (MBA: 600 ppm / active ingredient) modified with a polyethyleneimine polymer (BASF type of Polymin HM), at a level of 5% of active material.
Pour ce faire, la polyéthylèneimine est mélangée au monomère de DADMAC et au MBA dans le réacteur.To do this, the polyethyleneimine is mixed with the DADMAC monomer and the MBA in the reactor.
L'acrylamide sera incorporée en coulée continu pendant 2h, dans un milieu réactionnel maintenu à 85°C. La polymérisation est catalysée en présence de SPS (sodium persulfate) et de MBS (sodium metabisulfite), catalyseurs bien connus de l'homme de métier. Le polymère précurseur ainsi obtenu présente une viscosité de 5500 cps (25°C, Brookfield LV3, 12 rpm).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).
La dégradation Hofmann en elle-même se déroule de la même manière que dans l'exemple 1 du document de la Demanderesse
Le polymère cationique B est obtenu par une réaction de dégradation d'Hofmann (alpha = 1) sur un copolymère base (20% en matière active) d'acrylamide (60% molaire), d'acide acrylique (10% molaire) et de chlorure de dimethyldiallyl ammonium (DADMAC) (30% molaire) ramifié (MBA : 600 ppm / matière active) modifié avec un polymère de polyéthylèneimine (de type Polymin HM de BASF), à hauteur de 5% en matière active.
Pour ce faire, la polyéthylèneimine est mélangée au monomère de DADMAC et au MBA dans le réacteur.The cationic polymer B is obtained by a Hofmann degradation reaction (alpha = 1) on a base copolymer (20% of active material) of acrylamide (60 mol%), acrylic acid (10 mol%) and dimethyldiallyl ammonium chloride (DADMAC) (30% molar) branched (MBA: 600 ppm / active ingredient) modified with a polyethyleneimine polymer (BASF type Polymin HM), at a level of 5% active ingredient.
To do this, the polyethyleneimine is mixed with the DADMAC monomer and the MBA in the reactor.
L'acrylamide et l'acide acrylique seront incorporés en coulée continu pendant 2h, dans un milieu réactionnel maintenu à 85°C. La polymérisation est catalysée en présence de SPS et de MBS, catalyseurs bien connus de l'homme de métier. Le polymère précurseur ainsi obtenu présente une viscosité de 4500 cps (25°C, Brookfield LV3, 12 rpm).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).
La dégradation Hofmann en elle-même se déroule de la même manière que dans l'exemple 1 du document de la Demanderesse
Ces polymères seront comparés à (1) un copolymère poudre acrylamide/ADAME MeCl de haut poids moléculaire (FO 4190 PG1, de SNF Floerger), agent standard de rétention, et (2) le Luredur PR 8351 de BASF, copolymère amphotère à base de PVA (issue de l'hydrolyse de NVF), référence actuelle en tant qu'agent de rétention de charge et de maintien de performances DSR.These 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.
Des formettes de papier sont réalisées avec une formette dynamique automatique.Paper forms are made with an automatic dynamic form.
Le « slurry » de pâte est réalisé par désintégration de pâte sèche afin d'obtenir une concentration finale de 3%.The "slurry" of the dough is made by disintegrating dry pulp in order to obtain a final concentration of 3%.
La quantité nécessaire de pâte est prélevée de manière à obtenir au final une feuille présentant un grammage de 60g/m2.The necessary amount of pulp is removed so as to finally obtain a sheet having a basis weight of 60 g / m 2 .
La pâte concentrée est introduite dans le cuvier de la formette dynamique et y est agitée. A cette pâte est ajouté un « slurry » de charges, injecté simultanément (mais de façon séparée) au polymère A, B ou au Luredur PR 8351 de BASF. Cette pâte est ensuite diluée jusqu'à une concentration de 0,32%.The concentrated paste is introduced into the vat of the dynamic form and stirred there. To this paste is added 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%.
En mode manuel, la pâte est pompée jusqu'au niveau de la buse afin d'amorcer le circuit.In manual mode, the dough is pumped to the nozzle level to prime the circuit.
Un buvard et la toile de formation sont placés dans le bol de la formette dynamique avant de démarrer la rotation du bol à 900m/min et de construire le mur d'eau. Potentiellement, un agent de rétention sera injecté 10 secondes avant le démarrage du cycle de fabrication de la feuille. La feuille est alors réalisée (en mode automatique) par 22 aller-retours de la buse projetant la pâte dans le mur d'eau. Une fois que l'eau est drainée et que la séquence automatique est terminée, la toile de formation avec le réseau de fibres formé est retirée du bol de la formette dynamique et placée sur une table. Un buvard sec est déposé du côté du matelas de fibres humides et est pressé une fois avec un rouleau. L'ensemble est retourné et la toile est délicatement séparée du matelas fibreux. Un second buvard sec est déposé et la feuille (entre les deux buvards) est pressée une fois sous une presse délivrant 4 bars puis est séchée sur un sécheur tendu pendant 9 min à 107°C. Les deux buvards sont ensuite retirés et la feuille est stockée pendant une nuit dans une pièce à humidité et température contrôlées (50% d'humidité relative et 23°C). Les propriétés de résistance à sec de toutes les feuilles obtenues par cette procédure sont alors évaluées.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.
L'éclatement (Burst index) est mesuré avec un éclatomètre Messmer Buchel M 405 (moyenne sur 14 mesures).The burst index is measured with a Messmer Buchel M 405 (average of 14 measurements).
La traction à sec est mesurée dans le sens machine avec un appareil de traction Testometric AX (moyenne sur 5 échantillons).Dry traction is measured in the machine direction with a Testometric AX tensile tester (average of 5 samples).
Le taux de charges dans la feuille est mesuré à l'aide d'un four à moufle selon une procédure standard de mesure de matière non organique (570°C pendant 5 heures)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)
Les tests sont réalisés avec une pâte à pH neutre de composition suivante, en poids par rapport au poids sec de la composition : (cette composition dépasse 100% de matière)
- 70% de fibres de kraft de feuillus blanchis
- 10% de fibres de kraft de résineux blanchis
- 20% de fibres de pâte mécanique à base de pin
- 70% bleached hardwood kraft fiber
- 10% bleached softwood kraft fiber
- 20% pinewood mechanical pulp fibers
Nous pouvons observer que le polymère A apporte plus de rétention de charges mais aussi plus de performances DSR que le Luredur PR 8351.We can observe that polymer A provides more charge retention but also more DSR performance than Luredur PR 8351.
Le polymère B, amphotère, donne des performances équivalentes au Luredur PR 8351 mais inférieures au polymère A.
De manière connue de l'homme de métier, l'utilisation simple d'un agent de rétention apporte en rétention de charges, mais détériore fortement les performances physiques.In a manner known to those skilled in the art, the simple use of a retention agent provides charge retention, but greatly deteriorates the physical performance.
En combinaison avec un agent de rétention, le polymère A permet d'obtenir la plus haute quantité de charges dans la feuille de papier tout en conservant de bonnes propriétés de résistances physique de la feuille.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.
Claims (10)
- Process for manufacturing a sheet of paper and/or board and the like, according to which, in a plant comprising a fan pump and a head box:- a cellulose fibre suspension, referred to as thick stock, is prepared;- the white waters resulting from the drainage of the sheet are introduced into the thick stock;- the mixture thus obtained is homogenized in the fan pump;- the thin stock resulting from the homogenization is transferred to the head box;- the sheet is formed;- the sheet is dried,characterized in that, before homogenization of the mixture in the fan pump, a cationic copolymer obtained by Hofmann degradation reaction is introduced into the white waters and/or the thick stock and/or the mixture formed by the white waters and the thick stock.
- Process according to Claim 1, characterized in that fillers are introduced into the thick stock and in that the cationic polymer is introduced in the immediate vicinity of the filler introduction point or points.
- Process according to Claim 1, characterized in that fillers are introduced into the thick stock and in that the cationic polymer is introduced simultaneously with the fillers.
- Process according to Claim 3, characterized in that the fillers are introduced in the form of a slurry and in that the cationic polymer is introduced into the filler slurry or during the preparation thereof.
- Process according to Claim 1, characterized in that the cationic polymer is introduced into the white waters, preferably just before introducing said white waters into the thick stock.
- Process according to one of Claims 2 to 4, characterized in that the fillers are selected from the group comprising clays, kaolins, ground calcium carbonate (GCC), precipitated calcium carbonate (PCC), titanium dioxide, and mixtures thereof.
- Process according to one of the preceding claims, characterized in that the cationic copolymer is obtained by Hofmann degradation reaction on a precursor based on acrylamide or derivatives, otherwise referred to as base (co)polymer, previously modified with at least one polyfunctional compound containing at least 3 identical or different heteroatoms that each have at least one mobile hydrogen.
- Process according to Claim 7, characterized in that the polyfunctional compound is selected from the group comprising polyethyleneimines (PEIs), polyamines (primary or secondary), polyallylamines, polyamine amides (PAAs), polythiols, polyalcohols, polyamide-epichlorohydrin (PAE) resins, and mixtures thereof.
- Process according to Claim 7, characterized in that the base (co)polymer is branched by addition of a polyfunctional branching agent and optionally a transfer agent.
- Process according to one of Claims 7 to 9, characterized in that the hypohalide/nonionic monomer Alpha coefficient (expressed as molar ratio) used for preparation of the polymer is between 0.8 and 1 inclusive.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
Publications (2)
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EP2870287A1 EP2870287A1 (en) | 2015-05-13 |
EP2870287B1 true EP2870287B1 (en) | 2016-08-17 |
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EP13737326.2A Active EP2870287B1 (en) | 2012-07-09 | 2013-06-17 | Improved method for manufacturing paper using a cationic polymer obtained by hofmann degradation |
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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) |
FR (1) | FR2992981B1 (en) |
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 |
US20190232522A1 (en) * | 2016-09-19 | 2019-08-01 | 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 |
US8778139B2 (en) | 2004-12-17 | 2014-07-15 | Basf Aktiengesellschaft | 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 |
CN102803605A (en) * | 2009-06-16 | 2012-11-28 | 巴斯夫欧洲公司 | 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 |
-
2012
- 2012-07-09 FR FR1256575A patent/FR2992981B1/en not_active Expired - Fee Related
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2013
- 2013-06-17 WO PCT/FR2013/051406 patent/WO2014009621A1/en active Application Filing
- 2013-06-17 KR KR1020147035842A patent/KR102123132B1/en active IP Right Grant
- 2013-06-17 EP EP13737326.2A patent/EP2870287B1/en active Active
- 2013-06-17 US US14/408,889 patent/US9303359B2/en not_active Expired - Fee Related
- 2013-06-17 CN CN201380031028.5A patent/CN104395525A/en active Pending
- 2013-06-17 CA CA2876609A patent/CA2876609C/en active Active
- 2013-06-17 BR BR112014031379A patent/BR112014031379A2/en not_active Application Discontinuation
- 2013-06-17 ES ES13737326.2T patent/ES2590528T3/en active Active
Also Published As
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KR102123132B1 (en) | 2020-06-15 |
FR2992981A1 (en) | 2014-01-10 |
WO2014009621A1 (en) | 2014-01-16 |
US9303359B2 (en) | 2016-04-05 |
KR20150035723A (en) | 2015-04-07 |
EP2870287A1 (en) | 2015-05-13 |
FR2992981B1 (en) | 2014-07-04 |
CA2876609A1 (en) | 2014-01-16 |
CA2876609C (en) | 2020-02-11 |
CN104395525A (en) | 2015-03-04 |
US20150176208A1 (en) | 2015-06-25 |
BR112014031379A2 (en) | 2017-06-27 |
ES2590528T3 (en) | 2016-11-22 |
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