NO336351B1 - Method of making paper - Google Patents
Method of making paperInfo
- Publication number
- NO336351B1 NO336351B1 NO20043623A NO20043623A NO336351B1 NO 336351 B1 NO336351 B1 NO 336351B1 NO 20043623 A NO20043623 A NO 20043623A NO 20043623 A NO20043623 A NO 20043623A NO 336351 B1 NO336351 B1 NO 336351B1
- Authority
- NO
- Norway
- Prior art keywords
- anionic
- polymer
- cationic
- aromatic
- vinyl addition
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000642 polymer Polymers 0.000 claims description 77
- 239000000178 monomer Substances 0.000 claims description 48
- 229920002554 vinyl polymer Polymers 0.000 claims description 44
- 239000000725 suspension Substances 0.000 claims description 34
- 125000000129 anionic group Chemical group 0.000 claims description 32
- 125000002091 cationic group Chemical group 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 229920006318 anionic polymer Polymers 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 239000000123 paper Substances 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 5
- 239000011111 cardboard Substances 0.000 claims description 4
- 150000002561 ketenes Chemical class 0.000 claims description 4
- 239000011087 paperboard Substances 0.000 claims description 4
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 2
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000007792 addition Methods 0.000 description 53
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 27
- 150000003839 salts Chemical group 0.000 description 17
- 229920006317 cationic polymer Polymers 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 16
- -1 dimethylaminoethyl Chemical group 0.000 description 15
- 229920002678 cellulose Polymers 0.000 description 13
- 239000001913 cellulose Substances 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- 229920002472 Starch Polymers 0.000 description 6
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000003926 acrylamides Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 4
- 238000004026 adhesive bonding Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004823 Reactive adhesive Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical group CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical group CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000002408 directed self-assembly Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- FAMIQNOUNCNXNK-UHFFFAOYSA-M 1-chloro-3-pyridin-1-ium-1-ylpropan-2-ol;chloride Chemical compound [Cl-].ClCC(O)C[N+]1=CC=CC=C1 FAMIQNOUNCNXNK-UHFFFAOYSA-M 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical group CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- NVNLLIYOARQCIX-NIMBGDMISA-N CC[C@H](C)[C@H](N)C(=O)N\C(=C/C)C(=O)N[C@@H]1CSC[C@H](NC(=O)[C@H](CC(C)C)NC(=O)C(=C)NC(=O)[C@@H](NC1=O)[C@@H](C)CC)C(=O)N[C@@H]1[C@H](C)SC[C@H](NC(=O)CNC(=O)[C@@H]2CCCN2C1=O)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H]1[C@H](C)SC[C@H](NC(=O)CNC(=O)[C@H](CCSC)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)CNC1=O)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H]1[C@H](C)SC[C@@H]2NC(=O)[C@H](NC(=O)[C@H](C)NC1=O)[C@H](C)SC[C@H](NC(=O)[C@H](CC1=CN=CN1)NC2=O)C(=O)N[C@@H](CO)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CC1=CN=CN1)C(=O)N[C@@H](C(C)C)C(=O)NC(=C)C(=O)N[C@@H](CCCCN)C(O)=O Chemical compound CC[C@H](C)[C@H](N)C(=O)N\C(=C/C)C(=O)N[C@@H]1CSC[C@H](NC(=O)[C@H](CC(C)C)NC(=O)C(=C)NC(=O)[C@@H](NC1=O)[C@@H](C)CC)C(=O)N[C@@H]1[C@H](C)SC[C@H](NC(=O)CNC(=O)[C@@H]2CCCN2C1=O)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H]1[C@H](C)SC[C@H](NC(=O)CNC(=O)[C@H](CCSC)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)CNC1=O)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H]1[C@H](C)SC[C@@H]2NC(=O)[C@H](NC(=O)[C@H](C)NC1=O)[C@H](C)SC[C@H](NC(=O)[C@H](CC1=CN=CN1)NC2=O)C(=O)N[C@@H](CO)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CC1=CN=CN1)C(=O)N[C@@H](C(C)C)C(=O)NC(=C)C(=O)N[C@@H](CCCCN)C(O)=O NVNLLIYOARQCIX-NIMBGDMISA-N 0.000 description 1
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical class NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Chemical group OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- NRGNIRIWTPPPCH-UHFFFAOYSA-N [3-(dimethylamino)-3-hydroxypropyl] prop-2-enoate Chemical compound CN(C)C(O)CCOC(=O)C=C NRGNIRIWTPPPCH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- LMIZORQOLSLQRY-UHFFFAOYSA-N benzene;naphthalene Chemical compound C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 LMIZORQOLSLQRY-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- AAZVLNHLLNLZEE-UHFFFAOYSA-M benzyl-(3-chloro-2-hydroxypropyl)-dimethylazanium;chloride Chemical compound [Cl-].ClCC(O)C[N+](C)(C)CC1=CC=CC=C1 AAZVLNHLLNLZEE-UHFFFAOYSA-M 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- OKFVXVIKDVLAQH-UHFFFAOYSA-N chloromethylbenzene prop-2-enamide Chemical compound C(C=C)(=O)N.C(C1=CC=CC=C1)Cl OKFVXVIKDVLAQH-UHFFFAOYSA-N 0.000 description 1
- ZTUMLBMROBHIIH-UHFFFAOYSA-N chloromethylbenzene;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group ClCC1=CC=CC=C1.CN(C)CCOC(=O)C(C)=C ZTUMLBMROBHIIH-UHFFFAOYSA-N 0.000 description 1
- CEJFYGPXPSZIID-UHFFFAOYSA-N chloromethylbenzene;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClCC1=CC=CC=C1.CN(C)CCOC(=O)C=C CEJFYGPXPSZIID-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical group C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011976 maleic acid Chemical group 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 150000004780 naphthols Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Chemical group OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Chemical group CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 239000002351 wastewater Substances 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
- D21H23/06—Controlling the addition
- D21H23/14—Controlling the addition by selecting point of addition or time of contact between components
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- 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
- D21H21/14—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 characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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- 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
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
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- D—TEXTILES; PAPER
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- 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
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- 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
- D21H3/00—Paper or cardboard prepared by adding substances to the pulp or to the formed web on the paper-making machine and by applying substances to finished paper or cardboard (on the paper-making machine), also when the intention is to impregnate at least a part of the paper body
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- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
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- 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
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- D—TEXTILES; PAPER
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- 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
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
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- 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
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- 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
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- 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
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- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
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Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for tilvirkning av papir og papp omfattende tilsetningen av to forskjellige polymerer til en vandig cellulosehol-dig suspensjon der én er en aromatholdig kationisk vinyladdisjonspolymer og den andre er en ionisk polymer med en vektgjennomsnittlig molekylvekt i området fra omtrent 6 000 opptil omtrent 100 000 valgt fra gruppen bestående av vinyladdisjonspolymerer og kondensasjonspolymerer. The present invention relates to a method for the production of paper and cardboard comprising the addition of two different polymers to an aqueous cellulose-containing suspension, where one is an aromatic cationic vinyl addition polymer and the other is an ionic polymer with a weight average molecular weight in the range from approximately 6,000 to approximately 100,000 selected from the group consisting of vinyl addition polymers and condensation polymers.
Bakgrunn Background
Interne limmidler tilsettes vanligvis til våtenden av papirfremstillingsprosessen der Internal sizing agents are usually added to the wet end of the papermaking process there
papirets adsorpsjonsevne for væsker senkes. Vanlige anvendte interne limmidler er lim basert på harpiksderivater og cellulosereaktive limmidler, nemlig keten, dimerer og syreanhydrider. Flerformål kontorpapir må være ganske hardt limt for å fungere ordentlig i dagens høyhastighets reproduksjonsmaskiner. En måte å oppnå papir som er fullstendig limt, dvs. har et cobb60tall under 30 eller å måle kontaktvinkelen av en vanndråpe på papiret der vinkler større enn 80 grader etter 10 sekunder indikerer god liming, er å tilsette mer limmiddel til suspensjonen. Derimot øker sann-synligheten for å ende opp med kjørbarhetsproblemer i papirfabrikken samt pro-duksjonskostnadene. the paper's adsorption capacity for liquids is lowered. Commonly used internal adhesives are adhesives based on resin derivatives and cellulose-reactive adhesives, namely ketene, dimers and acid anhydrides. Multi-purpose office paper must be fairly hard-glued to function properly in today's high-speed reproduction machines. One way to obtain paper that is fully bonded, i.e. has a cobb60 number below 30 or to measure the contact angle of a water drop on the paper where angles greater than 80 degrees after 10 seconds indicate good bonding, is to add more adhesive to the suspension. On the other hand, the likelihood of ending up with drivability problems in the paper mill as well as production costs increases.
Bortsett fra tilsetningen av limmidler til massesuspensjonen, tilsettes også avvanning- og retensjonsmidler til suspensjonen. Som navnet indikerer, forbedrer den sistnevnte både avvanning og retensjon av massesuspensjonen. Ifølge foreliggende oppfinnelse er det overraskende blitt funnet at limeffektiviteten forbedres ved tilsetningen av minst to forskjellige typer polymerer til massesuspensjonen hvilke polymerer samtidig fungerer som avvanning og retensjonsmidler. Ved derved å anvende den foreliggende prosessen blir både liming, avvanning og retensjon posi-tivt påvirket. Effekten observeres også på suspensjoner med høye konduktiviteter. Apart from the addition of adhesives to the pulp suspension, dewatering and retention agents are also added to the suspension. As the name indicates, the latter improves both dewatering and retention of the pulp suspension. According to the present invention, it has surprisingly been found that the glue efficiency is improved by the addition of at least two different types of polymers to the pulp suspension, which polymers simultaneously function as dewatering and retention agents. By thereby applying the present process, both gluing, dewatering and retention are positively affected. The effect is also observed on suspensions with high conductivities.
US 5595629 beskriver en fremgangsmåte for papirfremstilling omfattende dannelse av en vandig cellulosepapirfremstillingsslurry og tilsetning av en kationisk polymer og en anionisk polymer til slurrien for å øke retensjon og/eller drenering. US 5595629 describes a process for papermaking comprising forming an aqueous cellulosic papermaking slurry and adding a cationic polymer and an anionic polymer to the slurry to increase retention and/or drainage.
US 5584966 beskriver en fremgangsmåte for å forbedre dannelsen av papir under papirfremstillingsprosessen ved benyttelse av en kombinasjon av polysilikatmikro-geler (PSM) i kombinasjon med kationiske og anioniske polymerer. US 5584966 describes a method for improving the formation of paper during the papermaking process using a combination of polysilicate microgels (PSM) in combination with cationic and anionic polymers.
Nærmere bestemt er det ifølge foreliggende oppfinnelse blitt funnet at spesielt for-bedret liming kan oppnås ved en fremgangsmåte for tilvirkning av papir og papp omfattende å tilveiebringe en suspensjon omfattende cellulosefibere og minst et limmiddel valgt fra gruppen bestående av ketendimerer og syreanhydrider, avvanne suspensjonen som derved danner en papirbane, som er kjennetegnet ved at det til suspensjonen tilsettes en aromatholdig kationisk vinyladdisjonspolymer, og en anionisk polymer med en vektgjennomsnittlig molekylvekt i området fra omtrent 6 000 opptil 100 000 valgt fra gruppen bestående av vinyladdisjonspolymerer og kondensasjonspolymerer. More specifically, according to the present invention, it has been found that particularly improved gluing can be achieved by a method for the production of paper and cardboard comprising providing a suspension comprising cellulose fibers and at least one adhesive selected from the group consisting of ketene dimers and acid anhydrides, dewatering the suspension which thereby forms a paper web, which is characterized by adding to the suspension an aromatic cationic vinyl addition polymer, and an anionic polymer with a weight average molecular weight in the range from approximately 6,000 up to 100,000 selected from the group consisting of vinyl addition polymers and condensation polymers.
Detaljert beskrivelse av oppfinnelsen Detailed description of the invention
Foreliggende oppfinnelse er ikke begrenset til spesifikke typer cellulosesuspensjoner men kan anvendes på cellulosesuspensjoner som inneholder jomfru- eller resir-kulert masse og forskjellige fyllstoff slik som kalsiumkarbonat. pH av suspensjonen kan også variere fra å være sur, som er tilfellet dersom limmidler avledet fra har-pikser anvendes, til være nøytrale eller alkaliske. Dersom cellulosereaktive limmidler anvendes er pH av cellulosesuspensjonen nøytral til alkalisk, dvs. i området fra omtrent 5 opptil 10, som også gjør det mulig å inkludere uorganiske fyllstoff-materialer i suspensjonen, dvs. utfelt kalsiumkarbonat og leirer. De to forskjellige polymerene er egnet tilsatt til en relativ fortynnet lignocellulosesuspensjon vanligvis referert til som tynnmasse med en konsentrasjon på fra 0,1 til opptil 3,0 vekt% basert på tørre fibere. The present invention is not limited to specific types of cellulose suspensions but can be applied to cellulose suspensions containing virgin or recycled pulp and various fillers such as calcium carbonate. The pH of the suspension can also vary from being acidic, which is the case if adhesives derived from resin pix are used, to being neutral or alkaline. If cellulose-reactive adhesives are used, the pH of the cellulose suspension is neutral to alkaline, i.e. in the range from approximately 5 to 10, which also makes it possible to include inorganic filler materials in the suspension, i.e. precipitated calcium carbonate and clays. The two different polymers are suitably added to a relatively dilute lignocellulosic suspension commonly referred to as thin pulp at a concentration of from 0.1 to up to 3.0% by weight based on dry fibers.
Prosessen er videre ikke avhengig av typen av limmiddel tilsatt, derved kan ethvert limmiddel eller blanding av limmiddel være til stede i cellulosesuspensjonen. Fortrinnsvis inneholder cellulosesuspensjonen cellulosereaktive limmidler, normalt til stede i en mengde på fra 0,01 til 5 vekt% basert på tørre fibere, og har en pH-verdi der cellulosereaktive limmidler fortsatt fungerer ordentlig, dvs. en pH i området fra 5 opptil 10. Egnede cellulosereaktive limmidler er ketendimerer, ketenmultimerer, syreanhydrider, organiske isocyanater, karbamoylklorider og blandinger derav, der ketendimerer og syreanhydrider er foretrukket. Furthermore, the process does not depend on the type of adhesive added, whereby any adhesive or mixture of adhesives can be present in the cellulose suspension. Preferably, the cellulose suspension contains cellulose reactive sizing agents, normally present in an amount of from 0.01 to 5% by weight based on dry fibers, and has a pH value at which cellulose reactive sizing agents still function properly, i.e. a pH in the range from 5 to 10. Suitable cellulose reactive adhesives are ketene dimers, ketene multimers, acid anhydrides, organic isocyanates, carbamoyl chlorides and mixtures thereof, where ketene dimers and acid anhydrides are preferred.
Ifølge foreliggende prosess tilsettes en aromatholdig vinyladdisjonspolymer og en anionisk vinyladdisjonspolymer med en vektgjennomsnittlig molekylvekt i området fra omtrent 6 000 opptil 100 000 til cellulosesuspensjonen. Vanligvis tilsettes den kationiske polymeren før tilsetningen av en anionisk polymer. Egnet blir tilsetningen av den kationiske polymeren etterfulgt av et skjærtrinn eller flere trinn, mens den anioniske polymeren tilsettes etter ethvert trinn som tilveiebringer betydelig skjær men før dannelsen av papirhanen. According to the present process, an aromatic vinyl addition polymer and an anionic vinyl addition polymer having a weight average molecular weight in the range of about 6,000 up to 100,000 are added to the cellulose suspension. Typically, the cationic polymer is added before the addition of an anionic polymer. Suitably, the addition of the cationic polymer is followed by a shear step or steps, while the anionic polymer is added after any step that provides significant shear but before the formation of the paper tap.
Aromatholdig vinvladdisionspolvmer Aromatic wine-laden addition polymer
Den aromatholdige kationiske vinyladdisjonspolymer kan være lineær eller forgrenet og inneholde monomerer med anioniske eller potensielt anioniske grupper så lenge den totale ladningen av polymeren er kationisk. Derimot oppnås den kationiske polymeren fortrinnsvis ved å polymerisere en reaksjonsblanding hovedsakelig fri for monomerer med anioniske grupper eller grupper som kan gjøres anioniske i vandige sammensetninger. Den kationiske polymeren kan være en homopolymer eller en kopolymer inneholdende kationiske aromatiske monomerer, kationiske ik-ke-aromatiske monomerer og ikke-ioniske monomerer, de siste kan også være ik-ke-aromatiske. Egnet inneholder den kationiske vinyladdisjonspolymeren kationiske aromatiske monomerer valgt fra gruppen bestående av akrylamid, (met)akrylamid, akrylat og (met)akrylat, mens de kationiske monomerene fortrinnsvis har minst en aromatisk gruppe kovalent bundet til et nitrogenatom enten direkte eller via hydro-karbongrupper som kan ha heteroatomer. Fortrinnsvis inneholder den aromatholdige kationiske vinyladdisjonspolymer aromatiske (met)akrylamid og/eller (met)akrylatmonomerer som er til stede i polymeren i en mengde som er fra omtrent 2 mol% opptil omtrent 97 mol%. Den aromatholdige kationiske vinyladdisjonspolymer er egnet oppnådd ved å polymerisere en kationisk monomer eller en reaksjonsblanding inneholdende en monomerblanding omfattende en kationisk monomer fremstilt ved den generelle formel (I): The aromatic cationic vinyl addition polymer may be linear or branched and contain monomers with anionic or potentially anionic groups as long as the total charge of the polymer is cationic. In contrast, the cationic polymer is preferably obtained by polymerizing a reaction mixture essentially free of monomers with anionic groups or groups that can be made anionic in aqueous compositions. The cationic polymer may be a homopolymer or a copolymer containing cationic aromatic monomers, cationic non-aromatic monomers and non-ionic monomers, the latter may also be non-aromatic. Suitably, the cationic vinyl addition polymer contains cationic aromatic monomers selected from the group consisting of acrylamide, (meth)acrylamide, acrylate and (meth)acrylate, while the cationic monomers preferably have at least one aromatic group covalently bonded to a nitrogen atom either directly or via hydrocarbon groups which may have heteroatoms. Preferably, the aromatic cationic vinyl addition polymer contains aromatic (meth)acrylamide and/or (meth)acrylate monomers present in the polymer in an amount ranging from about 2 mol% to about 97 mol%. The aromatic-containing cationic vinyl addition polymer is suitably obtained by polymerizing a cationic monomer or a reaction mixture containing a monomer mixture comprising a cationic monomer prepared by the general formula (I):
hvor Ri er H eller CH3; R2og R3er uavhengig fra hverandre et hydrogen eller en alkylgruppe med fra 1 til 3 karbonatomer, vanligvis 1 til 2 karbonatomer; Ai er O eller NH; B]. er en alkylengruppe med fra 2 til 8 karbonatomer, egnet fra 2 til 4 karbonatomer, en hydroksypropylengruppe eller en hydroksyetylengruppe; Q er en substituent inneholdende en aromatisk gruppe, egnet en fenyl eller substituert fe-nylgruppe som kan være festet til nitrogenet ved hjelp av en alkylengruppe vanligvis med fra 1 til 3 karbonatomer, egnet 1 til 2 karbonatomer, og fortrinnsvis er Q en benzylgruppe (-CH2-C6H5); og X" er et anionisk motion, vanligvis et halid som wherein R 1 is H or CH 3 ; R 2 and R 3 are independently of one another hydrogen or an alkyl group having from 1 to 3 carbon atoms, usually 1 to 2 carbon atoms; Ai is O or NH; B]. is an alkylene group with from 2 to 8 carbon atoms, suitably from 2 to 4 carbon atoms, a hydroxypropylene group or a hydroxyethylene group; Q is a substituent containing an aromatic group, suitably a phenyl or substituted phenyl group which may be attached to the nitrogen by means of an alkylene group usually of from 1 to 3 carbon atoms, suitably 1 to 2 carbon atoms, and preferably Q is a benzyl group (- CH2-C6H5); and X" is an anionic counterion, usually a halide which
klorid. Eksempler på egnede monomerer representert ved den generelle formel (I) inkluderer kvarternære monomerer oppnådd ved å behandle dialkylaminoalkyl (met)akrylater, f.eks. dimetylaminoetyl (met)akrylat, dietylaminoetyl (met)akrylat og dimetylaminohydroksypropyl (met)akrylat og dialkylaminoalkyl (met)akryl-amider, f.eks. dimetylaminoetyl (met)akrylamid, dietylaminoetyl (met)akrylamid, dimetylaminopropyl (met)akrylamid, og dietylaminopropyl (met)akrylamid med benzylklorid. Foretrukne kationiske monomerer av den generelle formel (I) inkluderer dimetylaminoetylakrylat benzylklorid kvarternær salt, dimetylamino-etylmetakrylat benzylklorid kvarternært salt og dimetylaminopropyl(met)akrylamid benzylklorid kvarternært salt. chloride. Examples of suitable monomers represented by the general formula (I) include quaternary monomers obtained by treating dialkylaminoalkyl (meth)acrylates, e.g. dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and dimethylaminohydroxypropyl (meth)acrylate and dialkylaminoalkyl (meth)acrylamides, e.g. dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and diethylaminopropyl (meth)acrylamide with benzyl chloride. Preferred cationic monomers of the general formula (I) include dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt and dimethylaminopropyl (meth)acrylamide benzyl chloride quaternary salt.
Den kationiske vinyladdisjonspolymer kan være en homopolymer fremstilt fra en kationisk monomer med en aromatisk gruppe eller en kopolymer fremstilt fra en monomerblanding omfattende en kationisk monomer med en aromatisk gruppe og én eller flere kopolymeriserbare monomerer. Egnede kopolymeriserbare ikke-ioniske monomerer inkluderer monomerer representert ved den generelle formel The cationic vinyl addition polymer may be a homopolymer prepared from a cationic monomer with an aromatic group or a copolymer prepared from a monomer mixture comprising a cationic monomer with an aromatic group and one or more copolymerizable monomers. Suitable copolymerizable nonionic monomers include monomers represented by the general formula
(II): (II):
hvor R4er H eller CH3; R5og R6er hver H eller en hydrokarbongruppe, egnet alkyl, med fra 1 til 6 egnet fra 1 til 4 og vanligvis fra 1 til 2 karbonatomer; A2er O eller NH; B2er en alkylengruppe med fra 2 til 8 karbonatomer, vanligvis fra 2 til 4 karbonatomer eller en hydroksypropylengruppe eller alternativt er både A og B ingen-ting mens det er en enkelbinding mellom C og N (0=C-NR5R6). Eksempler på egnede kopolymeriserbare monomerer av denne typen inkluderer (met)akrylamid; akrylamid baserte monomerer som N-alkyl (met)akrylamider og N,N-dialkyl (met)akrylamider, f.eks. N-n-propylakrylamid, N-isoprolyl(met)akrylamid, N-n-butyl(met)akrylamid, N-isobutyl (met)akrylamid og N-t-butyl (met)akrylamid; og dialkylaminoalkyl (met)akrylamider, f.eks. dimetylaminoetyl (met)akrylamid, dietylaminoetyl (met)akrylamid, dimetylaminopropyl (met)akrylamid og dietylaminopropyl (met)akrylamid; akrylatbaserte monomerer som dialkylaminoalkyl (met)akrylater, f.eks. dimetylaminoetyl (met)akrylat, dietylaminoetyl (met)akrylat, t-butylaminoetyl (met)akrylat og dimetylaminohydrokspropyl akrylat; og vinylami-der, f.eks. N-vinylformamid og N-vinylacetamid. Foretrukne kopolymeriserbare ik- where R 4 is H or CH 3 ; R 5 and R 6 are each H or a hydrocarbon group, suitably alkyl, having from 1 to 6, suitably from 1 to 4 and usually from 1 to 2 carbon atoms; A 2 is O or NH; B2 is an alkylene group with from 2 to 8 carbon atoms, usually from 2 to 4 carbon atoms or a hydroxypropylene group or alternatively both A and B are nothing while there is a single bond between C and N (O=C-NR5R6). Examples of suitable copolymerizable monomers of this type include (meth)acrylamide; acrylamide-based monomers such as N-alkyl (meth)acrylamides and N,N-dialkyl (meth)acrylamides, e.g. N-n-propylacrylamide, N-isoprolyl(meth)acrylamide, N-n-butyl(meth)acrylamide, N-isobutyl (meth)acrylamide and N-t-butyl (meth)acrylamide; and dialkylaminoalkyl (meth)acrylamides, e.g. dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide and diethylaminopropyl (meth)acrylamide; acrylate-based monomers such as dialkylaminoalkyl (meth)acrylates, e.g. dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate and dimethylaminohydroxypropyl acrylate; and vinylamides, e.g. N-vinylformamide and N-vinylacetamide. Preferred copolymerizable ik-
ke-ioniske monomerer inkluderer akrylamid og metakrylamid, dvs. (met)akrylamid og hovedpolymeren er fortrinnsvis en akrylamid basert polymer. non-ionic monomers include acrylamide and methacrylamide, i.e. (meth)acrylamide and the main polymer is preferably an acrylamide based polymer.
Egnede kopolymeriserbare kationiske monomerer inkluderer monomerene representert ved den generelle formel (III): Suitable copolymerizable cationic monomers include the monomers represented by the general formula (III):
hvor R7er H eller CH3; R8og R9er fortrinnsvis en hydrokarbongruppe, egnet en alkylgruppe med fra 1 til 3 karbonatomer; R10kan være et hydrogen eller fortrinnsvis en hydrokarbongruppe, egnet en alkylgruppe med fra 1 til 8 karbonatomer, vanligvis 1 til 2 karbonatomer; A3er O eller NH; B3er en alkylengruppe med fra 2 til 4 karbonatomer, egnet fra 2 til 4 karbonatomer, eller en hydroksypropylengruppe, og X" er et anionisk motion, vanligvis metylsulfat eller et halid som klorid. Eksempler på egnede kationiske kopolymeriserbare monomerer inkluderer syreaddisjonssalter og kvarternære ammoniumsalter av dialkylaminoalkyl (met) akrylater og dialkylaminoalkyl (met)akrylamidene nevnt over, vanligvis fremstilt anvendende syrer som HCI, H2S04, etc, eller kvarterniseringsmidler som metylklorid, dimetylsulfat etc; og diallyldimetylammoniumklorid. Foretrukne kopolymeriserende kationiske monomerer inkluderer dimetylaminoetyl (met) akrylatmetylklorid kvarternært salt, diallyldimetylammoniumklorid og dimetylaminopropyl(met) where R 7 is H or CH 3 ; R8 and R9 are preferably a hydrocarbon group, suitably an alkyl group with from 1 to 3 carbon atoms; R 10 can be a hydrogen or preferably a hydrocarbon group, suitably an alkyl group with from 1 to 8 carbon atoms, usually 1 to 2 carbon atoms; A 3 is O or NH; B3 is an alkylene group of from 2 to 4 carbon atoms, suitably from 2 to 4 carbon atoms, or a hydroxypropylene group, and X" is an anionic counterion, usually methyl sulfate or a halide such as chloride. Examples of suitable cationic copolymerizable monomers include acid addition salts and quaternary ammonium salts of dialkylaminoalkyl (meth)acrylates and the dialkylaminoalkyl (meth)acrylamides mentioned above, usually prepared using acids such as HCI, H2SO4, etc, or quaternizing agents such as methyl chloride, dimethyl sulfate, etc; and diallyldimethylammonium chloride. Preferred copolymerizing cationic monomers include dimethylaminoethyl (meth)acrylate methyl chloride quaternary salt, diallyldimethylammonium chloride and dimethylaminopropyl(met)
akrylamidbenzylklorid kvarternært salt. Kopolymeriserbare anioniske monomerer slik som akrylsyre, metakrylsyre, itakonsyre, forskjellige sulfonerte vinyladdisjons-monomerer, etc. kan også benyttes og fortrinnsvis i små mengder. acrylamide benzyl chloride quaternary salt. Copolymerizable anionic monomers such as acrylic acid, methacrylic acid, itaconic acid, various sulfonated vinyl addition monomers, etc. can also be used and preferably in small amounts.
Den kationiske vinyladdisjonsmonomeren kan fremstilles fra en monomerblanding The cationic vinyl addition monomer can be prepared from a monomer mixture
vanligvis omfattende fra 1 til 99 mol%, egnet fra 2 til 50 mol% og fortrinnsvis fra 5 til 20 mol% av kationisk monomer med en aromatisk gruppe, fortrinnsvis representert ved den generelle formelen (I), og fra 99 til 1 mol%, egnet fra 98 til 50 mol%, og fortrinnsvis fra 95 til 65 mol% av andre kopolymeriserbare monomerer som fortrinnsvis omfatter fra 96 til 50 mol% og fortrinnsvis fra 95 til 80 mol% av akrylamid eller metakrylamid ((met)akrylamid), monomerblandingen omfatter egnet (met)akrylamid, resten opptil 100% fortrinnsvis av forbindelser ifølge formel I og usually comprising from 1 to 99 mol%, suitably from 2 to 50 mol% and preferably from 5 to 20 mol% of cationic monomer with an aromatic group, preferably represented by the general formula (I), and from 99 to 1 mol%, suitable from 98 to 50 mol%, and preferably from 95 to 65 mol% of other copolymerizable monomers which preferably comprise from 96 to 50 mol% and preferably from 95 to 80 mol% of acrylamide or methacrylamide ((meth)acrylamide), the monomer mixture comprises suitable (meth)acrylamide, the remainder up to 100% preferably of compounds according to formula I and
II. II.
Alternativt kan den kationiske polymeren være en polymer utsatt for aromatisk modifikasjon anvendende et middel som inneholder en aromatisk gruppe. Egnede modifiserende midler av denne typen inkluderer benzylklorid, benzylbromid, N-(3-klor-2-hydroksypropyl)-N-benzyl-N,N-dimetylammoniumklorid, og N-(3-klor-2-hydroksypropyl) pyridiniumklorid. Egnede polymerer for en slik aromatisk modifikasjon inkluderer vinyladdisjonspolymerer. Dersom polymeren inneholder et tertiært nitrogen som kan bli kvarternisert av det modifiserende middel, resulterer anven-delsen av slike midler vanligvis i at polymeren gjøres kationisk. Alternativt kan polymeren som skal utsettes for aromatisk modifikasjon være kationisk, for eksempel en kationisk vinyladdisjonspolymer. Alternatively, the cationic polymer may be a polymer subjected to aromatic modification using an agent containing an aromatic group. Suitable modifiers of this type include benzyl chloride, benzyl bromide, N-(3-chloro-2-hydroxypropyl)-N-benzyl-N,N-dimethylammonium chloride, and N-(3-chloro-2-hydroxypropyl)pyridinium chloride. Suitable polymers for such aromatic modification include vinyl addition polymers. If the polymer contains a tertiary nitrogen which can be quaternized by the modifying agent, the use of such agents usually results in the polymer being made cationic. Alternatively, the polymer to be subjected to aromatic modification may be cationic, for example a cationic vinyl addition polymer.
Vanligvis er ladningstettheten av den kationiske polymeren innen området av fra 0,1 til 6,0 meqv/g av tørr polymer, egnet fra 0,2 til 4,0 og fortrinnsvis fra 0,5 til 3,0. Den vektgjennomsnittlige molekylvekten av den kationiske polymeren er vanligvis minst omtrent 500 000, egnet over omtrent 1 000 000 og fortrinnsvis over omtrent 2 000 000. Den øvre grensen er ikke kritisk, den kan være omtrent 30 000 000 vanligvis 20 000 000 og egnet 10 000 000. Typically the charge density of the cationic polymer is in the range of from 0.1 to 6.0 meqv/g of dry polymer, suitably from 0.2 to 4.0 and preferably from 0.5 to 3.0. The weight average molecular weight of the cationic polymer is usually at least about 500,000, suitably above about 1,000,000 and preferably above about 2,000,000. The upper limit is not critical, it may be about 30,000,000, usually 20,000,000 and suitably 10,000 000.
Den kationiske vinyladdisjonspolymeren kan tilsettes i suspensjonen i mengder som kan variere innen brede grenser avhengig av blant annet typen av suspensjon, saltinnhold, typer av salt, fyllstoffinnhold, type fyllstoff, tilsetningspunkt etc. Vanligvis tilsettes den kationiske vinyladdisjonspolymeren i en mengde som gir bedre liming, avvanning og retensjon enn det som oppnås når uten å tilsette det, forutsatt at den anioniske addisjonspolymeren tilsettes. Den kationiske polymeren tilsettes vanligvis 1 en mengde på minst 0,002%, ofte minst 0,005 vekt%, basert på tørr masse, mens den øvre grensen vanligvis er 1,0% og egnet 0,5 vekt%. The cationic vinyl addition polymer can be added to the suspension in amounts that can vary within wide limits depending on, among other things, the type of suspension, salt content, types of salt, filler content, type of filler, point of addition, etc. Generally, the cationic vinyl addition polymer is added in an amount that provides better bonding, dewatering and retention than that achieved without adding it, provided that the anionic addition polymer is added. The cationic polymer is usually added in an amount of at least 0.002%, often at least 0.005% by weight, based on dry mass, with the upper limit usually being 1.0% and suitably 0.5% by weight.
Anionisk vinyladdisjonspolymer Anionic vinyl addition polymer
I tillegg til den over beskrevne aromatholdige kationiske vinyladdisjonspolymeren, tilsettes en anionisk polymer med en vektgjennomsnittlig molekylvekt i området fra omtrent 6 000 opptil omtrent 100 000 valgt fra gruppen bestående av vinyladdisjonspolymerer og kondensasjonspolymerer til cellulosesuspensjonen. Den anioniske polymeren kan være lineær, forgrenet eller fornettet, men egnet hovedsakelig lineær, og vanligvis vannløselig eller vanndispergerbar. Den anioniske polymeren kan videre være en homopolymer eller kopolymer inneholdende minst to forskjellige typer monomerer. Fortrinnsvis er den anioniske polymeren en vinyladdisjonspolymer med en vektgjennomsnittlig molekylvekt i området fra omtrent 6 000 opp til omtrent 100 000. Egnede anioniske vinyladdisjonspolymerer er polymerer oppnådd fra en reaksjonsblanding som omfatter vinyliske umettede monomerer, fortrinnsvis vinylumettede aromatholdige monomerer, med en eller flere anioniske grupper eller grupper som er gjort anioniske i vandige løsninger, egnet minst en sulfonert gruppe. Eksempler på anioniske grupper festet til vinylumettede monomerer er fosfatgrupper, fosfonatgrupper, sulfatgrupper, sulfonsyregrupper, sulfonatgrupper, karboksylsyregrupper, karboksylatgrupper slik som akrylsyre, metakrylsyre, etylakrylsyre, krotonsyre, itakonsyre, maleinsyre eller salter derav, alkoksid-grupper, maleinsyregrupper og fenolgrupper, dvs. hydroksysubstituerte fenyler og naftyler. Grupper som bærer en anionisk ladning er vanligvis salter av et alkalime-tall, jordalkalimetall eller ammoniakk. Den anioniske vinyladdisjonspolymer kan også i noe utstrekning inneholde kationiske grupper slik som monomerer med kationiske grupper, selv om foretrukket, er de eneste ioniske gruppene til stede i vinyladdisjonspolymeren anioniske. Fortrinnsvis er de anioniske gruppene bundet til aromatiske vinyl (etylenske) umettede monomerer slik som styrener, dvs. styren-sulfonat. Dersom den anioniske vinyladdisjonspolymeren er en kopolymer, kan den nevnte polymeren oppnås fra en reaksjonsblanding omfattende ikke-ioniske vinylumettede monomerer, f.eks. akrylamid, (met)akrylamid. Den anioniske vinyladdisjonspolymeren kan omfatte fra omtrent 20 mol% opptil omtrent 100 mol% av anioniske monomerer inneholdende minst en anionisk ladning. In addition to the aromatic cationic vinyl addition polymer described above, an anionic polymer having a weight average molecular weight in the range of about 6,000 to about 100,000 selected from the group consisting of vinyl addition polymers and condensation polymers is added to the cellulose suspension. The anionic polymer may be linear, branched or cross-linked, but is suitably mainly linear, and usually water-soluble or water-dispersible. The anionic polymer can further be a homopolymer or copolymer containing at least two different types of monomers. Preferably, the anionic polymer is a vinyl addition polymer with a weight average molecular weight in the range of from about 6,000 up to about 100,000. Suitable anionic vinyl addition polymers are polymers obtained from a reaction mixture comprising vinylic unsaturated monomers, preferably vinylic unsaturated aromatic monomers, with one or more anionic groups or groups which are made anionic in aqueous solutions, suitable at least one sulphonated group. Examples of anionic groups attached to vinyl unsaturated monomers are phosphate groups, phosphonate groups, sulfate groups, sulfonic acid groups, sulfonate groups, carboxylic acid groups, carboxylate groups such as acrylic acid, methacrylic acid, ethylacrylic acid, crotonic acid, itaconic acid, maleic acid or salts thereof, alkoxide groups, maleic acid groups and phenolic groups, i.e. hydroxy substituted phenyls and naphthyls. Groups that carry an anionic charge are usually salts of an alkali metal number, alkaline earth metal, or ammonia. The anionic vinyl addition polymer may also contain cationic groups to some extent such as monomers with cationic groups, although preferably the only ionic groups present in the vinyl addition polymer are anionic. Preferably, the anionic groups are bound to aromatic vinyl (ethylenic) unsaturated monomers such as styrenes, ie styrene sulphonate. If the anionic vinyl addition polymer is a copolymer, said polymer can be obtained from a reaction mixture comprising non-ionic vinyl unsaturated monomers, e.g. acrylamide, (meth)acrylamide. The anionic vinyl addition polymer may comprise from about 20 mol% up to about 100 mol% of anionic monomers containing at least one anionic charge.
Egnede anioniske kondensasjonspolymerer med en vektgjennomsnittlig molekylvekt i området fra omtrent 6 000 opptil omtrent 100 000 er kondensater av et al-dehyd slik som formaldehyd med en eller flere aromatiske forbindelser inneholdende en eller flere anioniske grupper, og valgfritt andre komonomerer nyttige i kondensasjonspolymeriseringen slik som urea og melamin. Eksempler på egnede aromatiske forbindelser inneholdende anioniske grupper omfatter benzen- og naf-talenbaserte forbindelser inneholdende anioniske grupper slik som fenol og naftol-forbindelser, f.eks. fenol, naftol, resorcinol og derivater derav, aromatiske syrer og salter derav, f.eks. fenyl, fenol, naftyl og naftolsyrer og salter, vanligvis sulfonsyrer og sulfonater, f.eks. benzensulfonsyre og sulfonat, xylensulfonsyre og sulfonater, naftalensulfonsyre og sulfonat, fenolsulfonsyre og sulfonat. Eksempler på egnede anioniske kondensasjonspolymerer inkluderer anioniske benzenbaserte og naftalen-baserte kondensasjonspolymerer, fortrinnsvis naftalensulfonsyrebaserte og naf-talensulfonbaserte kondensasjonspolymerer. Suitable anionic condensation polymers having a weight average molecular weight in the range of from about 6,000 to about 100,000 are condensates of an aldehyde such as formaldehyde with one or more aromatic compounds containing one or more anionic groups, and optionally other comonomers useful in the condensation polymerization such as urea and melamine. Examples of suitable aromatic compounds containing anionic groups include benzene- and naphthalene-based compounds containing anionic groups such as phenol and naphthol compounds, e.g. phenol, naphthol, resorcinol and their derivatives, aromatic acids and their salts, e.g. phenyl, phenol, naphthyl and naphtholic acids and salts, usually sulphonic acids and sulphonates, e.g. benzenesulfonic acid and sulfonate, xylenesulfonic acid and sulfonates, naphthalene sulfonic acid and sulfonate, phenolsulfonic acid and sulfonate. Examples of suitable anionic condensation polymers include anionic benzene-based and naphthalene-based condensation polymers, preferably naphthalenesulfonic acid-based and naphthalene-sulfone-based condensation polymers.
Den vektgjennomsnittlige molekylvekten av den anioniske vinyladdisjonspolymeren og kondensasjonspolymeren er i området fra omtrent 6 000 opptil omtrent 100 000. Den nedre grensen er egnet fra omtrent 7 000, fortrinnsvis fra omtrent 8 000, fortrinnsvis fra omtrent 15 000, fortrinnsvis fra omtrent 25 000, mens den øvre grensen er egnet opptil omtrent 80 000, fortrinnsvis opptil omtrent 75 000, fortrinnsvis opptil 45 000, fortrinnsvis opptil omtrent 40 000. Enhver kombinasjon av nedre og øvre grense kan være et foretrukket område. Dersom den anioniske polymeren er en vinyladdisjonspolymer, er de foretrukne områder av den vektgjennomsnittlige molekylvekt fra omtrent 10 000 opptil omtrent 100 000, mer foretrukket fra omtrent 15 000 opptil omtrent 75 000, mest foretrukket fra omtrent 25 000 opptil omtrent 45 000. The weight average molecular weight of the anionic vinyl addition polymer and condensation polymer ranges from about 6,000 to about 100,000. The lower limit is suitable from about 7,000, preferably from about 8,000, preferably from about 15,000, preferably from about 25,000, while the upper limit is suitable up to about 80,000, preferably up to about 75,000, preferably up to 45,000, preferably up to about 40,000. Any combination of lower and upper limits may be a preferred range. If the anionic polymer is a vinyl addition polymer, the preferred ranges of the weight average molecular weight are from about 10,000 to about 100,000, more preferably from about 15,000 to about 75,000, most preferably from about 25,000 to about 45,000.
Den anioniske polymeren kan ha en grad av anionisk substitusjon (DSA) som varie-rer over et bredt område avhengig av blant annet typen polymer anvendt; DSAer vanligvis fra 0,01 til 2,0, egnet fra 0,02 til 1,8 og fortrinnsvis fra 0,025 til 1,5; og graden av aromatisk substitusjon (DSQ) kan være fra 0,001 til 1,0, vanligvis fra 0,01 til 1,0, egnet fra 0,02 til 0,7 og fortrinnsvis fra 0,025 til 0,5. I tilfellet der den anioniske polymeren inneholder kationiske grupper, kan graden av kationisk substitusjon (DSC) for eksempel være fra 0 til 0,2, egnet fra 0 til 0,1 og fortrinnsvis fra 0 til 0,05, den anioniske polymeren har en total anionisk ladning. Vanligvis er den anioniske ladningstettheten av den anioniske polymeren innen området fra 0,1 til 6,0 meqv/g av tørr polymer, egnet fra 0,5 til 5,0 og fortrinnsvis fra 1,0 til 5,0. The anionic polymer can have a degree of anionic substitution (DSA) which varies over a wide range depending, among other things, on the type of polymer used; DSAs usually from 0.01 to 2.0, suitably from 0.02 to 1.8 and preferably from 0.025 to 1.5; and the degree of aromatic substitution (DSQ) may be from 0.001 to 1.0, usually from 0.01 to 1.0, suitably from 0.02 to 0.7 and preferably from 0.025 to 0.5. In the case where the anionic polymer contains cationic groups, the degree of cationic substitution (DSC) may for example be from 0 to 0.2, suitably from 0 to 0.1 and preferably from 0 to 0.05, the anionic polymer having a total anionic charge. Generally, the anionic charge density of the anionic polymer is in the range of from 0.1 to 6.0 meqv/g of dry polymer, suitably from 0.5 to 5.0 and preferably from 1.0 to 5.0.
Den anioniske polymeren kan tilsettes til suspensjonen i mengder som kan variere innen vide grenser avhengig av blant annet, typen av masse, saltinnhold, type salter, fyllstoffinnhold, type fyllstoff, tilsetningspunkt, etc. Vanligvis tilsettes den anioniske polymeren i en mengde som gir bedre liming, avvanning og retensjon enn det som oppnås når det ikke tilsettes anionisk polymer forutsatt at den kationiske vinyladdisjonspolymeren tilsettes. Den anioniske polymeren tilsettes vanligvis i en mengde på minst 0,001%, ofte minst 0,005 vekt%, basert på tørr masse, mens den øvre grensen vanligvis er 3,0% og egnet 1,0 vekt%. The anionic polymer can be added to the suspension in amounts that can vary within wide limits depending, among other things, on the type of pulp, salt content, type of salts, filler content, type of filler, point of addition, etc. Usually, the anionic polymer is added in an amount that provides better bonding , dewatering and retention than that obtained when no anionic polymer is added provided that the cationic vinyl addition polymer is added. The anionic polymer is usually added in an amount of at least 0.001%, often at least 0.005% by weight, based on dry mass, with the upper limit usually being 3.0% and suitably 1.0% by weight.
Ifølge en foretrukket utførelse av den foreliggende oppfinnelsen kan den aromatholdige vinyladdisjonspolymeren utstyres med en vandig sammensetning, egnet en vandig løsning, fortrinnsvis omfattende ytterligere kationiske polymerer, for eksempel syntetiske kationiske polymerer og naturlig forekommende polymerer. Egnede syntetiske kationiske polymerer er vinyladdisjonspolymerer slik som akryla-midbaserte polymerer eller akrylatbaserte polymerer. Andre syntetiske kationiske polymerer inkluderer kationiske kondensasjonspolymerer som epihalohydrinpoly-merer, f.eks. polymerer dannet ved å reagere alifatiske aminer og epiklorhydrin, polyamidamin polymerer, polyetylenimin polymerer, Foretrukne naturlig forekommende kationiske polymerer som kationiske polysakkarider, spesielt kationisk stivelse og aromatisk substituert kationisk stivelse. Den vandige løsningen inneholder fortrinnsvis den aromatholdige kationiske vinyladdisjonspolymeren i en domineren-de mengde, dvs. ved minst 50 vekt%, selv om effektene er til stede ved betydelig mindre mengder, ned til mengder på minst 10 vekt%. De ytterligere kationiske polymerene referert til i dette avsnittet kan også tilsettes separat. According to a preferred embodiment of the present invention, the aromatic vinyl addition polymer can be equipped with an aqueous composition, suitable an aqueous solution, preferably comprising further cationic polymers, for example synthetic cationic polymers and naturally occurring polymers. Suitable synthetic cationic polymers are vinyl addition polymers such as acrylamide-based polymers or acrylate-based polymers. Other synthetic cationic polymers include cationic condensation polymers such as epihalohydrin polymers, e.g. polymers formed by reacting aliphatic amines and epichlorohydrin, polyamidamine polymers, polyethyleneimine polymers, Preferred naturally occurring cationic polymers such as cationic polysaccharides, especially cationic starch and aromatically substituted cationic starch. The aqueous solution preferably contains the aromatic cationic vinyl addition polymer in a predominant amount, i.e. at least 50% by weight, although the effects are present at considerably smaller amounts, down to amounts of at least 10% by weight. The additional cationic polymers referred to in this section may also be added separately.
Ifølge enda en annen foretrukket utførelse av foreliggende oppfinnelse tilsettes uorganiske anioniske mikropartikulære materialer slik som anioniske silikabaserte partikler, polykiselsyre og leirer av smektittypen til suspensjonen. Det uorganiske anioniske mikropartikulære materialet kan tilsettes separat til suspensjonen eller er fortrinnsvis omfattet i en vandig sammensetning som også omfatter den anioniske polymeren. According to yet another preferred embodiment of the present invention, inorganic anionic microparticulate materials such as anionic silica-based particles, polysilicic acid and clays of the smectite type are added to the suspension. The inorganic anionic microparticulate material can be added separately to the suspension or is preferably included in an aqueous composition which also includes the anionic polymer.
Videre kan prosessen også være nyttig i tilvirkningen av papir og papp fra cellulosesuspensjoner med høy konduktivitet. I slike tilfeller er konduktiviteten av suspensjonen som avvannes på viren vanligvis minst 1,0 mS/cm, egnet minst 2,0 mS/cm, og fortrinnsvis minst 3,5 mS/cm. Konduktivitet kan måles ved standard utstyr slik som for eksempel, et WTW LF 539 instrument levert av Christian Berner. Verdiene referert til over er egnet bestemt ved å måle konduktiviteten av cellulosesuspensjonen som mates i eller er til stede i innløpskassen av papirmaskinen eller alternativt ved å måle konduktiviteten av bakvann oppnådd ved å avvanne suspensjonen. Høye konduktivitetsnivåer betyr høye innhold av salter (elektrolytter) som kan være avledet fra materialene anvendt for å danne massen, fra forskjellige additiver introdusert i massen, fra ferskvannet levert til prosessen, etc. Videre er innholdet av salter vanligvis høyere i prosessene der bakvann resirkuleres ekstensivt, som kan føre til betydelig akkumulering av salter i vannet som sirkulerer i prosessen. Furthermore, the process can also be useful in the production of paper and cardboard from cellulose suspensions with high conductivity. In such cases, the conductivity of the suspension dewatered on the wire is usually at least 1.0 mS/cm, suitably at least 2.0 mS/cm, and preferably at least 3.5 mS/cm. Conductivity can be measured with standard equipment such as, for example, a WTW LF 539 instrument supplied by Christian Berner. The values referred to above are suitably determined by measuring the conductivity of the cellulose suspension fed into or present in the headbox of the paper machine or alternatively by measuring the conductivity of tailwater obtained by dewatering the suspension. High conductivity levels mean high contents of salts (electrolytes) which may be derived from the materials used to form the pulp, from various additives introduced into the pulp, from the fresh water supplied to the process, etc. Furthermore, the content of salts is usually higher in processes where waste water is extensively recycled , which can lead to significant accumulation of salts in the water circulating in the process.
Oppfinnelsen er videre illustrert i de følgende eksempler som derimot, ikke er ment å begrense det samme. Deler og % vedrører deler i hhv. vekt og vekt% basert på tørre fibere, med mindre annet er fremsatt. Alle forbindelser tilsatt til massen er beregnet som tørt materiale dersom ikke annet er indikert. I eksemplene er god retensjon vist ved en lav turbiditetsverdi i bakvannet, dvs. mer finstoff og fyllstoff holdes tilbake i det dannede arket. En turbiditetsverdi under 120 er akseptabel, og en verdi under 90 er i dette eksperimentsettet utmerket. Avvanningstallet bør også være lavt. Limingen av papiret ble målt ved kontaktvinkelen av en vanndråpe på papiret. Kontaktvinkler større enn 80 grader etter 10 sekunder indikerer en god liming. The invention is further illustrated in the following examples which, however, are not intended to limit the same. Parts and % relate to parts in the respective weight and weight% based on dry fibres, unless otherwise stated. All compounds added to the mass are calculated as dry material unless otherwise indicated. In the examples, good retention is shown by a low turbidity value in the tailwater, i.e. more fines and filler are retained in the formed sheet. A turbidity value below 120 is acceptable, and a value below 90 is excellent in this set of experiments. The dewatering figure should also be low. The adhesion of the paper was measured by the contact angle of a drop of water on the paper. Contact angles greater than 80 degrees after 10 seconds indicate good bonding.
Eksempel 1 Example 1
Massen (ved 3%) anvendt var en 80/20 blanding av hardved/mykved kraft. Malt kalsiumkarbonatfyllstoff (GCC) ble tilsatt til massen, til en fyllstoffkonsentrasjon på 40% på tørt faststoff. Den resulterende massen ble fortynnet til 0,3% før tilleggs-kjemikalier ble tilsatt. Kjemikalietilsetningene er uttrykt som % på tørt faststoff i massen. The pulp (at 3%) used was an 80/20 mixture of hardwood/softwood kraft. Ground calcium carbonate filler (GCC) was added to the pulp, to a filler concentration of 40% on dry solids. The resulting stock was diluted to 0.3% before additional chemicals were added. The chemical additions are expressed as % of dry solids in the mass.
I dette eksemplet ble to masser anvendt der én hadde en lav konduktivitet på 500 uS/cm (masse I), den andre hadde en høy konduktivitet på 4,0 uS/cm (masse II). Konduktiviteten ble justert ved tilsetning av natriumsulfat. En dispersjon inneholdende et konvensjonelt ketendimerlim og 1% kationisk stivelse ble tilsatt til massene. Påfølgende til disse tilsetningene ble enten 0,1% av et aromatisk kationisk polyakrylamid med benzyldimetylammoniumgrupper (A-PAM) eller 0,1% av en kon-vensjonell ikke-aromatisk kationisk polyakrylamid (C-PAM) tilsatt før tilsetningen av enten 0,1% av en silikasol eller 0,1% av et anionisk polystyrensulfonat med en vektgjennomsnittlig molekylvekt på 70 000 (PSS). De tilsatte mengdene av forbindelser er indikert i tabell I og II. Retensjons- og avvanningsegenskapene av de dannede massene ble evaluert ved å måle avvanningstidene anvendende Dynamic Drainage Analyser (DDA-enhet). En lav verdi i denne testen betyr bedre avvan-ningseffektivitet. Retensjonen ble evaluert ved å måle turbiditeten av bakvannet med et Nephleometer 156 fra Novasine. En lavere turbiditetsverdi betyr høyere retensjon av faststoff i DDA-enheten. Videre ble limingen av det dannede, tørkede og herdede papiret evaluert ved å måle kontaktvinkelen av vann etter 10 sekunder anvendende en Dynamic Absoption og kontaktvinkel tester fra Fibro Systems (DAT). En høyere verdi av kontaktvinkelen betyr en bedre limeffektivitet. In this example, two masses were used where one had a low conductivity of 500 uS/cm (mass I), the other had a high conductivity of 4.0 uS/cm (mass II). The conductivity was adjusted by adding sodium sulfate. A dispersion containing a conventional ketene dimer glue and 1% cationic starch was added to the pulps. Subsequent to these additions, either 0.1% of an aromatic cationic polyacrylamide with benzyldimethylammonium groups (A-PAM) or 0.1% of a conventional non-aromatic cationic polyacrylamide (C-PAM) was added prior to the addition of either 0.1 % of a silica sol or 0.1% of an anionic polystyrene sulphonate with a weight average molecular weight of 70,000 (PSS). The added amounts of compounds are indicated in Tables I and II. The retention and dewatering properties of the formed masses were evaluated by measuring the dewatering times using the Dynamic Drainage Analyzer (DDA unit). A low value in this test means better dewatering efficiency. The retention was evaluated by measuring the turbidity of the bottom water with a Nephleometer 156 from Novasine. A lower turbidity value means higher retention of solids in the DDA unit. Furthermore, the bonding of the formed, dried and cured paper was evaluated by measuring the contact angle of water after 10 seconds using a Dynamic Absoption and contact angle tester from Fibro Systems (DAT). A higher value of the contact angle means a better adhesive efficiency.
Som vist i tabell I, øker tilsetningen av en aromatmodifisert kationisk vinyladdisjonspolymer og en anionisk vinyladdisjonspolymer ikke bare avvanning og retensjon betydelig, men også limeffektiviteten. As shown in Table I, the addition of an aromatic modified cationic vinyl addition polymer and an anionic vinyl addition polymer not only significantly increases dewatering and retention, but also adhesive efficiency.
<*>Ingen tilsetning av verken kationisk polyakrylamid eller anionisk forbindelse, ellers var betingelsene de samme som for tester 1 og 2. ; ; Eksempel 2 ;Massen anvendt var den samme som anvendt i eksempel 1, i dette eksemplet derimot, ble massen justert til en konduktivitet på 400 uS/cm. ;Limdispersjonen som anvendt i eksempel 1 ble tilsatt til massen etterfulgt av tilsetningen av kationisk stivelse. Doseringen av stivelsen var 0,03% (beregnet som ak-tiv ketendimer på tørr masse) og for den kationiske stivelsen 1,0%. Påfølgende disse tilsetningene ble 0,1% av et aromatisk kationisk polyakrylamid med benzyldimetylammoniumgrupper tilsatt før tilsetningen av 0,07% av et anionisk polystyrensulfonat med forskjellige vektgjennomsnittlige molekylvekter som indikert i tabell III og et anionisk naftalensulfonat henholdsvis. De tilsatte mengdene av forbindelser er indikert i tabell III. Retensjons- og avvanningsegenskapene av de dannede massene ble evaluert ved å måle avvanningstiden anvendende en DDA-enhet. Retensjonen ble evaluert ved å måle turbiditeten av bakvannet med en Nephelo-meter 156 fra Novasin. Videre ble limingen av det dannede, tørkede og herdete papiret evaluert ved å måle kontaktvinkelen av vann etter 10 sekunder anvendende et DAT utstyr. ; Tester 1 til 5 er ifølge foreliggende oppfinnelse, dvs. den anioniske polymeren med en vektgjennomsnittlig molekylvekt i området, fra omtrent 6 000 opptil 100 000. Som det kan sees i tabell III er limeffektiviteten betydelig økt mens turbiditeten og avvanningsytelsen samtidig høy med hensyn til tester 1 til 5 sammenlignet med den blanke. I tillegg, ved sammenligning av test 6 med tester 1 til 5 (de siste fem ifølge oppfinnelsen) er limeffektiviteten mye høyere, mens turbiditetsverdien samtidig indikerer god retensjon. Videre er en kontaktvinkel på 69,2 som oppnådd i test 6 ikke en akseptabel limingsgrad. Derved utklasser den totale ytelsen av testene 1 til 5 med hensyn til retensjon, avvanning og ikke minst liming, klart test 6. ;<*>Ingen tilsetning av verken kationisk polyakrylamid eller anionisk forbindelse, ellers var betingelsene de samme som for tester 1 til 6. <*>No addition of either cationic polyacrylamide or anionic compound, otherwise the conditions were the same as for tests 1 and 2. ; ; Example 2: The mass used was the same as used in example 1, in this example, however, the mass was adjusted to a conductivity of 400 uS/cm. The adhesive dispersion as used in example 1 was added to the mass followed by the addition of cationic starch. The dosage of the starch was 0.03% (calculated as active ketene dimer on dry mass) and for the cationic starch 1.0%. Following these additions, 0.1% of an aromatic cationic polyacrylamide with benzyldimethylammonium groups was added prior to the addition of 0.07% of an anionic polystyrene sulfonate of various weight average molecular weights as indicated in Table III and an anionic naphthalene sulfonate, respectively. The added amounts of compounds are indicated in Table III. The retention and dewatering properties of the formed masses were evaluated by measuring the dewatering time using a DDA unit. The retention was evaluated by measuring the turbidity of the tailwater with a Nephelo meter 156 from Novasin. Furthermore, the gluing of the formed, dried and hardened paper was evaluated by measuring the contact angle of water after 10 seconds using a DAT equipment. ; Tests 1 to 5 are according to the present invention, i.e. the anionic polymer with a weight average molecular weight in the range, from about 6,000 up to 100,000. As can be seen in Table III, the adhesive efficiency is significantly increased while the turbidity and dewatering performance are simultaneously high with respect to tests 1 to 5 compared to the blank. In addition, when comparing test 6 with tests 1 to 5 (the last five according to the invention), the adhesive efficiency is much higher, while the turbidity value at the same time indicates good retention. Furthermore, a contact angle of 69.2 as obtained in test 6 is not an acceptable degree of bonding. Thereby, the overall performance of tests 1 to 5 with regard to retention, dewatering and not least gluing clearly outclasses test 6. ;<*>No addition of either cationic polyacrylamide or anionic compound, otherwise the conditions were the same as for tests 1 to 6 .
Claims (13)
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| EP02445012 | 2002-01-31 | ||
| PCT/SE2003/000112 WO2003064767A1 (en) | 2002-01-31 | 2003-01-22 | Process for manufacturing paper |
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| ATE329085T1 (en) | 2002-11-28 | 2006-06-15 | Canon Kk | SIZING AGENT AND RECORDING SHEET Glued Therewith |
| US7955473B2 (en) * | 2004-12-22 | 2011-06-07 | Akzo Nobel N.V. | Process for the production of paper |
| US20060254464A1 (en) | 2005-05-16 | 2006-11-16 | Akzo Nobel N.V. | Process for the production of paper |
| US8273216B2 (en) | 2005-12-30 | 2012-09-25 | Akzo Nobel N.V. | Process for the production of paper |
| KR101318317B1 (en) | 2005-12-30 | 2013-10-15 | 아크조 노벨 엔.브이. | A process for the production of paper |
| EP2087171B1 (en) | 2006-12-01 | 2011-09-07 | Akzo Nobel N.V. | Cellulosic product |
| US8088250B2 (en) * | 2008-11-26 | 2012-01-03 | Nalco Company | Method of increasing filler content in papermaking |
| JP5288538B2 (en) * | 2008-05-20 | 2013-09-11 | ハイモ株式会社 | Paper making method |
| CN101613977B (en) * | 2009-07-15 | 2011-05-11 | 金东纸业（江苏）股份有限公司 | Fortifying fibre for making paper as well as preparation method and application thereof |
| US8852400B2 (en) * | 2010-11-02 | 2014-10-07 | Ecolab Usa Inc. | Emulsification of alkenyl succinic anhydride with an amine-containing homopolymer or copolymer |
| WO2013072277A2 (en) * | 2011-11-14 | 2013-05-23 | Basf Se | Akd composition and manufacture of paper and paperboard |
| FR2982887B1 (en) * | 2011-11-18 | 2014-01-31 | Coatex Sas | LOW ANIONIC POLYMERS FOR COATING SAUCES FOR PAPERS FOR INKJET TYPE PRINTING |
| JP6307439B2 (en) * | 2011-12-15 | 2018-04-04 | インヴェンティア・アクチボラゲットＩｎｎｖｅｎｔｉａ Ａｂ | Paper and paperboard improvement systems and methods |
| CA2890226C (en) * | 2013-01-31 | 2020-11-10 | Glatfelter Gernsbach Gmbh & Co. Kg | Crosslinking/functionalization system for a paper or non-woven web |
| US9556558B2 (en) * | 2014-01-07 | 2017-01-31 | Api Intellectual Property Holdings, Llc | Processes for producing high-yield pulp and paper products |
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| US5584966A (en) | 1994-04-18 | 1996-12-17 | E. I. Du Pont De Nemours And Company | Paper formation |
| US5595629A (en) | 1995-09-22 | 1997-01-21 | Nalco Chemical Company | Papermaking process |
| FR2740482B1 (en) * | 1995-10-30 | 1997-11-21 | Snf Sa | PROCESS FOR IMPROVING RETENTION IN A PAPER, CARDBOARD AND THE LIKE PROCESS |
| US5969011A (en) * | 1997-02-05 | 1999-10-19 | Akzo Nobel Nv | Sizing of paper |
| US6033524A (en) * | 1997-11-24 | 2000-03-07 | Nalco Chemical Company | Selective retention of filling components and improved control of sheet properties by enhancing additive pretreatment |
| EP0953680A1 (en) * | 1998-04-27 | 1999-11-03 | Akzo Nobel N.V. | A process for the production of paper |
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| AR038336A1 (en) | 2005-01-12 |
| JP2005516135A (en) | 2005-06-02 |
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| BR0307252A (en) | 2004-12-14 |
| EP1470292A1 (en) | 2004-10-27 |
| BR0307252B1 (en) | 2014-02-04 |
| AU2003238688B2 (en) | 2006-04-06 |
| RU2281994C2 (en) | 2006-08-20 |
| PT1470292E (en) | 2014-09-03 |
| PL371243A1 (en) | 2005-06-13 |
| CN1625631A (en) | 2005-06-08 |
| TW593840B (en) | 2004-06-21 |
| ZA200405126B (en) | 2005-08-31 |
| KR20040075104A (en) | 2004-08-26 |
| ES2501166T3 (en) | 2014-10-01 |
| PL214002B1 (en) | 2013-06-28 |
| MXPA04006655A (en) | 2004-10-04 |
| WO2003064767A1 (en) | 2003-08-07 |
| EP1470292B1 (en) | 2014-06-25 |
| NO20043623L (en) | 2004-11-01 |
| TW200400305A (en) | 2004-01-01 |
| RU2004126318A (en) | 2005-03-10 |
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