EP4323586A1 - Method for manufacturing paper and cardboard - Google Patents
Method for manufacturing paper and cardboardInfo
- Publication number
- EP4323586A1 EP4323586A1 EP22723053.9A EP22723053A EP4323586A1 EP 4323586 A1 EP4323586 A1 EP 4323586A1 EP 22723053 A EP22723053 A EP 22723053A EP 4323586 A1 EP4323586 A1 EP 4323586A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- water
- reaction
- weight
- aqueous solution
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000011111 cardboard Substances 0.000 title claims abstract description 18
- 239000011087 paperboard Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 87
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims abstract description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims abstract description 7
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- 150000001299 aldehydes Chemical group 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 abstract description 3
- 229920003043 Cellulose fiber Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000000835 fiber Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- 239000000123 paper Substances 0.000 description 8
- 229920002401 polyacrylamide Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229910019093 NaOCl Inorganic materials 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- -1 poly( isobutenyl Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000007762 w/o emulsion Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 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
- 125000000217 alkyl group Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- ORQYPOUSZINNCB-UHFFFAOYSA-N potassium;hypobromite Chemical compound [K+].Br[O-] ORQYPOUSZINNCB-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- PUMJJNHOWLBVRE-UHFFFAOYSA-N 1-(trioxidanyl)butane Chemical group CCCCOOO PUMJJNHOWLBVRE-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-UHFFFAOYSA-N 2-(1,2-dihydroxyethyl)oxolane-3,4-diol Polymers OCC(O)C1OCC(O)C1O JNYAEWCLZODPBN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 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
- HVUMOYIDDBPOLL-UHFFFAOYSA-N 2-(3,4-Dihydroxyoxolan-2-yl)-2-hydroxyethyl octadecanoate Polymers CCCCCCCCCCCCCCCCCC(=O)OCC(O)C1OCC(O)C1O HVUMOYIDDBPOLL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 1
- OUEBZMGRFLTABC-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)(C)CNC(=O)C=C OUEBZMGRFLTABC-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- DNHDSWZXBHTLDP-UHFFFAOYSA-N 3-(2-ethenylpyridin-1-ium-1-yl)propane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCC[N+]1=CC=CC=C1C=C DNHDSWZXBHTLDP-UHFFFAOYSA-N 0.000 description 1
- BLGRSDRGCZQJMW-UHFFFAOYSA-N 3-(dimethylamino)propane-1-sulfonic acid ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C.CN(C)CCCS(O)(=O)=O BLGRSDRGCZQJMW-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- QDQHWKZZJJDBND-UHFFFAOYSA-M 4-ethyl-4-hexadecylmorpholin-4-ium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CCCCCCCCCCCCCCCC[N+]1(CC)CCOCC1 QDQHWKZZJJDBND-UHFFFAOYSA-M 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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFEOXCGSEROQQN-UHFFFAOYSA-N C(C(=C)C)(=O)OCC.C(C)[N+](C)(C)C Chemical compound C(C(=C)C)(=O)OCC.C(C)[N+](C)(C)C UFEOXCGSEROQQN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- LWZFANDGMFTDAV-UHFFFAOYSA-N Sorbitan laurate Polymers CCCCCCCCCCCC(=O)OCC(O)C1OCC(O)C1O LWZFANDGMFTDAV-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Polymers CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Polymers CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- LWZFANDGMFTDAV-URHIDPGUSA-N [(2r)-2-[(3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Polymers CCCCCCCCCCCC(=O)OC[C@@H](O)C1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-URHIDPGUSA-N 0.000 description 1
- LWZFANDGMFTDAV-WYDSMHRWSA-N [2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Polymers CCCCCCCCCCCC(=O)OCC(O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-WYDSMHRWSA-N 0.000 description 1
- LWZFANDGMFTDAV-IOVMHBDKSA-N [2-[(2r,3s,4r)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Polymers CCCCCCCCCCCC(=O)OCC(O)[C@H]1OC[C@@H](O)[C@@H]1O LWZFANDGMFTDAV-IOVMHBDKSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 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
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- MURATLQCNSCUID-UHFFFAOYSA-N dimethyl(3-sulfopropyl)azanium 2-methyl-N-propylprop-2-enimidate Chemical compound CCCN=C([O-])C(C)=C.C[NH+](C)CCCS(O)(=O)=O MURATLQCNSCUID-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FQKWHGOHXVHGMR-UHFFFAOYSA-N hexadecoxybenzene Chemical compound CCCCCCCCCCCCCCCCOC1=CC=CC=C1 FQKWHGOHXVHGMR-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920006007 hydrogenated polyisobutylene Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 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 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000008389 polyethoxylated castor oil Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 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
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- JNYAEWCLZODPBN-CTQIIAAMSA-N sorbitan Polymers OCC(O)C1OCC(O)[C@@H]1O JNYAEWCLZODPBN-CTQIIAAMSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/06—Oxidation
-
- 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
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- 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
Definitions
- the present invention relates to a process for the manufacture of paper or board having improved drainage and runnability properties. More specifically, the subject of the invention is a process involving the reaction of a water-soluble polymer in the form of an inverse emulsion in a mixture of alkaline hydroxide and/or alkaline-earth hydroxide and hypo- alkali halide and/or alkaline-earth hypo-halide and then injecting it directly into the fibrous suspension used to manufacture the paper or cardboard.
- the present invention also relates to the papers and cardboards with improved physical properties obtained by this process.
- the drainage properties relate to the ability of the fibrous mat to evacuate or drain the maximum amount of water before drying. Improved drainage properties mean energy savings and increased production capacity.
- Runnability refers to the optimization of the operation of the paper machine by increasing productivity through better drainage on the table, better dryness in the press section, a reduction in breakages through greater cleanliness of the circuits and a reduction deposits.
- JP 2002-212898 describes the use of a polymer resulting from the Hofmann degradation reaction in a papermaking process. This document does not describe, during a chemical reaction, the addition of a polymer in the form of an inverse emulsion.
- WO 2020/094960 describes inverse emulsion compositions.
- EP 2 840 100 the functionalization of a polymer.
- Polyvinylamines are known to improve drainage during paper formation.
- Polyvinylamines can be obtained by reacting a solution of polyacrylamide in a mixture of alkali hydroxide and/or alkaline earth hydroxide and alkali hypohalide and/or hypohalide of alkaline earth metal followed by treatment in an acid medium.
- this reaction on polyacrylamide requires heating the reaction medium and also a need for an exchanger to regulate its temperature at the end of the reaction.
- This method also makes it possible to avoid all the logistics (transport or installation of a dissolution unit) inherent in the handling of solutions of water-soluble polymers.
- the process is all the more simple as from the addition of the polymer in the form of an inverse emulsion in the mixture of hydroxide and hypo-halide of alkaline and / or alkaline-earth metal the reaction medium is homogeneous and it is not necessary to heat the reaction medium or to use heat exchangers.
- alkaline denotes an alkali metal, advantageously lithium, sodium or potassium.
- alkali hydroxide designates a hydroxide (OH ) of at least one alkali metal, for example NaOH, KOH or NaOH+KOH. The same is true for alkaline earth hydroxide.
- alkaline-earth is meant an alkaline-earth metal, advantageously calcium or magnesium.
- a hypo-halide is an oxyanion, for example hypochlorite CIO.
- alkaline hypo-halide means a hypo-halide of at least one alkali metal and at least one hypo-halide, for example NaOCl, KOBr or NaOCl+KOBr. The same is true for the alkaline-earth hypo-halide.
- the process of the invention makes it possible to increase the range of drainage agents and current dry strength compared to a similar process using polyacrylamides in the form of an aqueous solution.
- the invention relates to a process for manufacturing a sheet of paper or cardboard from a fibrous suspension, comprising the following steps: a) injection of a polymer P2 into a fibrous suspension (advantageously a suspension of cellulosic fibers), b) forming a sheet of paper or cardboard, c) drying the sheet of paper or cardboard, the polymer P2 being prepared, prior to step a), from a water-soluble polymer PI in the form of an inverse emulsion, PI being a water-soluble polymer of at least one nonionic monomer chosen from acrylamide, methacrylamide, N,N-dimethylacrylamide, and acrylonitrile, the polymer P2 being obtained by a reaction Re consisting in adding the water-soluble polymer PI in the form of an inverse emulsion in an aqueous solution M1 of: (i) a an alkali metal hydroxide, or an alkaline earth metal hydroxide, or mixtures thereof (ii) an al
- step a) is carried out within a period not exceeding 24 hours from the start of the Re reaction, that is to say from the addition of the water-soluble polymer PI in the form of inverse emulsion in aqueous solution M1.
- the dry matter corresponds to the dry extract obtained after evaporation of the water from the fibrous suspension used in a process for manufacturing a sheet of paper or cardboard.
- the dry matter is generally based on cellulosic fibers and fillers, advantageously consisting of cellulosic fibers and fillers.
- the term "cellulosic fibers" encompasses any cellulosic entity, including fibers, fines, microfibrils or nanofibrils.
- fibrous suspension we mean the thick paste or the thin paste which is based on water and cellulosic fibers.
- the thick stock (Thick Stock), having a mass concentration of dry matter generally greater than 1%, or even greater than 3%, is upstream of the mixing pump (fan-pump).
- the dilute paste (Thin Stock), having a mass concentration of dry matter generally less than 1%, is located downstream of the mixing pump.
- polymer designates both homopolymers and copolymers of at least two distinct monomers.
- An amphoteric polymer is a polymer comprising cationic charges and anionic charges, preferably as many anionic charges as cationic charges.
- water-soluble polymer means a polymer which yields an aqueous solution without insoluble particles when dissolved with stirring for 4 hours at 25°C and with a concentration of 20 gL 1 in deionized water .
- the water-soluble polymer PI is a polymer of at least one nonionic monomer chosen from acrylamide, methacrylamide, N,N-dimethylacrylamide, and acrylonitrile.
- the polymer PI contains at least 50 mol% of at least one of these nonionic monomers.
- the polymer PI can also contain anionic and/or cationic and/or zwitterionic monomers.
- Polymer PI is advantageously devoid of nonionic monomer which is not chosen from acrylamide, methacrylamide, N,N-dimethylacrylamide, and acrylonitrile.
- the anionic monomers are preferably chosen from the group comprising monomers having a carboxylic acid function and their salts including acrylic acid, methacrylic acid, itaconic acid, maleic acid, monomers having a sulphonic acid function and their salts; including acrylamido tert-butyl sulfonic acid (ATBS), allyl sulfonic acid and methallyl sulfonic acid, and their salts, and monomers having a phosphonic acid function and their salts.
- monomers having a carboxylic acid function and their salts including acrylic acid, methacrylic acid, itaconic acid, maleic acid, monomers having a sulphonic acid function and their salts; including acrylamido tert-butyl sulfonic acid (ATBS), allyl sulfonic acid and methallyl sulfonic acid, and their salts, and monomers having a phosphonic acid function and their salts.
- ATBS acrylamid
- the anionic monomers of the polymer PI have as counterion an alkali metal, an alkaline-earth metal or an ammonium (preferably a quaternary ammonium).
- the cationic monomers are preferably chosen from the group comprising quaternized or salified dimethylaminoethyl acrylate (AD AME), quaternized or salified dimethylaminoethyl methacrylate (MADAME), diallyldimethylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC) , and methacrylamidopropyltrimethylammonium chloride (MAPTAC).
- AD AME quaternized or salified dimethylaminoethyl acrylate
- MADAME quaternized or salified dimethylaminoethyl methacrylate
- DDADMAC diallyldimethylammonium chloride
- ATAC acrylamidopropyltrimethylammonium chloride
- MATAC methacrylamidopropyltrimethylammonium chloride
- the cationic monomers of the polymer PI have as counterion a halide, preferably a chloride ion.
- the zwitterionic monomers are preferably chosen from the group comprising sulfobetaine monomers such as sulfopropyl dimethylammonium ethyl methacrylate, sulfopropyl dimethylammonium propyl methacrylamide, or sulfopropyl 2-vinylpyridinium; phosphobetaine monomers, such as phosphato ethyltrimethylammonium ethyl methacrylate; and carboxybetaine monomers.
- the water-soluble polymer PI is a homopolymer or a copolymer of acrylamide or of methacrylamide.
- the PI polymer can be linear, structured or cross-linked.
- the crosslinking agents allowing the structuring can in particular be chosen from sodium allyl sulfonate, sodium methallyl sulfonate, sodium methallyl disulfonate, methylenebisacrylamide, triallylamine, triallylammonium chloride.
- the structuring of the polymer PI can also be obtained with at least one polyfunctional compound containing at least 3 heteroatoms chosen from N, S, O, P and each having at least one mobile hydrogen.
- This polyfunctional compound can in particular be a polyethyleneimine or a polyamine.
- the reaction Re is carried out by adding an inverse emulsion of water-soluble polymer PI to the aqueous solution Ml.
- the inverse emulsion (water-in-oil emulsion) comprises:
- An aqueous phase comprising at least the polymer PI
- At least one emulsifying agent and at least one reversing agent At least one emulsifying agent and at least one reversing agent.
- the oily phase can be a mineral oil, a vegetable oil, a synthetic oil or a mixture of several of these oils.
- mineral oil examples include mineral oils containing saturated hydrocarbons of the aliphatic, naphthenic, paraffinic, isoparaffinic, cycloparaffinic or naphthyl type.
- Examples of synthetic oil are hydrogenated polydecene or hydrogenated polyisobutene, an ester such as octyl stearate or butyl oleate.
- Exxon's Exxsol® product line is a perfect fit.
- the weight ratio of water phase to oil phase in the invert emulsion is preferably 50/50 to 90/10. This ratio includes the weight of the various constituents of the emulsion, in particular the water-soluble polymer PI.
- the water-in-oil emulsion preferably comprises from 15 to 40% by weight of oil, from 20 to 55% by weight of water, from 15 and 50% by weight of polymer PI, the percentages being expressed relative to the total weight of the inverse emulsion of the polymer PI.
- emulsifying agent designates an agent capable of emulsifying water in an oil
- an “inverting agent” is an agent capable of emulsifying an oil in water. More specifically, it is considered that a reversing agent is a surfactant having an HLB greater than or equal to 10, and that an emulsifying agent is a surfactant having an HLB strictly less than 10.
- the hydrophilic-lipophilic balance (HLB) of a chemical compound is a measure of its degree of hydrophilicity or lipophilicity, determined by calculating the values of different regions of the molecule, as described by Griffin in 1949 (Griffin WC, Classification of Surface-Active Agents by HLB, Journal of the Society of Cosmetic Chemists, 1949, 1, pages 311-326).
- Griffin's method based on calculating a value based on the chemical groups of the molecule.
- Griffin assigned a dimensionless number between 0 and 20 to give information about water and oil solubility.
- Substances with an HLB value of 10 are distributed between the two phases, so that the hydrophilic group (molecular mass Mh) projects completely into the water while the hydrophobic hydrocarbon group (molecular mass Mp) is adsorbed in the non-phase. watery.
- HLB 20 (Mh/M).
- the inverse emulsion containing the polymer PI advantageously contains from 0.1% to 10% by weight of at least one emulsifying agent, the percentages being expressed by weight relative to the weight of the emulsion.
- This emulsifying agent is advantageously chosen from sorbitan esters, polyethoxylated sorbitan esters, polyethoxylated fatty acids, polyethoxylated fatty alcohols, polyesters having an average molecular weight of between 1000 and 3000 daltons resulting from the condensation between a poly( isobutenyl) succinic or its anhydride and a polyethylene glycol, block copolymers with an average molecular weight of between 2500 and 3500 daltons resulting from the condensation between hydroxystearic acid and a polyethylene glycol, ethoxylated fatty amines, derivatives of di-alkanol amides , copolymers of stearyl methacrylate, and mixtures of these emulsifying agents.
- the inverse emulsion containing the polymer PI advantageously contains between 0.1 and 10% by weight of at least one inverting agent, the percentages being expressed by weight relative to the weight of the emulsion.
- This reversing agent is advantageously chosen from ethoxylated nonylphenols, preferably having 4 to 10 ethoxylations; ethoxylated/propoxylated alcohols preferably having an ethoxylation/propoxylation comprising between 12 and 25 carbon atoms; ethoxylated tridecyl alcohols; polyethoxylated fatty acids; poly(ethoxylated/propoxylated) fatty alcohols; ethoxylated sorbitan esters; polyethoxylated sorbitan laurate; polyethoxylated castor oil; heptaoxyethyl lauryl alcohol; polyethoxylated sorbitan monostearate; polyethoxylated alkyl phenol cetyl ether; poly ethylene
- the water-in-oil emulsion according to the invention can be prepared according to any method known to those skilled in the art. Generally, an aqueous solution comprising the monomer(s) and the emulsifying agent(s) is emulsified in an oily phase. Then, the polymerization is carried out by adding a free radical initiator.
- a free radical initiator We can refer to redox couples, with cumene hydroperoxide, tertiary butylhydroxyperoxide or persulfates among the oxidizing agents, sodium sulfite, sodium metabisulfite and Mohr's salt among the reducing agents.
- Azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-amidinopropane) hydrochloride can also be used.
- the polymerization is generally carried out in an isothermal, adiabatic or temperature-controlled manner.
- the temperature is advantageously kept constant, generally between 10 and 60°C (isothermal), or else the temperature is allowed to increase naturally (adiabatic) and in this case, the reaction is generally started at a temperature below 10°C and the final temperature is usually greater than 50°C or, finally, the increase in temperature is controlled so as to have a temperature curve between the isothermal curve and the adiabatic curve.
- the reversing agent(s) are added at the end of the polymerization reaction, preferably at a temperature below 50°C.
- Reaction Re consists of adding the inverse polymer emulsion PI to an aqueous solution M1 of: (i) an alkaline hydroxide and/or an alkaline-earth hydroxide, (ii) an alkaline hypo-halide and/or an alkaline earth hypo-halide, with a reaction time Re of 10 seconds to 5 hours to form the polymer P2.
- the aqueous solution M1 is an aqueous solution of soda (sodium hydroxide) and sodium hypochlorite.
- reaction time of the polymer PI in the aqueous solution M1 of hypohalide and hydroxide is from 10 seconds to 180 minutes.
- the Re reaction is advantageously carried out at a temperature comprised between 10 and 30°C, more advantageously between 15 and 25°C.
- reaction Re preferably between 0.1 and 20% by weight of polymer PI, relative to the weight of the aqueous solution Ml, more preferably between 0.3 and 10% and even more preferably between 0.5 and 3.0 % by weight, are added to the aqueous solution M1.
- the polymer P2 can be functionalized with a compound comprising at least one aldehyde function to give a polymer P3, for example by adding a compound comprising at least an aldehyde function.
- the compound comprising at least one aldehyde function is glyoxal.
- the pH of the reaction mixture resulting from the reaction Re and containing the polymer P2 can be adjusted by adding acid between 0.5 and 7.5, more preferably between 1.0 and 3, 0. A person skilled in the art knows how to adjust the pH of this type of reaction medium. The adjustment of the pH is advantageously carried out in the absence of formation of the polymer P3.
- the polymer P2 (or P3) is introduced into the white waters and/or the thick paste and/or the mixture formed by the white waters and the thick paste after homogenization of the fibrous suspension in the pump of dilution (fan-pump).
- the polymer P2 (or P3) can also be introduced into the papermaking process at the level of the forming table, for example by spraying or application in the form of a foam, or even at the level of the size press (coater)
- the fibrous suspension encompasses the possible use of different cellulosic fibers: virgin fibers, recycled fibers, chemical pulp, mechanical pulp, micro-fibrillated cellulose or nano-fibrillated cellulose.
- the fibrous suspension also encompasses the use of these different cellulosic fibers with all types of fillers such as TiCh, C aCC ⁇ (ground or precipitated), kaolin, organic fillers and mixtures thereof.
- Polymer P2 or P3 can be used within the papermaking process in combination with other products such as inorganic or organic coagulants, dry strength agents, wet strength agents, natural polymers such as starches or carboxymethylcellulose (CMC), inorganic microparticles such as bentonite microparticles and colloidal silica microparticles, organic polymers of any ionic nature (nonionic, cationic, anionic, or amphoteric) and which may be (without being limiting) linear, branched, cross-linked, hydrophobic, or associative.
- CMC carboxymethylcellulose
- organic polymers of any ionic nature nonionic, cationic, anionic, or amphoteric
- Recycled fiber pulp Wet pulp is obtained by disintegrating dry pulp to obtain a final aqueous concentration of 1% by weight. It is a pH-neutral pulp made from 100% recycled cardboard fibres. bl Evaluation of drainage performance (PDA!
- the DDA (“Dynamic Drainage Analyzer”) makes it possible to automatically determine the time (in seconds) required to drain under vacuum a fibrous suspension deposited on a cloth.
- the polymers are added to the wet paste (0.6 liters of paste at 1.0% by weight) in the cylinder of the DDA with stirring at 1000 revolutions per minute:
- the necessary quantity of paste is removed so as to obtain a sheet having a basis weight of 90 gm 2 .
- the wet paste is introduced into the vat of the dynamic molder and is kept under agitation.
- the different components of the system are injected into this paste according to the predefined sequence.
- a contact time of 30 to 45 seconds is generally respected between each addition of polymer.
- Formettes of paper are produced with an automatic dynamic former: a blotter and the forming fabric are placed in the bowl of the dynamic former before starting the rotation of the bowl at 1000 rpm and building the water wall.
- the treated pulp is spread over the water wall to form the fibrous mat on the forming fabric.
- the fibrous mat is recovered, pressed under a press delivering 4 bar, then dried at 117°C.
- the sheet obtained is conditioned 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 measured.
- the burst (Burst Index) is measured with a Messmer Buchel M 405 burst tester according to the TAPPI T403 om-02 standard. The result is expressed in kPa or in percentage compared to a reference.
- the bursting index expressed in kPa.m 2 /g, is determined by dividing this value by the basis weight of the sheet tested.
- the dry breaking length is measured in the machine direction (DBL SM) and in the transverse direction (DBL ST) with a Testometric AX tensile device according to TAPPI T494 om-01. The result is expressed in km or in percentage compared to a reference.
- 310 g of water are introduced into a 1 liter reactor equipped with a mechanical stirrer, a thermometer, a condenser and a gaseous nitrogen plunger.
- the pH of the reaction medium is adjusted to 3.3 using a pH buffer (NaOH 30% by weight in water and H 3 PO 4 75% by weight in water).
- the medium is heated and maintained at a temperature of between 79 and 81° C. using a water bath.
- 400 g of 50% acrylamide, 237.8 g of water and 2.40 g of 100% sodium hypophosphite are incorporated (cast 1) for 180 minutes. Pour 2, 0.48 g of 100% sodium persulfate and 48 g of water for 180 minutes.
- the polymer solution is maintained at 80° C. for 120 minutes after the end of the casting.
- the solution of polymer P1-A obtained has a pH of 5.7, a concentration by weight of polymer P1-A of 20% and a viscosity of 6000 cps.
- Pl-B polymer Acrylamide homopolymer in the form of an inverse emulsion marketed by SNF under the name: FlopamTMEM 230.
- Polymers Pl-A (in aqueous solution) and Pl-B (invert emulsion) are acrylamide homopolymers which are distinguished only by their physical form.
- An aqueous solution of sodium hypochlorite 14.29 g (NaOCl) at 14.6% (by weight in water) and 7.5 g of sodium hydroxide at 30% (by weight in water) is prepared by function of the alpha (0.5) and beta (2.0) coefficients for the Re reaction.
- Pl-A polymer solution is at 50°C
- the aqueous solution of sodium hypochlorite and sodium hydroxide is added to Pl -HAS.
- 138.20 g of water is added.
- a solution of polymer P2-A is obtained at a concentration of 2% by weight.
- An aqueous solution M1 of 3.66 g of sodium hypochlorite (NaOCl) at 14.6% (by weight in water) and 1.92 g of sodium hydroxide at 30% (by weight in water) is prepared according to the coefficients alpha (0.5) and beta (2.0) for the Re reaction. 93.60 g of water are then added.
- PDA Drip performance
- Table 1 Drainage according to the polymer. An improvement in drainage is observed with the use of polymer P2-B compared to polymer P2-A.
- Table 2 Dry strength depending on the polymer. Burst performance is improved by using the P2-B polymer. The same trend is observed for the breaking length measurement in the forward direction (DBL SM) and in the cross direction (DBL ST).
Abstract
The present invention relates to a method for manufacturing a sheet of paper or cardboard from a fibrous suspension, comprising the following steps: a) injecting a polymer P2 into a suspension of cellulose fibres; b) forming a sheet of paper or cardboard; and c) drying the sheet of paper or cardboard, the polymer P2 being prepared, prior to step a), from a water-soluble polymer P1 in the form of an invert emulsion, P1 consisting of at least one non-ionic monomer selected from acrylamide, methacrylamide, N,N-dimethylacrylamide and acrylonitrile, the polymer P1 being subjected to a reaction Re to give a polymer P2, the reaction Re consisting of adding the polymer P1 in the form of an invert emulsion in an aqueous solution M1 of: (i) an alkali hydroxide and/or an alkaline earth hydroxide, (ii) an alkali hypohalide and/or an alkaline earth hypohalide before a reaction time of 10 seconds to 5 hours.
Description
PROCEDE DE FABRICATION DE PAPIER ET DE CARTON PAPER AND CARDBOARD MANUFACTURING PROCESS
Domaine de l’invention Field of invention
La présente invention concerne un procédé pour la fabrication de papier ou de carton présentant des propriétés d’égouttage et de machinabilité améliorées. Plus précisément, l’invention a pour objet un procédé impliquant la réaction d’un polymère hydrosoluble sous forme d’émulsion inverse dans un mélange d’hydroxyde d’alcalin et/ou d’hydroxyde d’alcalino-terreux et d’hypo-halogénure d’alcalin et/ou d’hypo-halogénure d’alcalino-terreux pour ensuite l’injecter directement dans la suspension fibreuse servant à fabriquer le papier ou le carton. The present invention relates to a process for the manufacture of paper or board having improved drainage and runnability properties. More specifically, the subject of the invention is a process involving the reaction of a water-soluble polymer in the form of an inverse emulsion in a mixture of alkaline hydroxide and/or alkaline-earth hydroxide and hypo- alkali halide and/or alkaline-earth hypo-halide and then injecting it directly into the fibrous suspension used to manufacture the paper or cardboard.
La présente invention a également pour objet les papiers et cartons aux propriétés physiques améliorées obtenus par ce procédé. The present invention also relates to the papers and cardboards with improved physical properties obtained by this process.
Etat antérieur de la technique Prior state of the art
L’industrie papetière est en recherche constante d’optimisation de ses procédés de fabrication, de papier ou de carton, plus particulièrement en termes de rendement, de productivité, de réduction des coûts et de qualité des produits finis. The paper industry is constantly seeking to optimize its manufacturing processes, paper or cardboard, more particularly in terms of yield, productivity, cost reduction and quality of finished products.
L’utilisation de polymères comme agents de résistance à sec, d’égouttage et de machinabilité est très largement décrite. The use of polymers as dry strength, drainage and runnability agents is widely described.
Les propriétés d’égouttage (ou drainage) concernent la capacité du matelas fibreux à évacuer ou drainer le maximum d’eau avant la sécherie. Des propriétés d’égouttage améliorées impliquent un gain d’énergie et une augmentation de la capacité de production. The drainage properties (or drainage) relate to the ability of the fibrous mat to evacuate or drain the maximum amount of water before drying. Improved drainage properties mean energy savings and increased production capacity.
Par machinabilité, on désigne l’optimisation du fonctionnement de la machine à papier en augmentant la productivité par un meilleur égouttage sur la table, une meilleure siccité à la section de presse, une diminution des casses par une plus grande propreté des circuits et une diminution des dépôts. Runnability refers to the optimization of the operation of the paper machine by increasing productivity through better drainage on the table, better dryness in the press section, a reduction in breakages through greater cleanliness of the circuits and a reduction deposits.
JP 2002-212898 décrit l’utilisation d’un polymère issu de la réaction de dégradation d’Hofmann dans un procédé de fabrication du papier. Ce document ne décrit pas, lors d’une réaction chimique, l’addition d’un polymère sous la forme d’une émulsion inverse.
WO 2020/094960 décrit des compositions d’émulsion inverse. EP 2 840 100 la fonctionnarisation d’un polymère. JP 2002-212898 describes the use of a polymer resulting from the Hofmann degradation reaction in a papermaking process. This document does not describe, during a chemical reaction, the addition of a polymer in the form of an inverse emulsion. WO 2020/094960 describes inverse emulsion compositions. EP 2 840 100 the functionalization of a polymer.
Les polyvinylamines sont connues pour améliorer le drainage lors de la formation du papier.Polyvinylamines are known to improve drainage during paper formation.
Les polyvinylamines peuvent être obtenues par réaction d’une solution de polyacrylamide dans un mélange d’hydroxyde d’alcalin et/ou d’hydroxyde d’alcalino-terreux et d’hypo- halogénure d’alcalin et/ou d’hypo-halogénure d’alcalino-terreux suivie d’un traitement en milieu acide. Polyvinylamines can be obtained by reacting a solution of polyacrylamide in a mixture of alkali hydroxide and/or alkaline earth hydroxide and alkali hypohalide and/or hypohalide of alkaline earth metal followed by treatment in an acid medium.
Lorsque la réaction est effectuée directement avant injection du produit dans la suspension fibreuse pour l’obtention du papier ou du carton, seule la réaction du polyacrylamide en solution avec les hydroxydes et hypo-halogénures d’alcalin ou d’alcalino terreux est effectuée. When the reaction is carried out directly before injection of the product into the fibrous suspension to obtain paper or cardboard, only the reaction of the polyacrylamide in solution with the hydroxides and hypo-halides of alkaline or alkaline earth metal is carried out.
Toutefois, cette nécessité d’avoir des solutions de polyacrylamide implique leur acheminement jusqu’à la papeterie ou la nécessité d’avoir un équipement de dissolution du polymère dans la papeterie. Dans les deux cas, l’empreinte au sol des stocks de solutions de polymère ou des équipements de dissolution reste importante. However, this need to have polyacrylamide solutions implies their transport to the paper mill or the need to have equipment for dissolving the polymer in the paper mill. In both cases, the footprint of polymer solution stocks or dissolution equipment remains significant.
De plus cette réaction sur le polyacrylamide nécessite de chauffer le milieu réactionnel et aussi un besoin d’échangeur pour réguler sa température en fin de réaction. In addition, this reaction on polyacrylamide requires heating the reaction medium and also a need for an exchanger to regulate its temperature at the end of the reaction.
Exposé de l’invention Disclosure of Invention
De manière inattendue, la Demanderesse a découvert qu’un procédé impliquant la réaction d’un polymère hydrosoluble sous forme d’émulsion inverse (eau dans huile) dans un mélange d’hydroxyde (hydroxyde de métal alcalin et/ou hydroxyde de métal alcalino-terreux) et d’hypo-halogénure (hypo-halogénure de métal alcalin et/ou hypo-halogénure de métal alcalino-terreux) pour ensuite l’injecter directement dans la suspension fibreuse servant à fabriquer le papier ou le carton permet d’améliorer les propriétés d’égouttage et de résistance à sec. Unexpectedly, the Applicant has discovered that a process involving the reaction of a water-soluble polymer in the form of an inverse emulsion (water in oil) in a mixture of hydroxide (alkali metal hydroxide and/or alkaline metal hydroxide) earth metal) and hypo-halide (alkali metal hypo-halide and/or alkaline-earth metal hypo-halide) and then injecting it directly into the fibrous suspension used to manufacture paper or cardboard makes it possible to improve drainage and dry resistance properties.
Ce procédé permet également d’éviter toute une logistique (transport ou installation d’une unité de dissolution) inhérente à la manipulation de solutions de polymères hydrosolubles.
De plus le procédé est d’autant plus simple que dès l’addition du polymère sous forme d’émulsion inverse dans le mélange d’hydroxyde et d’hypo-halogénure d’alcalin et/ou d’alcalino-terreux le milieu réactionnel est homogène et il n’est pas nécessaire de chauffer le milieu réactionnel ni d’utiliser des échangeurs thermiques. This method also makes it possible to avoid all the logistics (transport or installation of a dissolution unit) inherent in the handling of solutions of water-soluble polymers. In addition, the process is all the more simple as from the addition of the polymer in the form of an inverse emulsion in the mixture of hydroxide and hypo-halide of alkaline and / or alkaline-earth metal the reaction medium is homogeneous and it is not necessary to heat the reaction medium or to use heat exchangers.
Par « alcalin », on désigne un métal alcalin, avantageusement le lithium, le sodium ou le potassium. Un « hydroxyde d’alcalin » désigne un hydroxyde (OH ) d’au moins un métal alcalin, par exemple NaOH, KOH ou NaOH+KOH. Il en est de même pour l’hydroxyde d’ alcalino-terreux. The term "alkaline" denotes an alkali metal, advantageously lithium, sodium or potassium. An “alkali hydroxide” designates a hydroxide (OH ) of at least one alkali metal, for example NaOH, KOH or NaOH+KOH. The same is true for alkaline earth hydroxide.
Par « alcalino-terreux », on désigne un métal alcalino-terreux, avantageusement le calcium ou le magnésium. By “alkaline-earth”, is meant an alkaline-earth metal, advantageously calcium or magnesium.
Un hypo-halogénure est un oxyanion, par exemple l’hypochlorite CIO . A hypo-halide is an oxyanion, for example hypochlorite CIO.
Un « hypo-halogénure d’alcalin » désigne un hypo-halogénure d’au moins un métal alcalin et d’au moins un hypo-halogénure, par exemple NaOCl, KOBr ou NaOCl+KOBr. Il en est de même pour l’hypo-halogénure d’ alcalino-terreux. An "alkaline hypo-halide" means a hypo-halide of at least one alkali metal and at least one hypo-halide, for example NaOCl, KOBr or NaOCl+KOBr. The same is true for the alkaline-earth hypo-halide.
Enfin, la gamme de poids moléculaire des polymères hydrosolubles sous forme d’émulsion inverse étant large, le procédé de l’invention permet d’augmenter la gamme d’agents d’égouttage et de résistance à sec actuelle par rapport à un procédé similaire utilisant des polyacrylamides sous forme de solution aqueuse. Finally, the molecular weight range of water-soluble polymers in the form of an inverse emulsion being wide, the process of the invention makes it possible to increase the range of drainage agents and current dry strength compared to a similar process using polyacrylamides in the form of an aqueous solution.
Plus précisément, l’invention concerne un procédé de fabrication d’une feuille de papier ou de carton à partir d’une suspension fibreuse, comprenant les étapes suivantes : a) injection d’un polymère P2 dans une suspension fibreuse (avantageusement une suspension de fibres cellulosiques), b) formation d’une feuille de papier ou de carton, c) séchage de la feuille de papier ou de carton, le polymère P2 étant préparé, préalablement à l’étape a), à partir d’un polymère hydrosoluble PI sous forme d’émulsion inverse, PI étant un polymère hydrosoluble d’au moins un monomère non ionique choisi parmi l’acrylamide, le méthacrylamide, le N,N- diméthylacrylamide, et l’acrylonitrile, le polymère P2 étant obtenu par une réaction Re consistant à ajouter le polymère hydrosoluble PI sous forme d’émulsion inverse dans une solution aqueuse Ml de : (i) un
hydroxyde de métal alcalin, ou un hydroxyde de métal alcalino-terreux, ou leurs mélanges (ii) un hypo-halogénure de métal alcalin, ou un hypo-halogénure de métal alcalino-terreux, ou leurs mélanges la réaction Re ayant un temps de réaction de 10 secondes à 5 heures après l’ajout du polymère hydrosoluble PI sous forme d’émulsion inverse. More specifically, the invention relates to a process for manufacturing a sheet of paper or cardboard from a fibrous suspension, comprising the following steps: a) injection of a polymer P2 into a fibrous suspension (advantageously a suspension of cellulosic fibers), b) forming a sheet of paper or cardboard, c) drying the sheet of paper or cardboard, the polymer P2 being prepared, prior to step a), from a water-soluble polymer PI in the form of an inverse emulsion, PI being a water-soluble polymer of at least one nonionic monomer chosen from acrylamide, methacrylamide, N,N-dimethylacrylamide, and acrylonitrile, the polymer P2 being obtained by a reaction Re consisting in adding the water-soluble polymer PI in the form of an inverse emulsion in an aqueous solution M1 of: (i) a an alkali metal hydroxide, or an alkaline earth metal hydroxide, or mixtures thereof (ii) an alkali metal hypo-halide, or an alkaline earth metal hypo-halide, or mixtures thereof, the reaction Re having a reaction time from 10 seconds to 5 hours after the addition of the water-soluble polymer PI in the form of an inverse emulsion.
De manière avantageuse, l’étape a) est réalisée dans un délai n’excédant pas 24 heures à compter du début de la réaction Re, c’est-à-dire à compter de l’ajout du polymère hydrosoluble PI sous forme d’émulsion inverse dans la solution aqueuse Ml. Advantageously, step a) is carried out within a period not exceeding 24 hours from the start of the Re reaction, that is to say from the addition of the water-soluble polymer PI in the form of inverse emulsion in aqueous solution M1.
Dans la suite de la description et dans les revendications, tous les dosages de polymère exprimés en g.t 1 ou kg.t 1 sont donnés en poids de polymère par tonne de matière sèche. La matière sèche correspond à l’extrait sec obtenu après évaporation de l’eau de la suspension fibreuse utilisée dans un procédé de fabrication d’une feuille de papier ou de carton. La matière sèche est généralement à base de fibres cellulosiques et de charges, avantageusement constituée de fibres cellulosiques et de charges. Le terme « fibres cellulosiques » englobe toute entité cellulosique, incluant les fibres, les fines, les microfibrilles ou les nanofibrilles.In the rest of the description and in the claims, all the polymer dosages expressed in gt 1 or kg.t 1 are given in weight of polymer per tonne of dry matter. The dry matter corresponds to the dry extract obtained after evaporation of the water from the fibrous suspension used in a process for manufacturing a sheet of paper or cardboard. The dry matter is generally based on cellulosic fibers and fillers, advantageously consisting of cellulosic fibers and fillers. The term "cellulosic fibers" encompasses any cellulosic entity, including fibers, fines, microfibrils or nanofibrils.
Par suspension fibreuse, on entend la pâte épaisse ou la pâte diluée qui sont à base d’eau et de fibres cellulosiques. La pâte épaisse (Thick Stock), ayant une concentration massique en matière sèche généralement supérieure à 1 %, voire supérieure à 3 %, est en amont de la pompe de mélange (fan-pump). La pâte diluée ( Thin Stock), ayant une concentration massique en matière sèche généralement inférieure à 1 %, est située en aval de la pompe de mélange.By fibrous suspension, we mean the thick paste or the thin paste which is based on water and cellulosic fibers. The thick stock (Thick Stock), having a mass concentration of dry matter generally greater than 1%, or even greater than 3%, is upstream of the mixing pump (fan-pump). The dilute paste (Thin Stock), having a mass concentration of dry matter generally less than 1%, is located downstream of the mixing pump.
Le terme « polymère », désigne aussi bien les homopolymères que les copolymères d’au moins deux monomères distincts. The term "polymer" designates both homopolymers and copolymers of at least two distinct monomers.
Un polymère amphotère est un polymère comprenant des charges cationiques et des charges anioniques, préférentiellement autant de charges anioniques que de charges cationiques.An amphoteric polymer is a polymer comprising cationic charges and anionic charges, preferably as many anionic charges as cationic charges.
Tel qu’utilisé ici, le terme "polymère hydrosoluble" désigne un polymère qui donne une solution aqueuse sans particule insoluble lorsqu’il est dissous sous agitation pendant 4 heures à 25 °C et avec une concentration de 20 g.L 1 dans l’eau déionisée. As used herein, the term "water-soluble polymer" means a polymer which yields an aqueous solution without insoluble particles when dissolved with stirring for 4 hours at 25°C and with a concentration of 20 gL 1 in deionized water .
Les plages de valeurs incluent les bornes inférieure et supérieure. Ainsi, les plages de valeurs « entre 0,1 et 1,0 » et « de 0,1 à 1 » incluent les valeurs 0,1 et 1,0.
Le polymère hydrosoluble PI est un polymère d’au moins un monomère non ionique choisi parmi l’acrylamide, le méthacrylamide, le N,N-diméthylacrylamide, et l’acrylonitrile. Préférentiellement, le polymère PI contient au moins 50 mol% d’au moins un de ces monomères non ioniques. Value ranges include lower and upper bounds. Thus, the ranges of values "between 0.1 and 1.0" and "from 0.1 to 1" include the values 0.1 and 1.0. The water-soluble polymer PI is a polymer of at least one nonionic monomer chosen from acrylamide, methacrylamide, N,N-dimethylacrylamide, and acrylonitrile. Preferably, the polymer PI contains at least 50 mol% of at least one of these nonionic monomers.
Le polymère PI peut aussi contenir des monomères anioniques et/ou cationiques et/ou zwitterioniques. Le polymère PI est avantageusement dépourvu de monomère non ionique qui ne soit pas choisi parmi l’acrylamide, le méthacrylamide, le N,N-diméthylacrylamide, et l’acrylonitrile. The polymer PI can also contain anionic and/or cationic and/or zwitterionic monomers. Polymer PI is advantageously devoid of nonionic monomer which is not chosen from acrylamide, methacrylamide, N,N-dimethylacrylamide, and acrylonitrile.
Les monomères anioniques sont préférentiellement choisis dans le groupe comprenant les monomères possédant une fonction acide carboxylique et leurs sels dont l’acide acrylique, l’acide méthacrylique, l’acide itaconique, l’acide maléique, les monomères possédant une fonction acide sulfonique et leurs sels ; dont l’acide acrylamido tertio butyl sulfonique (ATBS), l’acide allyl sulfonique et l’acide méthallyl sulfonique, et leurs sels, et les monomères ayant une fonction acide phosphonique et leurs sels. The anionic monomers are preferably chosen from the group comprising monomers having a carboxylic acid function and their salts including acrylic acid, methacrylic acid, itaconic acid, maleic acid, monomers having a sulphonic acid function and their salts; including acrylamido tert-butyl sulfonic acid (ATBS), allyl sulfonic acid and methallyl sulfonic acid, and their salts, and monomers having a phosphonic acid function and their salts.
De manière générale, les monomères anioniques du polymère PI ont comme contre-ion un métal alcalin, un métal alcalino-terreux ou un ammonium (préférentiellement un ammonium quaternaire). In general, the anionic monomers of the polymer PI have as counterion an alkali metal, an alkaline-earth metal or an ammonium (preferably a quaternary ammonium).
Les monomères cationiques sont préférentiellement choisis dans le groupe comprenant l’acrylate de diméthylaminoéthyle (AD AME) quatemisé ou salifié, le méthacrylate de diméthylaminoéthyle (MADAME) quatemisé ou salifié, le chlorure de diallyldiméthylammonium (DADMAC), le chlorure d’acrylamidopropyltriméthylammonium (APTAC), et le chlorure de méthacrylamidopropyltriméthylammonium (MAPTAC). The cationic monomers are preferably chosen from the group comprising quaternized or salified dimethylaminoethyl acrylate (AD AME), quaternized or salified dimethylaminoethyl methacrylate (MADAME), diallyldimethylammonium chloride (DADMAC), acrylamidopropyltrimethylammonium chloride (APTAC) , and methacrylamidopropyltrimethylammonium chloride (MAPTAC).
De manière avantageuse, les monomères cationiques du polymère PI ont comme contre-ion un halogénure, de préférence un ion chlorure. Advantageously, the cationic monomers of the polymer PI have as counterion a halide, preferably a chloride ion.
Les monomères zwitterioniques sont préférentiellement choisis dans le groupe comprenant les monomères sulfobétaïnes comme le sulfopropyl diméthylammonium éthylméthacrylate, le sulfopropyl diméthylammonium propylméthacrylamide, ou le sulfopropyl 2-vinylpyridinium ; les monomères phosphobétaïnes, comme le phosphato éthyltriméthylammonium éthylméthacrylate ; et les monomères carboxybétaïnes.
De préférence, le polymère hydrosoluble PI est un homopolymère ou un copolymère d’acrylamide ou de méthacrylamide. The zwitterionic monomers are preferably chosen from the group comprising sulfobetaine monomers such as sulfopropyl dimethylammonium ethyl methacrylate, sulfopropyl dimethylammonium propyl methacrylamide, or sulfopropyl 2-vinylpyridinium; phosphobetaine monomers, such as phosphato ethyltrimethylammonium ethyl methacrylate; and carboxybetaine monomers. Preferably, the water-soluble polymer PI is a homopolymer or a copolymer of acrylamide or of methacrylamide.
Le polymère PI peut être linéaire, structuré ou réticulé. Les agents réticulant permettant la structuration peuvent notamment être choisis parmi l’allyl sulfonate de sodium, le méthallyl sulfonate de sodium, le méthallyl disulfonate de sodium, le méthylènebisacrylamide, la triallylamine, le chlorure de triallylammonium. The PI polymer can be linear, structured or cross-linked. The crosslinking agents allowing the structuring can in particular be chosen from sodium allyl sulfonate, sodium methallyl sulfonate, sodium methallyl disulfonate, methylenebisacrylamide, triallylamine, triallylammonium chloride.
La structuration du polymère PI peut aussi être obtenue avec au moins un composé polyfonctionnel contenant au moins 3 hétéroatomes choisis parmi N, S, O, P et présentant chacun au moins un hydrogène mobile. Ce composé polyfonctionnel peut notamment être une polyéthylèneimine ou une polyamine. The structuring of the polymer PI can also be obtained with at least one polyfunctional compound containing at least 3 heteroatoms chosen from N, S, O, P and each having at least one mobile hydrogen. This polyfunctional compound can in particular be a polyethyleneimine or a polyamine.
La réaction Re est effectuée par ajout d’une émulsion inverse de polymère hydrosoluble PI dans la solution aqueuse Ml. Préférentiellement, l’émulsion inverse (émulsion eau dans huile) comprend : The reaction Re is carried out by adding an inverse emulsion of water-soluble polymer PI to the aqueous solution Ml. Preferably, the inverse emulsion (water-in-oil emulsion) comprises:
Une phase aqueuse comprenant au moins le polymère PI, An aqueous phase comprising at least the polymer PI,
Une phase huileuse, An oily phase,
Au moins un agent émulsifiant et au moins un agent d’inversion. At least one emulsifying agent and at least one reversing agent.
La phase huileuse peut être une huile minérale, une huile végétale, une huile synthétique ou un mélange de plusieurs de ces huiles. The oily phase can be a mineral oil, a vegetable oil, a synthetic oil or a mixture of several of these oils.
Des exemples d’huile minérale sont les huiles minérales contenant des hydrocarbures saturés de type aliphatique, naphténique, paraffinique, isoparaffinique, cycloparaffinique ou naphtyle.Examples of mineral oil are mineral oils containing saturated hydrocarbons of the aliphatic, naphthenic, paraffinic, isoparaffinic, cycloparaffinic or naphthyl type.
Des exemples d’huile synthétique sont le polydécène hydrogéné ou le polyisobutène hydrogéné, un ester tel que le stéarate d’octyle ou l’oléate de butyle. La gamme de produits Exxsol® d’Exxon convient parfaitement. Examples of synthetic oil are hydrogenated polydecene or hydrogenated polyisobutene, an ester such as octyl stearate or butyl oleate. Exxon's Exxsol® product line is a perfect fit.
En général, le rapport pondéral de la phase aqueuse à la phase huileuse dans l’émulsion inverse est de préférence de 50/50 à 90/10. Ce rapport inclut le poids des différents constituants de l’émulsion, notamment le polymère hydrosoluble PI. In general, the weight ratio of water phase to oil phase in the invert emulsion is preferably 50/50 to 90/10. This ratio includes the weight of the various constituents of the emulsion, in particular the water-soluble polymer PI.
L'émulsion eau dans huile comprend préférentiellement de 15 à 40% en poids d’huile, de 20 à 55% en poids d’eau, de 15 et 50 % en poids de polymère PI, les pourcentages étant exprimés par rapport au poids total de l’émulsion inverse du polymère PI.
Dans la présente invention, le terme "agent émulsifiant" désigne un agent capable d’émulsifier de l’eau dans une huile alors qu’un "agent inverseur" est un agent capable d’émulsionner une huile dans de l’eau. Plus précisément, on considère qu’un agent inverseur est un tensioactif ayant un HLB supérieur ou égal à 10, et qu’un agent émulsifiant est un tensioactif ayant un HLB strictement inférieur à 10. The water-in-oil emulsion preferably comprises from 15 to 40% by weight of oil, from 20 to 55% by weight of water, from 15 and 50% by weight of polymer PI, the percentages being expressed relative to the total weight of the inverse emulsion of the polymer PI. In the present invention, the term “emulsifying agent” designates an agent capable of emulsifying water in an oil whereas an “inverting agent” is an agent capable of emulsifying an oil in water. More specifically, it is considered that a reversing agent is a surfactant having an HLB greater than or equal to 10, and that an emulsifying agent is a surfactant having an HLB strictly less than 10.
L’équilibre hydrophile-lipophile (HLB) d’un composé chimique est une mesure de son degré d’hydrophilie ou lipophilie, déterminé en calculant les valeurs des différentes régions de la molécule, comme décrit par Griffin en 1949 (Griffin WC, Classification of Surface-Active Agents by HLB, Journal of the Society of Cosmetic Chemists, 1949, 1, pages 311-326). The hydrophilic-lipophilic balance (HLB) of a chemical compound is a measure of its degree of hydrophilicity or lipophilicity, determined by calculating the values of different regions of the molecule, as described by Griffin in 1949 (Griffin WC, Classification of Surface-Active Agents by HLB, Journal of the Society of Cosmetic Chemists, 1949, 1, pages 311-326).
Dans la présente invention, nous avons adopté le procédé de Griffin basé sur le calcul d’une valeur basée sur les groupes chimiques de la molécule. Griffin a attribué un nombre sans dimension compris entre 0 et 20 pour donner des informations sur la solubilité dans l’eau et dans l’huile. Les substances ayant une valeur HLB de 10 sont réparties entre les deux phases, de sorte que le groupe hydrophile (masse moléculaire Mh) se projette complètement dans l’eau tandis que le groupe hydrocarboné hydrophobe (masse moléculaire Mp) est adsorbé dans la phase non aqueuse. In the present invention, we have adopted Griffin's method based on calculating a value based on the chemical groups of the molecule. Griffin assigned a dimensionless number between 0 and 20 to give information about water and oil solubility. Substances with an HLB value of 10 are distributed between the two phases, so that the hydrophilic group (molecular mass Mh) projects completely into the water while the hydrophobic hydrocarbon group (molecular mass Mp) is adsorbed in the non-phase. watery.
La valeur HLB d’une substance de masse moléculaire totale M dont la partie hydrophile a une masse moléculaire Mh, est HLB = 20 (Mh / M). The HLB value of a substance with total molecular mass M whose hydrophilic part has molecular mass Mh, is HLB = 20 (Mh/M).
L’émulsion inverse contenant le polymère PI contient avantageusement de 0,1 % à 10 % en poids d’au moins un agent émulsifiant, les pourcentages étant exprimés en poids par rapport au poids de l’émulsion. Cet agent émulsifiant est avantageusement choisi parmi les esters de sorbitan, les esters de sorbitan polyéthoxylés, les acides gras polyéthoxylés, les alcools gras polyéthoxylés, les polyesters ayant un poids moléculaire moyen compris entre 1000 et 3000 daltons résultant de la condensation entre un acide poly(isobutényl) succinique ou son anhydride et un polyéthylène glycol, les copolymères blocs de poids moléculaire moyen compris entre 2500 et 3500 daltons résultant de la condensation entre l’acide hydroxystéarique et un polyéthylène glycol, les amines grasses éthoxylées, les dérivés des di- alcanol amides, les copolymères du méthacrylate de stéaryle, et les mélanges de ces agents émulsifiants.
L’émulsion inverse contenant le polymère PI contient avantageusement entre 0.1 et 10% en poids d’au moins un agent inverseur, les pourcentages étant exprimés en poids par rapport au poids de l’émulsion. Cet agent inverseur est avantageusement choisi parmi les nonylphénol éthoxylés, ayant de préférence 4 à 10 éthoxylations ; les alcools éthoxylés / propoxylés ayant de préférence une éthoxylation / propoxylation comprenant entre 12 et 25 atomes de carbone ; les alcools tridécyliques éthoxylés ; les acides gras polyéthoxylés ; les alcool gras poly (éthoxylés / propoxylés) ; les esters de sorbitan éthoxylés ; le laurate de sorbitan polyéthoxylé ; l’huile de castor polyéthoxylée ; l’alcool laurique heptaoxyéthylé ; le monostéarate de sorbitan polyéthoxylé ; les alkyls phénol polyéthoxylés cétyl éther ; les poly oxyde d’éthylène alkyl aryl éther ; le N-cétyl-N-éthyl morpholinium éthosulfate ; le lauryl sulfate de sodium ; les produits de condensation d’alcools gras avec l’oxyde d’éthylène ; les produits de condensation des alkylphenols et de l’oxyde d’éthylène ; les produits de condensation d’amines grasses avec 5 équivalents molaire ou plus d’oxyde d’éthylène ; les tristyryl phénol éthoxylés ; les condensais de l’oxyde d’éthylène avec les alcools polyhydriques partiellement estérifiés avec des chaînes grasses ainsi que leur formes anhydres ; les oxydes d’amine ; les alkyl polyglucosides ; le glucamide ; les esters de phosphate ; les acides alkylbenzène sulfonique et leurs sels ; les polymères hydrosolubles tensioactifs ; et les mélanges de plusieurs de ces agents inverseurs. The inverse emulsion containing the polymer PI advantageously contains from 0.1% to 10% by weight of at least one emulsifying agent, the percentages being expressed by weight relative to the weight of the emulsion. This emulsifying agent is advantageously chosen from sorbitan esters, polyethoxylated sorbitan esters, polyethoxylated fatty acids, polyethoxylated fatty alcohols, polyesters having an average molecular weight of between 1000 and 3000 daltons resulting from the condensation between a poly( isobutenyl) succinic or its anhydride and a polyethylene glycol, block copolymers with an average molecular weight of between 2500 and 3500 daltons resulting from the condensation between hydroxystearic acid and a polyethylene glycol, ethoxylated fatty amines, derivatives of di-alkanol amides , copolymers of stearyl methacrylate, and mixtures of these emulsifying agents. The inverse emulsion containing the polymer PI advantageously contains between 0.1 and 10% by weight of at least one inverting agent, the percentages being expressed by weight relative to the weight of the emulsion. This reversing agent is advantageously chosen from ethoxylated nonylphenols, preferably having 4 to 10 ethoxylations; ethoxylated/propoxylated alcohols preferably having an ethoxylation/propoxylation comprising between 12 and 25 carbon atoms; ethoxylated tridecyl alcohols; polyethoxylated fatty acids; poly(ethoxylated/propoxylated) fatty alcohols; ethoxylated sorbitan esters; polyethoxylated sorbitan laurate; polyethoxylated castor oil; heptaoxyethyl lauryl alcohol; polyethoxylated sorbitan monostearate; polyethoxylated alkyl phenol cetyl ether; poly ethylene oxide alkyl aryl ether; N-cetyl-N-ethyl morpholinium ethosulfate; sodium lauryl sulphate; condensation products of fatty alcohols with ethylene oxide; condensation products of alkylphenols and ethylene oxide; condensation products of fatty amines with 5 or more molar equivalents of ethylene oxide; ethoxylated tristyryl phenols; condensates of ethylene oxide with partially esterified polyhydric alcohols with fatty chains as well as their anhydrous forms; amine oxides; alkyl polyglucosides; glucamide; phosphate esters; alkylbenzene sulfonic acids and their salts; surfactant water-soluble polymers; and mixtures of several of these reversing agents.
L’émulsion eau dans huile selon l’invention peut être préparée selon tout procédé connu de l’homme du métier. Généralement, une solution aqueuse comprenant le ou les monomères et le ou les agents émulsifiants est émulsionnée dans une phase huileuse. Ensuite, la polymérisation est réalisée en ajoutant un initiateur de radicaux libres. On peut faire référence aux couples rédox, avec l’hydropéroxyde de cumène, le butylhydroxypéroxyde tertiaire ou les persulfates parmi les agents oxydants, le sulfite de sodium, le métabisulfite de sodium et le sel de Mohr parmi les agents réducteurs. Des composés azoïques tels que le chlorhydrate de 2,2’- azobis (isobutyronitrile) et de 2,2’-azobis (2-amidinopropane) peuvent également être utilisés.The water-in-oil emulsion according to the invention can be prepared according to any method known to those skilled in the art. Generally, an aqueous solution comprising the monomer(s) and the emulsifying agent(s) is emulsified in an oily phase. Then, the polymerization is carried out by adding a free radical initiator. We can refer to redox couples, with cumene hydroperoxide, tertiary butylhydroxyperoxide or persulfates among the oxidizing agents, sodium sulfite, sodium metabisulfite and Mohr's salt among the reducing agents. Azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-amidinopropane) hydrochloride can also be used.
Classiquement, la polymérisation est généralement effectuée de manière isotherme, adiabatique ou à température contrôlée. Ainsi, la température est avantageusement maintenue constante, généralement entre 10 et 60 °C (isotherme), ou bien on laisse la température augmenter naturellement (adiabatique) et dans ce cas, la réaction est généralement commencée à une température inférieure à 10 °C et la température finale est généralement
supérieure à 50 °C ou, enfin, l'augmentation de la température est contrôlée de manière à avoir une courbe de température entre la courbe isotherme et la courbe adiabatique. Conventionally, the polymerization is generally carried out in an isothermal, adiabatic or temperature-controlled manner. Thus, the temperature is advantageously kept constant, generally between 10 and 60°C (isothermal), or else the temperature is allowed to increase naturally (adiabatic) and in this case, the reaction is generally started at a temperature below 10°C and the final temperature is usually greater than 50°C or, finally, the increase in temperature is controlled so as to have a temperature curve between the isothermal curve and the adiabatic curve.
Généralement, le ou les agents inverseurs sont ajoutés à la fin de la réaction de polymérisation, de préférence à une température inférieure à 50 °C. Generally, the reversing agent(s) are added at the end of the polymerization reaction, preferably at a temperature below 50°C.
La réaction Re consiste consistant à ajouter l’émulsion inverse de polymère PI dans une solution aqueuse Ml de : (i) un hydroxyde d’alcalin et/ou un hydroxyde d’alcalino-terreux, (ii) un hypo-halogénure d’alcalin et/ou un hypo-halogénure d’alcalino-terreux, avec un temps de réaction Re de 10 secondes à 5 heures pour former le polymère P2. Reaction Re consists of adding the inverse polymer emulsion PI to an aqueous solution M1 of: (i) an alkaline hydroxide and/or an alkaline-earth hydroxide, (ii) an alkaline hypo-halide and/or an alkaline earth hypo-halide, with a reaction time Re of 10 seconds to 5 hours to form the polymer P2.
Avantageusement, la solution aqueuse Ml est une solution aqueuse de soude (hydroxyde de sodium) et d’hypochlorite de sodium. Advantageously, the aqueous solution M1 is an aqueous solution of soda (sodium hydroxide) and sodium hypochlorite.
Avantageusement, le temps de réaction du polymère PI dans la solution aqueuse Ml d’hypo- halogénure et d’hydroxyde est de 10 secondes à 180 minutes. Advantageously, the reaction time of the polymer PI in the aqueous solution M1 of hypohalide and hydroxide is from 10 seconds to 180 minutes.
La réaction Re est avantageusement réalisée à une température comprise entre 10 et 30 °C, plus avantageusement entre 15 et 25°C. The Re reaction is advantageously carried out at a temperature comprised between 10 and 30°C, more advantageously between 15 and 25°C.
Préférentiellement, pour la réaction Re, le coefficient Alpha = moles d’hypo-halogénure (alcalin et/ou alcalino-terreux) / moles de monomère(s) non ionique(s) (acrylamide, méthacrylamide, N,N-diméthylacrylamide, acrylonitrile ou leurs mélanges) du polymère PI est compris entre 0,1 et 1,0 et le coefficient Béta = moles d’hydroxyde (alcalin et/ou alcalino- terreux) / moles d’hypo-halogénure (alcalin et/ou alcalino-terreux) est compris entre 0,5 et 4,0. Preferably, for the Re reaction, the Alpha coefficient = moles of hypo-halide (alkaline and/or alkaline-earth) / moles of nonionic monomer(s) (acrylamide, methacrylamide, N,N-dimethylacrylamide, acrylonitrile or their mixtures) of the polymer PI is between 0.1 and 1.0 and the coefficient Beta = moles of hydroxide (alkaline and/or alkaline-earth) / moles of hypo-halide (alkaline and/or alkaline-earth ) is between 0.5 and 4.0.
Pour la réaction Re, préférentiellement entre 0,1 et 20% en poids de polymère PI, par rapport au poids de la solution aqueuse Ml, plus préférentiellement entre 0,3 et 10% et encore plus préférentiellement entre 0,5 et 3,0% en poids, sont ajoutés à la solution aqueuse Ml. For the reaction Re, preferably between 0.1 and 20% by weight of polymer PI, relative to the weight of the aqueous solution Ml, more preferably between 0.3 and 10% and even more preferably between 0.5 and 3.0 % by weight, are added to the aqueous solution M1.
Avantageusement, au terme de la réaction Re, et avant son injection dans la suspension fibreuse, le polymère P2 peut être fonctionnalisé avec un composé comprenant au moins une fonction aldéhyde pour donner un polymère P3, par exemple par addition d’un composé comprenant au moins une fonction aldéhyde. Préférentiellement, le composé comprenant au moins une fonction aldéhyde est le glyoxal.
Préférentiellement, avant injection dans la suspension fibreuse, le pH du mélange réactionnel issu de la réaction Re et contenant le polymère P2 peut être ajusté par ajout d’acide entre 0,5 et 7,5, plus préférentiellement entre 1,0 et 3,0. L’homme du métier sait ajuster le pH de ce type de milieu réactionnel. L’ajustement du pH est avantageusement réalisé en l’absence de formation du polymère P3. Advantageously, at the end of the Re reaction, and before its injection into the fibrous suspension, the polymer P2 can be functionalized with a compound comprising at least one aldehyde function to give a polymer P3, for example by adding a compound comprising at least an aldehyde function. Preferably, the compound comprising at least one aldehyde function is glyoxal. Preferably, before injection into the fibrous suspension, the pH of the reaction mixture resulting from the reaction Re and containing the polymer P2 can be adjusted by adding acid between 0.5 and 7.5, more preferably between 1.0 and 3, 0. A person skilled in the art knows how to adjust the pH of this type of reaction medium. The adjustment of the pH is advantageously carried out in the absence of formation of the polymer P3.
Selon un mode de réalisation préféré, le polymère P2 (ou P3) est introduit dans les eaux blanches et/ou la pâte épaisse et/ou le mélange formé par les eaux blanches et la pâte épaisse après homogénéisation de la suspension fibreuse dans la pompe de dilution (fan pump). According to a preferred embodiment, the polymer P2 (or P3) is introduced into the white waters and/or the thick paste and/or the mixture formed by the white waters and the thick paste after homogenization of the fibrous suspension in the pump of dilution (fan-pump).
Avantageusement, le polymère P2 (ou P3) peut aussi être introduit au sein du procédé papetier au niveau de la table de formation par exemple par pulvérisation ou application sous forme de mousse, ou encore au niveau de la size press (coucheuse) Advantageously, the polymer P2 (or P3) can also be introduced into the papermaking process at the level of the forming table, for example by spraying or application in the form of a foam, or even at the level of the size press (coater)
De manière avantageuse, entre 0,1 et 10 kg.t 1, et préférentiellement entre 0,2 et 5,0 kg.t 1 de polymère P2 (ou P3) sont ajoutés à la suspension fibreuse. Advantageously, between 0.1 and 10 kg.t 1 , and preferably between 0.2 and 5.0 kg.t 1 of polymer P2 (or P3) are added to the fibrous suspension.
La suspension fibreuse englobe rutilisation possible de différentes fibres cellulosiques : fibres vierges, fibres recyclées, pâte chimique, pâte mécanique, cellulose micro fibrillée ou cellulose nano fibrillée. La suspension fibreuse englobe également rutilisation de ces différentes fibres cellulosiques avec tous types de charges tel que le TiCh, le C'aCCÇ (broyée ou précipitée), le kaolin, les charges organiques et leurs mélanges. The fibrous suspension encompasses the possible use of different cellulosic fibers: virgin fibers, recycled fibers, chemical pulp, mechanical pulp, micro-fibrillated cellulose or nano-fibrillated cellulose. The fibrous suspension also encompasses the use of these different cellulosic fibers with all types of fillers such as TiCh, C aCCÇ (ground or precipitated), kaolin, organic fillers and mixtures thereof.
Le polymère P2 ou P3 peut être utilisé au sein du procédé papetier en combinaison avec d’autres produits tels que les coagulants minéraux ou organiques, les agents de résistance à sec, les agents de résistance humide, les polymères naturels tels que les amidons ou la carboxyméthylcellulose (CMC), les microparticules inorganiques telles que les microparticules de bentonite et les microparticules de silice colloïdale, les polymères organiques de toute nature ionique (non ionique, cationique, anionique, ou amphotère) et qui peuvent être (sans être limitatil) linéaires, branchés, réticulés, hydrophobes, ou associatifs.Polymer P2 or P3 can be used within the papermaking process in combination with other products such as inorganic or organic coagulants, dry strength agents, wet strength agents, natural polymers such as starches or carboxymethylcellulose (CMC), inorganic microparticles such as bentonite microparticles and colloidal silica microparticles, organic polymers of any ionic nature (nonionic, cationic, anionic, or amphoteric) and which may be (without being limiting) linear, branched, cross-linked, hydrophobic, or associative.
Les exemples suivants illustrent l’invention sans toutefois en limiter la portée.
Exemples de réalisation de l’invention The following examples illustrate the invention without however limiting its scope. Examples of embodiments of the invention
Procédures utilisées dans les essais applicatifs : al Types de pâtes utilisées Procedures used in the application tests: al Types of pastes used
Pâte de fibres recyclées : La pâte humide est obtenue par désintégration de pâte sèche afin d’obtenir une concentration aqueuse finale de 1 % en poids. Il s’agit d’une pâte à pH neutre composée à 100 % de fibres de cartons recyclées. bl Evaluation des performances d’égouttage (PDA! Recycled fiber pulp: Wet pulp is obtained by disintegrating dry pulp to obtain a final aqueous concentration of 1% by weight. It is a pH-neutral pulp made from 100% recycled cardboard fibres. bl Evaluation of drainage performance (PDA!
Le DDA (« Dynamic Drainage Analyzer ») permet de déterminer, de manière automatique, le temps (en secondes) nécessaire pour égoutter sous vide une suspension fibreuse déposée sur une toile. Les polymères sont ajoutés à la pâte humide (0,6 litre de pâte à 1,0 % en poids) dans le cylindre du DDA sous agitation à 1000 tours par minute : The DDA (“Dynamic Drainage Analyzer”) makes it possible to automatically determine the time (in seconds) required to drain under vacuum a fibrous suspension deposited on a cloth. The polymers are added to the wet paste (0.6 liters of paste at 1.0% by weight) in the cylinder of the DDA with stirring at 1000 revolutions per minute:
T=0 s : mise en agitation de la pâte T=20 s : Ajout du polymère T=0 s: stirring the paste T=20 s: Adding the polymer
T=30 s : arrêt de l’agitation et égouttage sous vide à 200 mbar (1 bar = 105 Pa) pendant 70 secondes. T=30 s: stirring stopped and draining under vacuum at 200 mbar (1 bar=10 5 Pa) for 70 seconds.
La pression sous la toile est enregistrée en fonction du temps. Lorsque toute l’eau est évacuée du matelas fibreux, l’air passe à travers celui-ci faisant apparaître une rupture de pente sur la courbe représentant la pression sous toile en fonction du temps. Le temps, exprimé en secondes, relevé à cette rupture de pente correspond au temps d’égouttage. Plus le temps est faible, meilleur est donc l’égouttage sous vide. c) Performances en application DSR (résistance à sec) grammage à 90 g m~2 The pressure under the canvas is recorded as a function of time. When all the water is evacuated from the fibrous mattress, the air passes through the latter causing a break in slope to appear on the curve representing the pressure under the canvas as a function of time. The time, expressed in seconds, recorded at this break in slope corresponds to the dripping time. The shorter the time, the better the vacuum drainage. c) Performance in DSR application (dry strength) grammage at 90 gm ~2
La quantité nécessaire de pâte est prélevée de manière à obtenir une feuille présentant un grammage de 90 g.m2. The necessary quantity of paste is removed so as to obtain a sheet having a basis weight of 90 gm 2 .
La pâte humide est introduite dans le cuvier de la formette dynamique et est maintenue sous agitation. On injecte à cette pâte les différents composants du système selon la séquence prédéfinie. On respecte généralement un temps de contact de 30 à 45 secondes entre chaque ajout de polymère.
Des formettes de papier sont réalisées avec une formette dynamique automatique : un buvard et la toile de formation sont placés dans le bol de la formette dynamique avant de démarrer la rotation du bol à 1000 tr.min 1 et de construire le mur d’eau. La pâte traitée est répartie sur le mur d’eau pour former le matelas fibreux sur la toile de formation. The wet paste is introduced into the vat of the dynamic molder and is kept under agitation. The different components of the system are injected into this paste according to the predefined sequence. A contact time of 30 to 45 seconds is generally respected between each addition of polymer. Formettes of paper are produced with an automatic dynamic former: a blotter and the forming fabric are placed in the bowl of the dynamic former before starting the rotation of the bowl at 1000 rpm and building the water wall. The treated pulp is spread over the water wall to form the fibrous mat on the forming fabric.
Une fois que l’eau est drainée, le matelas fibreux est récupéré, pressé sous une presse délivrant 4 bar, puis séché à 117°C. La feuille obtenue est conditionnée 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 mesurées. Once the water is drained, the fibrous mat is recovered, pressed under a press delivering 4 bar, then dried at 117°C. The sheet obtained is conditioned 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 measured.
L’éclatement (Burst Index) est mesuré avec un éclatomètre Messmer Buchel M 405 selon la norme TAPPI T403 om-02. Le résultat est exprimé en kPa ou en pourcentage par rapport à une référence. On détermine l’indice d’éclatement, exprimé en kPa.m2/g, en divisant cette valeur par le grammage de la feuille testée. The burst (Burst Index) is measured with a Messmer Buchel M 405 burst tester according to the TAPPI T403 om-02 standard. The result is expressed in kPa or in percentage compared to a reference. The bursting index, expressed in kPa.m 2 /g, is determined by dividing this value by the basis weight of the sheet tested.
La longueur de rupture à l’état sec est mesurée dans le sens machine (DBL SM) et dans le sens travers (DBL ST) avec un appareil de traction Testometric AX selon la norme TAPPI T494 om-01. Le résultat est exprimé en km ou en pourcentage par rapport à une référence. The dry breaking length is measured in the machine direction (DBL SM) and in the transverse direction (DBL ST) with a Testometric AX tensile device according to TAPPI T494 om-01. The result is expressed in km or in percentage compared to a reference.
Produits testés dans les essais applicatifs : Products tested in application trials:
Polymères PI Synthèse Polymère Pl-A Polymers PI Synthesis Polymer Pl-A
Dans un réacteur de 1 litre équipé d’un agitateur mécanique, d’un thermomètre, d’un réfrigérant et d’une canne plongeante d’azote gazeux, on introduit 310 g d’eau. Le pH du milieu réactionnel est ajusté à 3,3 à l’aide d’un tampon pH (NaOH 30 % en poids dans l’eau et H3PO475 % en poids dans l’eau). Le milieu est chauffé et maintenu à température comprise entre 79 et 81°C grâce à un bain-marie. Grâce à deux coulées continues, on incorpore (coulée 1) 400 g d’acrylamide à 50%, 237,8 g d’eau et 2,40 g d’hypophosphite de sodium à 100 % pendant 180 minutes. Coulée 2, 0,48 g de sodium persulfate à 100 % et 48 g d’eau pendant 180 minutes. La solution de polymère est maintenue à 80°C pendant 120 minutes après la fin de la coulée.
La solution de polymère Pl-A obtenue présente un pH de 5,7, une concentration en poids de polymère Pl-A de 20 % et une viscosité de 6000 cps. 310 g of water are introduced into a 1 liter reactor equipped with a mechanical stirrer, a thermometer, a condenser and a gaseous nitrogen plunger. The pH of the reaction medium is adjusted to 3.3 using a pH buffer (NaOH 30% by weight in water and H 3 PO 4 75% by weight in water). The medium is heated and maintained at a temperature of between 79 and 81° C. using a water bath. By means of two continuous castings, 400 g of 50% acrylamide, 237.8 g of water and 2.40 g of 100% sodium hypophosphite are incorporated (cast 1) for 180 minutes. Pour 2, 0.48 g of 100% sodium persulfate and 48 g of water for 180 minutes. The polymer solution is maintained at 80° C. for 120 minutes after the end of the casting. The solution of polymer P1-A obtained has a pH of 5.7, a concentration by weight of polymer P1-A of 20% and a viscosity of 6000 cps.
Polymère Pl-B : Homopolymère d’acrylamide sous forme d’émulsion inverse commercialisé par SNF sous l’appellation : Flopam™EM 230. Pl-B polymer: Acrylamide homopolymer in the form of an inverse emulsion marketed by SNF under the name: Flopam™EM 230.
Les polymères Pl-A (en solution aqueuse) et Pl-B (émulsion inverse) sont des homopolymères d’acrylamide qui se distinguent uniquement par leur forme physique. Polymers Pl-A (in aqueous solution) and Pl-B (invert emulsion) are acrylamide homopolymers which are distinguished only by their physical form.
Polymères P2 P2 polymers
Synthèse polymère P2-A P2-A polymer synthesis
Préparation d’une solution de Pl-A à 10 % en poids dans l’eau, en diluant 20 g d’une solution de Pl-A à 20 % en poids dans l’eau avec 20 g d’eau. La solution de polymère est chauffée à 50°C. Preparation of a 10% by weight solution of Pl-A in water, by diluting 20 g of a 20% by weight solution of Pl-A in water with 20 g of water. The polymer solution is heated to 50°C.
Une solution aqueuse d’hypochlorite de sodium 14,29 g (NaOCl) à 14,6 % (en poids dans l’eau) et de 7,5 g de soude à 30 % (en poids dans l’eau) est préparée en fonction des coefficients alpha (0,5) et beta (2,0) pour la réaction Re. Lorsque la solution de polymère Pl- A est à 50°C, la solution aqueuse d’hypochlorite de sodium et de soude est ajoutée sur Pl-A. Après 30 secondes de réaction, 138,20 g d’eau est additionné. On obtient une solution de polymère P2-A à une concentration de 2 % en poids. An aqueous solution of sodium hypochlorite 14.29 g (NaOCl) at 14.6% (by weight in water) and 7.5 g of sodium hydroxide at 30% (by weight in water) is prepared by function of the alpha (0.5) and beta (2.0) coefficients for the Re reaction. When the Pl-A polymer solution is at 50°C, the aqueous solution of sodium hypochlorite and sodium hydroxide is added to Pl -HAS. After 30 seconds of reaction, 138.20 g of water is added. A solution of polymer P2-A is obtained at a concentration of 2% by weight.
Synthèse Polymère P2-B Synthesis Polymer P2-B
Une solution aqueuse Ml de 3,66 g d’hypochlorite de sodium (NaOCl) à 14,6 % (en poids dans l’eau) et de 1,92 g de soude à 30 % (en poids dans l’eau) est préparée en fonction des coefficients alpha (0,5) et beta (2,0) pour la réaction Re. 93,60 g d’eau sont ensuite ajoutés. An aqueous solution M1 of 3.66 g of sodium hypochlorite (NaOCl) at 14.6% (by weight in water) and 1.92 g of sodium hydroxide at 30% (by weight in water) is prepared according to the coefficients alpha (0.5) and beta (2.0) for the Re reaction. 93.60 g of water are then added.
3,20 g de polymère Pl-B (en émulsion inverse) est ajouté dans la solution aqueuse Ml à température ambiante et sous agitation. Le polymère est agité pendant 60 minutes dans la solution Ml. On obtient une solution de polymère P2-B, de concentration finale en poids de polymère égale à 1 %.
Essais applicatifs 3.20 g of polymer P1-B (in inverse emulsion) is added to the aqueous solution M1 at room temperature and with stirring. The polymer is stirred for 60 minutes in solution M1. A solution of polymer P2-B is obtained, with a final concentration by weight of polymer equal to 1%. Application tests
Performances d’égouttage (PDA)
Drip performance (PDA)
Tableau 1 : Egouttage en fonction du polymère. On observe une amélioration de l’égouttage avec Tutilisation du polymère P2-B par rapport au polymère P2-A. Table 1: Drainage according to the polymer. An improvement in drainage is observed with the use of polymer P2-B compared to polymer P2-A.
Performances en application DSR (résistance à sec)
Performance in DSR application (dry strength)
Tableau 2 : Résistance à sec en fonction du polymère. Les performances en Burst (éclatement) sont améliorées par Tutilisation du polymère P2-B. La même tendance est observée pour la mesure de longueur de rupture dans le sens marche (DBL SM) et dans le sens travers (DBL ST).
Table 2: Dry strength depending on the polymer. Burst performance is improved by using the P2-B polymer. The same trend is observed for the breaking length measurement in the forward direction (DBL SM) and in the cross direction (DBL ST).
Claims
1. Procédé de fabrication d’une feuille de papier ou de carton à partir d’une suspension fibreuse, comprenant les étapes suivantes : a) injection d’un polymère P2 dans une suspension fibreuse, b) formation d’une feuille de papier ou de carton, c) séchage de la feuille de papier ou de carton, le polymère P2 étant préparé, préalablement à l’étape a), à partir d’un polymère hydrosoluble PI sous forme d’émulsion inverse, PI étant un polymère hydrosoluble d’au moins un monomère non ionique choisi parmi l’acrylamide, le méthacrylamide, le N,N- diméthylacrylamide, et l’acrylonitrile, le polymère P2 étant obtenu par une réaction Re consistant à ajouter le polymère hydrosoluble PI sous forme d’émulsion inverse dans une solution aqueuse Ml de : (i) un hydroxyde de métal alcalin, ou un hydroxyde de métal alcalino-terreux, ou leurs mélanges (ii) un hypo-halogénure de métal alcalin, ou un hypo-halogénure de métal alcalino-terreux, ou leurs mélanges, la réaction Re ayant un temps de réactions de 10 secondes à 5 heures après l’ajout du polymère hydrosoluble PI sous forme d’émulsion inverse. 1. Process for manufacturing a sheet of paper or cardboard from a fibrous suspension, comprising the following steps: a) injecting a polymer P2 into a fibrous suspension, b) forming a sheet of paper or cardboard, c) drying the sheet of paper or cardboard, the polymer P2 being prepared, prior to step a), from a water-soluble polymer PI in the form of an inverse emulsion, PI being a water-soluble polymer d at least one nonionic monomer chosen from acrylamide, methacrylamide, N,N-dimethylacrylamide, and acrylonitrile, the polymer P2 being obtained by a Re reaction consisting in adding the water-soluble polymer PI in the form of an inverse emulsion in an aqueous solution M1 of: (i) an alkali metal hydroxide, or an alkaline-earth metal hydroxide, or mixtures thereof (ii) an alkali metal hypo-halide, or an alkaline-earth metal hypo-halide, or their mixtures, the Re reaction having a reaction time of 10 seconds to 5 hours after the addition of the water-soluble polymer PI in the form of an inverse emulsion.
2. Procédé selon la revendication 1, caractérisé en ce que le polymère PI contient au moins 50 mol% d’au moins un monomère non ionique choisi parmi l’acrylamide, le méthacrylamide, le N,N-diméthylacrylamide, et l’acrylonitrile. 2. Method according to claim 1, characterized in that the polymer PI contains at least 50 mol% of at least one nonionic monomer chosen from acrylamide, methacrylamide, N,N-dimethylacrylamide, and acrylonitrile.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le polymère PI est un homopolymère ou un copolymère d’acrylamide ou de méthacrylamide. 3. Method according to claim 1 or 2, characterized in that the polymer PI is a homopolymer or a copolymer of acrylamide or methacrylamide.
4. Procédé selon les revendications 1 à 3, caractérisé en ce que l’émulsion inverse comprend : 4. Process according to claims 1 to 3, characterized in that the inverse emulsion comprises:
Une phase aqueuse comprenant au moins le polymère PI, An aqueous phase comprising at least the polymer PI,
Une phase huileuse, An oily phase,
Au moins un agent émulsifiant et au moins un agent d’inversion. At least one emulsifying agent and at least one reversing agent.
5. Procédé selon la revendication précédente, caractérisé en ce que l’émulsion inverse du polymère PI comprend de 15 à 40% en poids d’huile, de 20 à 55% en poids d’eau, de 15 et 50% en poids de polymère, les pourcentages étant exprimés par rapport au poids total de l’émulsion inverse du polymère PI.
5. Method according to the preceding claim, characterized in that the inverse emulsion of the polymer PI comprises from 15 to 40% by weight of oil, from 20 to 55% by weight of water, from 15 and 50% by weight of polymer, the percentages being expressed relative to the total weight of the inverse emulsion of the polymer PI.
6. Procédé selon l’une des revendications 1 à 5, caractérisé en ce que, pour la réaction Re, le coefficient Alpha = moles d’hypo-halogénure / moles de monomère non ionique du polymère hydrosoluble PI est compris entre 0,1 et 1,0 et le coefficient Béta = moles d’hydroxyde / moles d’hypo-halogénure est compris entre 0,5 et 4,0. 6. Method according to one of claims 1 to 5, characterized in that, for the reaction Re, the coefficient Alpha = moles of hypo-halide / moles of nonionic monomer of the water-soluble polymer PI is between 0.1 and 1.0 and the coefficient Beta = moles of hydroxide / moles of hypo-halide is between 0.5 and 4.0.
7. Procédé selon l’une des revendication 1 à 6, caractérisé en ce qu’entre 0,1 et 20 % en poids de polymère PI, par rapport au poids de la solution aqueuse Ml, sont ajoutés à la solution aqueuse Ml. 7. Method according to one of claims 1 to 6, characterized in that between 0.1 and 20% by weight of polymer PI, relative to the weight of the aqueous solution Ml, are added to the aqueous solution Ml.
8. Procédé selon l’une des revendication 1 à 7, caractérisé en ce qu’au terme de la réaction Re, et avant injection dans la suspension fibreuse, le polymère P2 est fonctionnalisé avec un composé comprenant au moins une fonction aldéhyde pour donner un polymère P3. 8. Method according to one of claims 1 to 7, characterized in that at the end of the Re reaction, and before injection into the fibrous suspension, the polymer P2 is functionalized with a compound comprising at least one aldehyde function to give a polymer P3.
9. Procédé selon la revendication 8, caractérisé en ce que le composé comprenant au moins une fonction aldéhyde est le glyoxal. 9. Method according to claim 8, characterized in that the compound comprising at least one aldehyde function is glyoxal.
10. Procédé selon l’une des revendication 1 à 7, caractérisé en ce qu’avant injection dans la suspension fibreuse, le pH du mélange réactionnel issu de la réaction Re et contenant le polymère P2 est ajusté par ajout d’acide entre 0,5 et 7,5. 10. Method according to one of claims 1 to 7, characterized in that before injection into the fibrous suspension, the pH of the reaction mixture resulting from the reaction Re and containing the polymer P2 is adjusted by adding acid between 0, 5 and 7.5.
11. Procédé selon l’une des revendications 1 à 10, caractérisé en ce que le polymère P2 ou P3 est introduit dans les eaux blanches et/ou dans la pâte épaisse et/ou dans le mélange formé par les eaux blanches et la pâte épaisse après homogénéisation de la suspension fibreuse dans la pompe de dilution. 11. Method according to one of claims 1 to 10, characterized in that the polymer P2 or P3 is introduced into the white waters and/or into the thick paste and/or into the mixture formed by the white waters and the thick paste after homogenization of the fibrous suspension in the dilution pump.
12. Procédé selon l’une des revendications 1 à 11, caractérisé en ce que l’étape a) est réalisée dans un délai n’excédant pas 24 heures à compter de l’ajout du polymère hydrosoluble PI sous forme d’émulsion inverse dans la solution aqueuse Ml. 12. Method according to one of claims 1 to 11, characterized in that step a) is carried out within a period not exceeding 24 hours from the addition of the water-soluble polymer PI in the form of an inverse emulsion in the aqueous solution M1.
13. Procédé selon l’une des revendications 1 à 12, caractérisé en ce que la solution aqueuse Ml est une solution aqueuse d’hydroxyde de sodium et d’hypochlorite de sodium. 13. Method according to one of claims 1 to 12, characterized in that the aqueous solution M1 is an aqueous solution of sodium hydroxide and sodium hypochlorite.
14. Procédé selon l’une des revendications 1 à 13, caractérisé en ce que la réaction Re est réalisée à une température comprise entre 10 et 30 °C, avantageusement entre 15 et 25°C.
14. Process according to one of Claims 1 to 13, characterized in that the Re reaction is carried out at a temperature of between 10 and 30°C, advantageously between 15 and 25°C.
15. Procédé selon l’une des revendications 1 à 14, caractérisé en ce qu’entre 0,3 et 10 % en poids de polymère PI, par rapport au poids de la solution aqueuse Ml, sont ajoutés à la solution aqueuse Ml.
15. Method according to one of claims 1 to 14, characterized in that between 0.3 and 10% by weight of polymer PI, relative to the weight of the aqueous solution Ml, are added to the aqueous solution Ml.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2103912A FR3121942A1 (en) | 2021-04-15 | 2021-04-15 | PAPER AND CARDBOARD MANUFACTURING PROCESS |
| PCT/EP2022/059954 WO2022219086A1 (en) | 2021-04-15 | 2022-04-13 | Method for manufacturing paper and cardboard |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4323586A1 true EP4323586A1 (en) | 2024-02-21 |
Family
ID=76034834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP22723053.9A Pending EP4323586A1 (en) | 2021-04-15 | 2022-04-13 | Method for manufacturing paper and cardboard |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP4323586A1 (en) |
| CN (1) | CN117203392A (en) |
| AU (1) | AU2022256771A1 (en) |
| BR (1) | BR112023021202A2 (en) |
| FR (1) | FR3121942A1 (en) |
| WO (1) | WO2022219086A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002212898A (en) * | 2000-11-13 | 2002-07-31 | Hymo Corp | Method for freeness improvement |
| FR2880901B1 (en) * | 2005-01-17 | 2008-06-20 | Snf Sas Soc Par Actions Simpli | METHOD FOR MANUFACTURING PAPER AND CARDBOARD OF HIGH RESISTANCE BY DRY AND PAPERS AND CARTONS THUS OBTAINED |
| JP2009150009A (en) * | 2007-12-20 | 2009-07-09 | Hymo Corp | Internal additive for papermaking and method for using the same |
| FR3009830B1 (en) * | 2013-08-22 | 2015-08-14 | Snf Sas | NOVEL WATER-SOLUBLE POLYMER COMPLEXES AND USES THEREOF |
| FR3088068B1 (en) * | 2018-11-06 | 2020-11-06 | S N F Sa | AUTO INVERSIBLE REVERSE POLYMERIC EMULSION |
| FR3096985B1 (en) * | 2019-06-05 | 2021-05-14 | S N F Sa | PROCESS FOR PREPARING STRUCTURED POLYMERS IN THE FORM OF POWDER BY GEL ROUTING |
-
2021
- 2021-04-15 FR FR2103912A patent/FR3121942A1/en active Pending
-
2022
- 2022-04-13 CN CN202280028578.0A patent/CN117203392A/en active Pending
- 2022-04-13 AU AU2022256771A patent/AU2022256771A1/en active Pending
- 2022-04-13 WO PCT/EP2022/059954 patent/WO2022219086A1/en active Application Filing
- 2022-04-13 BR BR112023021202A patent/BR112023021202A2/en unknown
- 2022-04-13 EP EP22723053.9A patent/EP4323586A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN117203392A (en) | 2023-12-08 |
| AU2022256771A1 (en) | 2023-10-26 |
| WO2022219086A1 (en) | 2022-10-20 |
| BR112023021202A2 (en) | 2023-12-19 |
| FR3121942A1 (en) | 2022-10-21 |
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