EP4259671A1 - Copolymer having viscoelastic and suspensive properties - Google Patents
Copolymer having viscoelastic and suspensive propertiesInfo
- Publication number
- EP4259671A1 EP4259671A1 EP21835343.1A EP21835343A EP4259671A1 EP 4259671 A1 EP4259671 A1 EP 4259671A1 EP 21835343 A EP21835343 A EP 21835343A EP 4259671 A1 EP4259671 A1 EP 4259671A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acrylate
- copolymer
- methacrylate
- monomer
- compound
- 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
- 229920001577 copolymer Polymers 0.000 title claims abstract description 84
- 239000000203 mixture Substances 0.000 claims abstract description 93
- 239000000178 monomer Substances 0.000 claims abstract description 63
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 72
- 229940048053 acrylate Drugs 0.000 claims description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 47
- -1 n- butyl Chemical group 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 230000009477 glass transition Effects 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000002966 varnish Substances 0.000 claims description 9
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 6
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- DOEXKUOGPAEBAD-UHFFFAOYSA-N ethyl n-(2-methylprop-2-enoyl)carbamate Chemical compound CCOC(=O)NC(=O)C(C)=C DOEXKUOGPAEBAD-UHFFFAOYSA-N 0.000 claims description 6
- IPZIVCLZBFDXTA-UHFFFAOYSA-N ethyl n-prop-2-enoylcarbamate Chemical compound CCOC(=O)NC(=O)C=C IPZIVCLZBFDXTA-UHFFFAOYSA-N 0.000 claims description 6
- 125000005394 methallyl group Chemical group 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004816 latex Substances 0.000 claims description 4
- 229920000126 latex Polymers 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- JHSWSKVODYPNDV-UHFFFAOYSA-N 2,2-bis(prop-2-enoxymethyl)propane-1,3-diol Chemical compound C=CCOCC(CO)(CO)COCC=C JHSWSKVODYPNDV-UHFFFAOYSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 claims description 3
- VVYDVQWJZWRVPE-UHFFFAOYSA-L dimethyltin(2+);diiodide Chemical compound C[Sn](C)(I)I VVYDVQWJZWRVPE-UHFFFAOYSA-L 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- BKZFVHIMLVBUGP-UHFFFAOYSA-N (2-prop-2-enoyloxyphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1OC(=O)C=C BKZFVHIMLVBUGP-UHFFFAOYSA-N 0.000 claims description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 claims description 2
- KTRQRAQRHBLCSQ-UHFFFAOYSA-N 1,2,4-tris(ethenyl)cyclohexane Chemical compound C=CC1CCC(C=C)C(C=C)C1 KTRQRAQRHBLCSQ-UHFFFAOYSA-N 0.000 claims description 2
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 claims description 2
- HSOOIVBINKDISP-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CCC)OC(=O)C(C)=C HSOOIVBINKDISP-UHFFFAOYSA-N 0.000 claims description 2
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 claims description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 2
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003337 fertilizer Substances 0.000 claims description 2
- 125000003827 glycol group Chemical group 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- UBTYFVJZTZYJHZ-UHFFFAOYSA-N n-[2-(prop-2-enoylamino)propyl]prop-2-enamide Chemical compound C=CC(=O)NC(C)CNC(=O)C=C UBTYFVJZTZYJHZ-UHFFFAOYSA-N 0.000 claims description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 2
- 150000003021 phthalic acid derivatives Chemical class 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- OCAAZRFBJBEVPS-UHFFFAOYSA-N prop-2-enyl carbamate Chemical compound NC(=O)OCC=C OCAAZRFBJBEVPS-UHFFFAOYSA-N 0.000 claims description 2
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 1
- 235000019256 formaldehyde Nutrition 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 15
- 229920006243 acrylic copolymer Polymers 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229940059574 pentaerithrityl Drugs 0.000 description 6
- 238000000518 rheometry Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- XIPXCVZIOAPJIN-UHFFFAOYSA-N 79638-11-2 Chemical compound C12C=CCC2C2CC(OCCOC(=O)C=C)C1C2 XIPXCVZIOAPJIN-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- TYMYJUHDFROXOO-UHFFFAOYSA-N 1,3-bis(prop-2-enoxy)-2,2-bis(prop-2-enoxymethyl)propane Chemical compound C=CCOCC(COCC=C)(COCC=C)COCC=C TYMYJUHDFROXOO-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- BDKDHWOPFRTWPP-UHFFFAOYSA-N 2,2-bis(prop-2-enoxymethyl)butan-1-ol Chemical compound C=CCOCC(CO)(CC)COCC=C BDKDHWOPFRTWPP-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-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
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- YXCDZXGJZDGMEP-UHFFFAOYSA-N 4-hydroxy-3,3-bis(hydroxymethyl)butan-2-one Chemical compound CC(=O)C(CO)(CO)CO YXCDZXGJZDGMEP-UHFFFAOYSA-N 0.000 description 1
- ZHUWXKIPGGZNJW-UHFFFAOYSA-N 6-methylheptyl 3-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)CCS ZHUWXKIPGGZNJW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- WDUYWZBDUMTSAH-UHFFFAOYSA-N dodecyl dodecanoate;sodium Chemical compound [Na].CCCCCCCCCCCCOC(=O)CCCCCCCCCCC WDUYWZBDUMTSAH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KUQWZSZYIQGTHT-UHFFFAOYSA-N hexa-1,5-diene-3,4-diol Chemical compound C=CC(O)C(O)C=C KUQWZSZYIQGTHT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 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
- 230000010363 phase shift Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000003938 response to stress Effects 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 230000002441 reversible effect Effects 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
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000004296 sodium metabisulphite Substances 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8188—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bonds, and at least one being terminated by a bond to sulfur or by a hertocyclic ring containing sulfur; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q3/00—Manicure or pedicure preparations
- A61Q3/02—Nail coatings
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0062—Cross-linked polymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0065—Polymers characterised by their glass transition temperature (Tg)
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
Definitions
- the invention provides an acrylic copolymer P, sulfonated, crosslinked and prepared from at least four monomers and in the absence of methacrylic acid.
- the invention also comprises the preparation of an aqueous, viscoelastic and suspensive composition comprising this copolymer P.
- agents associating several properties.
- certain technical fields require controlling the rheology as well as the texture of a composition.
- the agents used for this purpose must also make it possible to stabilize these compositions.
- the agents used In the field of coating compositions, in particular for stain compositions, the agents used must make it possible to control the rheology but also to confer a suspensive effect on these compositions which comprise particles.
- Stain compositions usually combine a solvent, especially water, with a binder, for example an acrylic binder, an alkyd binder or an alkyd-urethane binder, and pigment particles. These compositions make it possible to protect the substrate on which they are applied, in particular a wooden or concrete substrate. The compatibility of the different constituents of a composition is therefore also essential.
- the rheology and texture control agents of a composition must have a glass transition temperature which allows them to be combined effectively with other substances present in these compositions, in particular with a binder, generally in the form of particles.
- the suspensive effect sought for a composition is the ability to maintain particles in suspension in a continuous phase, in a stable manner over time, for example during storage of the composition.
- Particles are generally solid, solid or hollow bodies. They can also be liquid entities immiscible with the continuous phase or be encapsulated or in gaseous form. Their shape, texture and structure can vary widely, in particular depending on the final properties expected.
- the suspensive performance can be evaluated by determining the value of the modulus of elasticity G', the value of the damping factor (Tan ô) and the value of the elastic resistance.
- compositions both for low or medium shear gradients and for high shear gradients.
- a composition can be subjected to numerous stresses requiring particularly complex rheological properties, in particular viscoelastic properties.
- the behavior of a linear viscoelastic material is intermediate between that of an ideal elastic solid symbolized by a spring of modulus E (or G) and that of a Newtonian viscous liquid symbolized by a viscosity damping factor.
- the elasticity of a material reflects its ability to retain and release energy after deformation.
- the viscosity of a material reflects its ability to dissipate energy.
- the viscoelasticity of a composition must therefore also be improved so that this composition exhibits both viscous and elastic characteristics when it undergoes deformation.
- the viscous component allows this composition to resist shear flow and exhibit a deformation that increases linearly with time when stress is applied.
- the elastic component allows a deformation when a stress is applied, then the return to the original state once the stress is interrupted.
- methacrylic acid in particular methacrylic acid prepared from acetone cyanohydrin which is a highly toxic compound, should be limited as much as possible.
- Documents US2017003717 and US20190315897 describe copolymers prepared with methacrylic acid.
- Document US20080193405 describes the preparation of hydraulic or alcoholic compositions comprising a combination of copolymers combined with a mixture of acrylic acid and a crosslinking compound.
- Document WO2014185381 relates to a binder composition for a lithium battery and which comprises a fluorinated copolymer.
- the invention provides a copolymer P prepared in the absence of methacrylic acid, by at least one polymerization reaction: has. at least one anionic monomer (a) chosen from acrylic acid, a salt of acrylic acid, oligomers of acrylic acid, salts of oligomers of acrylic acid and combinations thereof; b. at least one nonionic monomer (b) chosen from styrene, C 1 -C 8 esters of an acid chosen from acrylic acid, methacrylic acid and combinations thereof; vs.
- the copolymer P can be prepared from only compounds a, b, c and d.
- the monomer (a) is acrylic acid or a mixture of oligomers of acrylic acid of formula (I): in which m is an integer or decimal number ranging from 1 to 10, preferably ranging from 2 to 4. More preferably according to the invention, the monomer (a) is acrylic acid.
- the monomer (b) is chosen from:
- Ci-Cs-alkyl acrylate in particular Ci-Cs-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n- butyl, alkyl methacrylate, in particular Ci-Cs-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, n- butyl, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxy ethyl acryl ate,
- aryl methacrylate preferably phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate and
- the monomer (b) is chosen from ethyl acrylate and butyl acrylate, more preferably ethyl acrylate.
- the monomer (b) according to the invention is a non-fluorinated monomer or else the monomer (b) is different from 2,2,2-trifluoroethyl methacrylate.
- the preferred monomer (c) is chosen from 2-acrylamido-2-methylpropane sulphonic acid (AMPS) and its sodium or ammonium salts.
- the preferred compound (d) is chosen from polyunsaturated aromatic monomers such as divinylbenzene, divinyl naphthalene and trivinylbenzene, polyunsaturated alicyclic monomers, for example 1, 2, 4-trivinyl cyclohexane, difunctional phthalic acid esters such as diallyl phthalate , polyalkenyl ethers such as triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose and trimethylolpropane diallyl ether, polyunsaturated esters of polyalcohols or polyacids such as 1,6-hexanediol di(meth)acrylate, tetramethylene tri(meth)acrylate, allyl acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, trimethylolpropane tri(meth)acryl
- the dissymmetrical crosslinking compound (d) preferred according to the invention is chosen from:
- - L 1 represents CHz, monoalkoxylated CHz or polyalkoxylated CHz
- -C(CH 3 ) CH 2
- -C(H) C(H)C(O)OH
- - Q 1 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
- - Q 2 represents CH 2 , CH 2 -CH 2 , monoalkoxylated CH 2 , monoalkoxylated CH 2 -CH 2 , polyalkoxylated CH 2 or polyalkoxylated CH 2 -CH 2 ; preferably a compound of formula (II) in which:
- L 1 represents monoalkoxylated CH 2 or polyalkoxylated CH 2 ,
- - Q 1 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
- - Q 2 represents CH 2 , CH 2 -CH 2 , monoalkoxylated CH 2 , monoalkoxylated CH 2 -CH 2 , polyalkoxylated CH 2 or polyalkoxylated CH 2 -CH 2 ;
- L 2 represents CH 2 , monoalkoxylated CH 2 or polyalkoxylated CH 2 ,
- - Q 3 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
- - Q 4 represents CH2, CH2-CH2, monoalkoxylated CH2, monoalkoxylated CH2-CH2, polyalkoxylated CH2 or polyalkoxylated CH2-CH2; preferably a compound of formula (III) in which:
- - L 2 represents monoalkoxylated CH2 or polyalkoxylated CH2,
- Q 3 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
- - Q 4 represents CH2, CH2-CH2, monoalkoxylated CH2, monoalkoxylated CH2-CH2, polyalkoxylated CH2 or polyalkoxylated CH2-CH2;
- R 3 independently represents H or CH 3 ,
- - L 3 independently represents a linear or branched Ci-C2o-alkylene group
- - n independently represents 0 or an integer ranging from 1 to 30, for example from 1 to 20, in particular from 1 to 15, in particular from 1 to 10;
- di(meth)acrylates such as polyalkylene glycol di(meth)acrylate, in particular polypropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, di(meth)acrylate polyethylene glycol, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-butylene glycol di(meth)acrylate, 1,6-butylene glycol di(meth)acrylate, ,6-hexanediol, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, but also 2,2'-bis(4-(acryloxypropyloxy)-phenyl)propane, 2 ,2'-bis(4-(acryloxydiethoxy)-phenyl)propane; tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate
- TMPTA trimethylolpropane tri(meth)acrylate
- TMPTA 3OE ethoxylated trimethylolpropane tri(meth)acrylate
- EGDCPEA ethylene glycol dicyclopentenyl ether acrylate
- TMPTA EGDCPEA and TMPTA 3OE
- - R 4 independently represents H or CEE
- the amounts of the compounds used can vary.
- the copolymer P comprises:
- the copolymer P comprises:
- the copolymer P comprises:
- the copolymer P comprises:
- the copolymer P comprises from 39.89 to 59% by weight of monomer (b) relative to the quantity by weight of monomers (a), (c) and (d).
- the copolymer P is different from a copolymer prepared without methacrylic acid but from 30.0% by weight of acrylic acid, from 58.2% by weight of ethyl acrylate, from 7, 5% by weight of 2,2,2-trifluoroethyl methacrylate, 2.5% by weight of acrylamido-2-methylpropane sulfonic acid and 0.8% by weight of ethyl enedimethacryl ate.
- the copolymer P according to the invention has many particularly advantageous properties.
- the copolymer P has a particular glass transition temperature (Tg).
- the copolymer P according to the invention has a glass transition temperature (Tg), calculated using the Flory-Fox equation, of less than 60° C., preferably less than 30° C.
- the Flory-Fox equation makes it possible to calculate the glass transition temperature of the copolymer from the parameters of the monomers used for its preparation, with the exception of any monomers (e) used.
- the copolymer P according to the invention is totally or partially neutralized, preferably by means of a compound chosen from NaOH, KOH, LiOH, ammonium derivatives, ammonia, amino bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and combinations thereof.
- a compound chosen from NaOH, KOH, LiOH, ammonium derivatives, ammonia, amino bases for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and combinations thereof.
- the copolymer P according to the invention can be prepared by a polymerization reaction which also uses at least one hydrophobic monomer (e), in particular an associative hydrophobic monomer (e).
- the monomer (e) comprises a polymerizable olefinic unsaturation, polyalkylene glycol groups and a hydrophobic terminal group.
- the hydrophobic terminal group is a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group, comprising from 6 to 40 carbon atoms.
- the monomer (e) is a compound of formula (VI):
- - q and r identical or different, independently represent 0 or an integer or decimal number, less than 150, the sum q+r ranging from 5 to 150, preferably the sum q+r varies from 10 to 150, advantageously from 10 to 100, more preferably to - OE represents a CH2CH2O group,
- - OP independently represents a group chosen from CH(CH 3 )CH 2 O and CH 2 CH(CH 3 )O,
- R 6 represents a group comprising at least one polymerizable olefinic unsaturation, preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl, isoprenyl, an unsaturated urethane group, in particular acrylurethane, methacrylurethane, a-a '-dimethyl-isopropenyl-benzylurethane, allylurethane, more preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl and isoprenyl, even more preferably a methacrylate group,
- R 7 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms, preferably a hydrocarbon group comprising from 6 to 32 carbon atoms, more preferably from 8 to 30 carbon atoms. carbon.
- R 7 represents a linear alkyl or alkenyl group comprising from 6 to 40 carbon atoms, in particular a cyclohexyl group. According to the invention, R 7 can also represent an alkyl group derived from an alcohol obtained by an oxo reaction.
- R 7 can represent an aromatic group comprising from 6 to 40 carbon atoms, preferentially from 6 to 32 carbon atoms, more preferentially from 6 to 30 carbon atoms.
- R 7 can represent a group of formula (VIII): in which R 10 represents a hydrocarbon group of formula C15H31-S in which s represents 0, 2, 4 or 6; R 10 can thus comprise 0, 1, 2 or 3 ethylenic unsaturations (double bond).
- R 10 represents a hydrocarbon group of formula C15H31-S in which s represents 0, 2, 4 or 6; R 10 can thus comprise 0, 1, 2 or 3 ethylenic unsaturations (double bond).
- Such a group of formula (VIII) is advantageously derived from cardanol, and thus of bio-resourced origin.
- R 7 can represent a group comprising from 2 to 5 phenyl groups, such as a tristyrylphenyl (TSP) group of formula (IX): or a distyryl phenyl (DSP) group of formula (X) or of formula (XI): or a pentastyrylcumylphenyl group.
- TSP tristyrylphenyl
- DSP distyryl phenyl
- R 7 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon-based group comprising from 6 to 40 carbon atoms, preferably a linear or branched Cô-C4o-alkyl group, preferably a Cs- Cso-alkyl, linear or branched, a Ce-C-aryl group, preferably a Cs-Cso-aryl group, preferably comprising from 2 to 5 phenyl groups, for example a tristyrylphenyl group.
- q represents an integer or decimal number, advantageously an integer, greater than or equal to 10.
- each of r and q is different from 0.
- q and r which are identical or different, independently represent an integer or decimal number, advantageously a number ranging from 5 to 100, the sum q+r varying from 10 to 150, advantageously from 10 to 100, more advantageously from 10 to 60.
- the value of q is strictly greater than the value of r.
- r represents 0.
- the copolymer P can comprise from 0.4 to 30% by weight of monomer (e) relative to the total quantity of monomers.
- the copolymer P according to the invention can be prepared according to methods known as such. Specifically, the copolymer P according to the invention is prepared by a polymerization reaction implementing the various compounds a, b, c and d, optionally the compound e, by a radical polymerization reaction, for example a polymerization reaction in emulsion, in dispersion or in solution.
- the copolymer P is prepared in water, preferably in the presence of at least one surfactant compound, for example sodium dodecyl sulphate or sodium dodecyl laurate.
- the preparation of the copolymer P according to the invention can also implement one or more compounds, in particular at least one initiator compound, alone or in combination with at least one chain transfer agent.
- initiator compounds use may be made of a compound chosen from azo initiator compounds (for example azo-bis-isobutyronitrile), a peroxide compound, preferably hydrogen peroxide, benzoyl peroxide, benzoyl hydroperoxide and mixtures thereof.
- azo initiator compounds for example azo-bis-isobutyronitrile
- peroxide compound preferably hydrogen peroxide
- benzoyl peroxide benzoyl hydroperoxide and mixtures thereof.
- alkali metal persulfates in particular sodium persulfate and potassium persulfate, ammonium persulfate, partially water-soluble peroxides, in particular succinic peracid, t-butyl hydroperoxide, hydroperoxide cumyl, persulfates associated with a cuprous ion, a ferrous ion, a sulfite ion or a bisulfite ion and mixtures thereof.
- chain transfer agents use may be made of mercaptan compounds, in particular mercaptan compounds comprising at least 4 carbon atoms such as butyl mercaptan, n-octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan, isooctyl 3-mercaptopropionate.
- the radical initiator or generator compound can therefore be associated with at least one controlled radical polymerization transfer agent, in particular a transfer agent of the RAFT type (reversible addition-fragmentation chain transfer or radical polymerization controlled by transfer of reversible chain by addition-fragmentation).
- the reaction is a free radical emulsion polymerization reaction.
- the preparation in water of the copolymer P makes it possible to obtain an aqueous polymeric composition in the form of an emulsion.
- the copolymer P according to the invention can be used to improve the viscoelastic properties and the suspensive properties of a composition, in particular of an aqueous composition, preferably of an aqueous composition comprising particles.
- the invention provides an aqueous composition C comprising at least one copolymer P according to the invention.
- the aqueous composition C according to the invention comprises at least one copolymer P according to the invention and solid, liquid or gaseous particles, and optionally a binder compound.
- composition C according to the invention comprises from 0.1 to 5% by weight of copolymer P. More preferably, composition C according to the invention comprises from 0.5 to 3% by weight of copolymer P .
- the particles are particles of a product chosen from a cosmetic product, a phytosanitary product, a fertilizer, a coating product.
- aqueous composition C is a varnish composition comprising a copolymer P, particles of a pigment and a binder compound in latex form, optionally a pigment-dispersing compound.
- the binder compound has a glass transition temperature, calculated using the Flory-Fox equation, which is the same +/-10° C. as the glass transition temperature of the copolymer P.
- the binder compound has a glass transition temperature, calculated using the Flory-Fox equation, which is the same +/- 5° C. as the glass transition temperature of the copolymer P.
- the preferred binder compound is an acrylic compound, an alkyd compound or an alkyd-urethane compound or a styrene-acrylic compound or a styrene-butadiene compound.
- the properties of the copolymer P according to the invention allow it to be used under conditions which can vary significantly.
- the properties of the copolymer P can be implemented at variable pH values.
- the aqueous composition C according to the invention has a pH ranging from 3 to 13, preferably a pH ranging from 5 to 13.
- the pH of the aqueous composition C ranges from 4 to 8 or from 5 to 7.
- the invention also relates to a method for preparing an aqueous composition C, viscoelastic and suspending, comprising the introduction of at least one copolymer P according to the invention and the stirring of the composition C.
- the copolymer P makes it possible to improve the properties of composition C according to the invention.
- the copolymer P makes it possible to improve the stability of this composition, in particular for a varnish composition C.
- the invention also relates to a method for stabilizing a varnish composition C comprising the introduction into an aqueous varnish base composition C of at least one copolymer P according to the invention.
- the varnish base composition C comprises a binder compound in the form of a latex, the glass transition temperature of which is the same +/-10° C.
- the binder compound has a glass transition temperature, calculated using the Flory-Fox equation, which is the same +/-5°C as the glass transition temperature of the copolymer P.
- the copolymer P according to the invention has particularly advantageous properties for controlling various components of the rheology of an aqueous composition.
- the copolymer P according to the invention makes it possible to control the flow threshold of an aqueous composition.
- the yield stress corresponds to the value of the shear stress applied to an aqueous composition which causes this composition to flow. In the absence of sufficient constraint, the viscosity of this aqueous composition prevents its spontaneous flow on an acceptable time scale.
- the invention also provides a method for controlling the yield point of an aqueous composition comprising the introduction into the aqueous composition of at least one copolymer P according to the invention.
- the yield point of this aqueous composition measured according to the method described in the examples, is greater than 0.1 Pa, more preferably greater than 0.5 Pa or else greater than 2 Pa, preferably greater than 4 Pa.
- composition C according to the invention comprises from 0.1 to 5% by weight of copolymer P and has a yield point greater than 0.1 Pa, more preferably greater than 0.5 Pa, or else greater than 2 Pa, preferably greater than 4 Pa. Also more preferably, composition C according to the invention comprises from 0.5 to 3% by weight of copolymer P and has a yield point greater than 0.1 Pa, more preferably greater than 0.5 Pa, or else greater than 2 Pa, preferably greater than 4 Pa.
- the particular, advantageous or preferred characteristics of the copolymer P according to the invention define compositions according to the invention and methods according to the invention which are particular, advantageous or preferred compositions and methods according to the invention.
- Example 1 preparation and characterization of copolymers according to the invention
- - hydrophobic monomer e compound (el) of formula VI in which R 6 represents a methacrylate group, q represents 25, OE represents a CH2CH2O group, r represents 0 and R 7 represents a group of formula VII in which R 8 represents a group Linear C6-alkyl and R 9 represents a linear Cio-alkyl group.
- a third glass beaker weigh 0.100 g of sodium metabisulphite and dissolve it in 10 g of deionized water.
- a fourth container of the disposable syringe type, 5.27 g of compound (cl) at 50% by weight in water are weighed.
- the contents of the reactor are heated to a temperature of 76°C ⁇ 2°C.
- the reagents from the 4 containers are introduced into the polymerization reactor at a temperature of 76°C ⁇ 2°C.
- the pumps are flushed with deionized water.
- 0.3 g of ammonium persulfate dissolved in 20 g of deionized water are introduced into the reactor over 1 hour.
- a copolymer (PI) with 30.6% by weight of solids content (SD, measured with a microwave balance) is obtained. Its glass transition temperature (Tg) is calculated using the Flory-Fox equation. The composition and characteristics of the copolymer (PI) are shown in Table 1.
- Example 2 Preparation and characterization of the properties of aqueous compositions C1 to C3 according to the invention
- the PI copolymer prepared according to example 1 is mixed with deionized water in an amount by dry weight of 1% then an aqueous solution of sodium hydroxide (50% by weight) is added in order to completely neutralize the composition.
- the aqueous composition C1 according to the invention is obtained.
- the aqueous compositions C2 and C3 according to the invention are prepared analogously from the copolymers P2 and P3 according to the invention.
- the Brookfield viscosity is then measured at 25° C. and at 100 revolutions/min of these compositions by means of a Brookfield DV1 viscometer equipped with a rotor adapted to the viscosity range of the composition.
- the flow threshold of these compositions is also measured, which is the applied stress which causes the flow of the aqueous composition.
- a stress ramp varying from 0.01 to 1000 Pa is implemented over a period of 3000 seconds with an equilibration time of 30 seconds between each measurement.
- Yield stress was measured at 25°C using a Haake Mars III imposed stress rheometer (ThermoFisher Scientific) equipped with a CP60-1/S cone-plane type geometry (diameter of 60 mm, truncation angle of 1°) then using processing by the RheoWin Data Manager software. The results obtained are shown in Table 2.
- the viscoelasticity of the aqueous compositions Cl, Cl and C3 according to the invention is also determined as a function of the frequency at low deformations.
- the frequency co follows a logarithmic variation from high frequencies to low frequencies (from 100 to 0.01 Hz).
- the copolymers according to the invention therefore make it possible to thicken aqueous compositions significantly.
- the aqueous compositions obtained have a high flow threshold.
- the tangent value ⁇ of these aqueous compositions according to the invention is systematically between 0 and 1, thus demonstrating their viscoelastic character. These properties are obtained in the absence of methacrylic acid during the preparation of the copolymers according to the invention.
Abstract
The invention provides a crosslinked, sulphonated, acrylic copolymer P, prepared from at least four monomers and in the absence of methacrylic acid. The invention also comprises the preparation of an aqueous composition C having viscoelastic and suspensive properties and comprising said copolymer P.
Description
COPOLYMÈRE VISCOÉLASTIQUE ET SUSPENSIF VISCOELASTIC AND SUSPENSIVE COPOLYMER
L’invention fournit un copolymère acrylique P, sulfoné, réticulé et préparé à partir d’au moins quatre monomères et en l’absence d’acide méthacrylique. L’invention comprend également la préparation d’une composition aqueuse, viscoélastique et suspensive comprenant ce copolymère P. The invention provides an acrylic copolymer P, sulfonated, crosslinked and prepared from at least four monomers and in the absence of methacrylic acid. The invention also comprises the preparation of an aqueous, viscoelastic and suspensive composition comprising this copolymer P.
De nombreux domaines techniques requièrent l’utilisation d’agents associant plusieurs propriétés. En particulier, certains domaines techniques nécessitent de contrôler la rhéologie ainsi que la texture d’une composition. Les agents utilisés dans ce but doivent également permettre de stabiliser ces compositions. Many technical fields require the use of agents associating several properties. In particular, certain technical fields require controlling the rheology as well as the texture of a composition. The agents used for this purpose must also make it possible to stabilize these compositions.
Dans le domaine des compositions de revêtement, en particulier pour des compositions de lasure, les agents utilisés doivent permettre de contrôler la rhéologie mais également de conférer un effet suspensif à ces compositions qui comprennent des particules. Les compositions de lasure combinent habituellement un solvant, notamment de l’eau, avec un liant, par exemple un liant acrylique, un liant alkyde ou un liant alkyde-uréthane, et des particules de pigment. Ces compositions permettent de protéger le substrat sur lequel elles sont appliquées, en particulier un substrat en bois ou en béton. La compatibilité des différents constituants d’une composition est donc également essentielle. In the field of coating compositions, in particular for stain compositions, the agents used must make it possible to control the rheology but also to confer a suspensive effect on these compositions which comprise particles. Stain compositions usually combine a solvent, especially water, with a binder, for example an acrylic binder, an alkyd binder or an alkyd-urethane binder, and pigment particles. These compositions make it possible to protect the substrate on which they are applied, in particular a wooden or concrete substrate. The compatibility of the different constituents of a composition is therefore also essential.
En particulier, les agents de contrôle de la rhéologie et de la texture d’une composition doivent posséder une température de transition vitreuse qui permette de les combiner efficacement avec d’autres substances présentes dans ces compositions, notamment avec un liant, généralement sous forme de particules. In particular, the rheology and texture control agents of a composition must have a glass transition temperature which allows them to be combined effectively with other substances present in these compositions, in particular with a binder, generally in the form of particles.
L’effet suspensif recherché pour une composition est l’aptitude à maintenir en suspension des particules dans une phase continue, de manière stable dans le temps, par exemple lors du stockage de la composition. Les particules sont généralement des corps solides, pleins ou creux. Elles peuvent également être des entités liquides non miscibles avec la phase continue ou être encapsulées ou sous forme gazeuse. Leur forme, leur texture, leur structure peuvent varier largement, notamment en fonction des propriétés finales attendues. The suspensive effect sought for a composition is the ability to maintain particles in suspension in a continuous phase, in a stable manner over time, for example during storage of the composition. Particles are generally solid, solid or hollow bodies. They can also be liquid entities immiscible with the continuous phase or be encapsulated or in gaseous form. Their shape, texture and structure can vary widely, in particular depending on the final properties expected.
Les performances suspensives peuvent être évaluées en déterminant la valeur du module d’élasticité G’, la valeur du facteur d’amortissement (Tan ô) et la valeur de la résistance élastique. The suspensive performance can be evaluated by determining the value of the modulus of elasticity G', the value of the damping factor (Tan ô) and the value of the elastic resistance.
Par ailleurs, il est nécessaire de contrôler la viscosité de ces compositions, tant pour de faibles ou moyens gradients de cisaillement que pour des gradients de cisaillement élevés. En effet, au cours de sa préparation, de son stockage, de son application ou de son séchage,
une composition peut subir de nombreuses contraintes nécessitant des propriétés rhéologiques particulièrement complexes, notamment des propriétés de viscoélasticité.Furthermore, it is necessary to control the viscosity of these compositions, both for low or medium shear gradients and for high shear gradients. Indeed, during its preparation, its storage, its application or its drying, a composition can be subjected to numerous stresses requiring particularly complex rheological properties, in particular viscoelastic properties.
En rhéologie, le comportement d'un matériau viscoélastique linéaire est intermédiaire entre celui d'un solide élastique idéal symbolisé par un ressort de module E (ou G) et celui d'un liquide visqueux newtonien symbolisé par un facteur d’amortissement de viscosité. L'élasticité d'un matériau traduit sa capacité à conserver et restituer de l'énergie après déformation. La viscosité d'un matériau traduit sa capacité à dissiper de l'énergie. In rheology, the behavior of a linear viscoelastic material is intermediate between that of an ideal elastic solid symbolized by a spring of modulus E (or G) and that of a Newtonian viscous liquid symbolized by a viscosity damping factor. The elasticity of a material reflects its ability to retain and release energy after deformation. The viscosity of a material reflects its ability to dissipate energy.
La viscoélasticité d’une composition doit donc également être améliorée afin que cette composition présente des caractéristiques à la fois visqueuses et élastiques lorsqu'elle subit une déformation. La composante visqueuse permet à cette composition de résister à un écoulement en cisaillement et de présenter une déformation qui augmente linéairement avec le temps lorsqu'une contrainte est appliquée. La composante élastique permet une déformation lorsqu’une contrainte est appliquée, puis le retour à l’état d'origine une fois que la contrainte est interrompue. The viscoelasticity of a composition must therefore also be improved so that this composition exhibits both viscous and elastic characteristics when it undergoes deformation. The viscous component allows this composition to resist shear flow and exhibit a deformation that increases linearly with time when stress is applied. The elastic component allows a deformation when a stress is applied, then the return to the original state once the stress is interrupted.
Il existe donc un besoin de disposer d’agents qui permettent d’apporter des propriétés de viscoélasticité et d’effet suspensif à des compositions. There is therefore a need for agents which make it possible to provide viscoelastic properties and a suspensive effect to compositions.
Par ailleurs, et notamment pour des raisons environnementales, il existe également un fort besoin de pouvoir disposer de compositions ne comprenant pas d’acide méthacrylique, tout en offrant des performances maintenues ou améliorées par rapport aux compositions de l’état de la technique. En effet, l’utilisation d’acide méthacrylique, notamment d’acide méthacrylique préparé à partir de cyanhydrine d’acétone qui est un composé hautement toxique, devrait être limitée autant que possible. Furthermore, and in particular for environmental reasons, there is also a strong need to be able to have compositions that do not comprise methacrylic acid, while offering maintained or improved performance compared to the compositions of the state of the art. Indeed, the use of methacrylic acid, in particular methacrylic acid prepared from acetone cyanohydrin which is a highly toxic compound, should be limited as much as possible.
Les documents US2017003717 et US20190315897 décrivent des copolymères préparés avec de l’acide méthacrylique. Le document US20080193405 décrit la préparation de compositions hydrauliques ou alcooliques comprenant une combinaison de copolymères associée à un mélange d’acide acrylique et d’un composé réticulant. Le document WO2014185381 concerne une composition liante pour une batterie au lithium et qui comprend un copolymère fluoré. Documents US2017003717 and US20190315897 describe copolymers prepared with methacrylic acid. Document US20080193405 describes the preparation of hydraulic or alcoholic compositions comprising a combination of copolymers combined with a mixture of acrylic acid and a crosslinking compound. Document WO2014185381 relates to a binder composition for a lithium battery and which comprises a fluorinated copolymer.
Il existe donc un besoin de disposer d’un copolymère aux propriétés améliorées et qui permette d’apporter une solution à tout ou partie des problèmes des polymères de l’état de la technique. There is therefore a need to have a copolymer with improved properties and which makes it possible to provide a solution to all or part of the problems of the polymers of the state of the art.
Ainsi, l’invention fournit un copolymère P préparé en l’absence d’acide méthacrylique, par au moins une réaction de polymérisation :
a. d'au moins un monomère (a) anionique choisi parmi l’acide acrylique, un sel d’acide acrylique, les oligomères de l’acide acrylique, les sels d’oligomères de l’acide acrylique et leurs combinaisons ; b. d’au moins un monomère (b) non-ionique choisi parmi le styrène, les esters en Ci-Cs d’un acide choisi parmi acide acrylique, acide méthacrylique et leurs combinaisons ; c. d’au moins un composé (c) choisi parmi acide 2-acrylamido-2-méthylpropane sulfonique, méthacrylate de 2-sulfoéthyl, méthallyl sulfonate de sodium, styrène sulfonate, leurs sels et leurs combinaisons ; d. d’au moins un composé (d) réticulant ou comprenant au moins deux insaturations oléfiniques polymérisables. Thus, the invention provides a copolymer P prepared in the absence of methacrylic acid, by at least one polymerization reaction: has. at least one anionic monomer (a) chosen from acrylic acid, a salt of acrylic acid, oligomers of acrylic acid, salts of oligomers of acrylic acid and combinations thereof; b. at least one nonionic monomer (b) chosen from styrene, C 1 -C 8 esters of an acid chosen from acrylic acid, methacrylic acid and combinations thereof; vs. at least one compound (c) chosen from 2-acrylamido-2-methylpropane sulphonic acid, 2-sulphoethyl methacrylate, sodium methallyl sulphonate, styrene sulphonate, their salts and their combinations; d. at least one compound (d) crosslinking or comprising at least two polymerizable olefinic unsaturations.
De manière préférée selon l’invention, le copolymère P peut être préparé à partir des seuls composés a, b, c et d. Preferably according to the invention, the copolymer P can be prepared from only compounds a, b, c and d.
Également de manière préférée selon l’invention, le monomère (a) est l’acide acrylique ou un mélange d’oligomères de l’acide acrylique de formule (I) :
dans laquelle m est un nombre entier ou décimal allant de 1 à 10, de préférence allant de 2 à 4. De manière plus préférée selon l’invention, le monomère (a) est l’acide acrylique. Also preferably according to the invention, the monomer (a) is acrylic acid or a mixture of oligomers of acrylic acid of formula (I): in which m is an integer or decimal number ranging from 1 to 10, preferably ranging from 2 to 4. More preferably according to the invention, the monomer (a) is acrylic acid.
Également de manière préférée selon l’invention, le monomère (b) est choisi parmi : Also preferably according to the invention, the monomer (b) is chosen from:
- acrylate d’ alkyl e, en particulier acrylate de Ci-Cs-alkyl, préférentiellement acrylate de Ci-C4-alkyl, plus préférentiellement acrylate de méthyle, acrylate d’éthyle, acrylate de propyle, acrylate d’isobutyle, acrylate de n-butyle, méthacrylate d’alkyle, en particulier méthacrylate de Ci-Cs-alkyl, préférentiellement méthacrylate de Ci-C4-alkyl, plus préférentiellement méthacrylate de méthyle, méthacrylate d’éthyle, méthacrylate de propyle, méthacrylate d’isobutyle, méthacrylate de n-butyle, acrylate d’aryle, de préférence phényl acrylate, benzyl acrylate, phénoxy éthyl acryl ate, - alkyl acrylate, in particular Ci-Cs-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n- butyl, alkyl methacrylate, in particular Ci-Cs-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, n- butyl, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxy ethyl acryl ate,
- méthacrylate d’aryle, de préférence phénylméthacrylate, benzylméthacrylate, phénoxyéthylméthacrylate et - aryl methacrylate, preferably phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate and
- leurs combinaisons.
De manière plus préférée selon l’invention, le monomère (b) est choisi parmi acrylate d’éthyle et acrylate de butyle, plus préférentiellement acrylate d’éthyle. - their combinations. More preferably according to the invention, the monomer (b) is chosen from ethyl acrylate and butyl acrylate, more preferably ethyl acrylate.
De manière préférée, le monomère (b) selon l’invention est un monomère non-fluoré ou bien le monomère (b) est différent du 2,2,2-trifluoroethyl methacrylate. Selon l’invention, le monomère (c) préféré est choisi parmi l’acide 2-acrylamido-2-méthylpropane sulfonique (AMPS) et ses sels de sodium ou d’ammonium. Selon l’invention, le composé (d) préféré est choisi parmi les monomères aromatiques polyinsaturés comme divinylbenzene, divinyl naphthalène et trivinylbenzene, les monomères alicycliques polyinsaturés par exemple 1, 2, 4-trivinyl cyclohexane, esters d’acide phthalique difonctionnels comme diallyl phthalate, éthers polyalkenyl tels que triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose et triméthylolpropane diallyl éther, esters polyinsaturés de polyalcohols ou de polyacides comme 1,6-hexanediol di(méth)acrylate, tétraméthylène tri(méth)acrylate, allyl acrylate, diallyl itaconate, diallyl fumarate, diallyl maléate, triméthylolpropane tri(méth)acrylate, triméthylolpropane di(méth)acrylate, poly(alkylèneoxy) glycol di(méth)acrylate et polyéthylène glycol di(méth)acrylate, alkylène bisacrylamides comme méthylènebisacrylamide et propylène bisacrylamide, dérivés hydroxy ou carboxy de méthylène bis-acrylamide comme N,N'-bisméthylol méthylène bisacrylamide, polyalkylèneglycol di(méth)acrylates comme éthylèneglycol di(méth)acrylate, diéthylèneglycol di(méth)acrylate, triéthylèneglycol di(méth)acrylate, allyl méthacrylate, éthylène glycol diméthacrylate, butylène glycol diméthacrylate, pentaerythritol di-, tri- et tetra-acrylates, poly(alkylèneoxy)glycol di(méth)acrylates tels que polyéthylène glycol diacrylate, bisphenol A diacrylate, butanediol diméthacrylate, 2,2-diméthylpropanediol diméthacrylate, phénylène diacrylate, un composé réticulant dissymétrique et leurs combinaisons. Preferably, the monomer (b) according to the invention is a non-fluorinated monomer or else the monomer (b) is different from 2,2,2-trifluoroethyl methacrylate. According to the invention, the preferred monomer (c) is chosen from 2-acrylamido-2-methylpropane sulphonic acid (AMPS) and its sodium or ammonium salts. According to the invention, the preferred compound (d) is chosen from polyunsaturated aromatic monomers such as divinylbenzene, divinyl naphthalene and trivinylbenzene, polyunsaturated alicyclic monomers, for example 1, 2, 4-trivinyl cyclohexane, difunctional phthalic acid esters such as diallyl phthalate , polyalkenyl ethers such as triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose and trimethylolpropane diallyl ether, polyunsaturated esters of polyalcohols or polyacids such as 1,6-hexanediol di(meth)acrylate, tetramethylene tri(meth)acrylate, allyl acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, poly(alkyleneoxy) glycol di(meth)acrylate and polyethylene glycol di(meth)acrylate, alkylene bisacrylamides such as methylenebisacrylamide and propylene bisacrylamide, hydroxy or carboxy derivatives of methylene bis-acrylamide such as N,N'-bismethylol methylene bisacrylamide, polyalkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, pentaerythritol di-, tri- and tetra-acrylates, poly(alkyleneoxy)glycol di(meth)acrylates such as polyethylene glycol diacrylate, bisphenol A diacrylate, butanediol dimethacrylate, 2,2-dimethylpropanediol dimethacrylate, phenylene diacrylate, an unsymmetrical crosslinking compound and combinations thereof.
Le composé réticulant dissymétrique (d) préféré selon l’invention est choisi parmi : The dissymmetrical crosslinking compound (d) preferred according to the invention is chosen from:
• un composé de formule (II) :
dans laquelle : • a compound of formula (II): in which :
- L1 représente CHz, CHz monoalkoxylé ou CHz polyalkoxylé,
- R1 représente -C(H)=CH2, -C(CH3)=CH2, -C(H)=C(H)C(O)OH,- L 1 represents CHz, monoalkoxylated CHz or polyalkoxylated CHz, - R 1 represents -C(H)=CH 2 , -C(CH 3 )=CH 2 , -C(H)=C(H)C(O)OH,
-C(H)=C(H)CH3, -C(=CH2)CH2C(O)OH, -CH2C(=CH2)C(O)OH,-C(H)=C(H)CH 3 , -C(=CH 2 )CH 2 C(O)OH, -CH 2 C(=CH 2 )C(O)OH,
Q1OQ2OC(O)C(CH3)=CH2 OU Q1OQ2OC(O)C(H)=CH2, Q 1 OQ 2 OC(O)C(CH 3 )=CH 2 OR Q 1 OQ 2 OC(O)C(H)=CH 2 ,
- Q1 représente un résidu divalent d’un composé diisocyanate dissymétrique, de préférence choisi parmi tolyl-l,3-diisocyanate (TDI) et isophorone-diisocyanate (IPDI), - Q 1 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
- Q2 représente CH2, CH2-CH2, CH2 monoalkoxylé, CH2-CH2 monoalkoxylé, CH2 polyalkoxylé ou CH2-CH2 polyalkoxylé ; de préférence un composé de formule (II) dans laquelle : - Q 2 represents CH 2 , CH 2 -CH 2 , monoalkoxylated CH 2 , monoalkoxylated CH 2 -CH 2 , polyalkoxylated CH 2 or polyalkoxylated CH 2 -CH 2 ; preferably a compound of formula (II) in which:
- L1 représente CH2 et - L 1 represents CH 2 and
- R1 représente -C(H)=CH2, -C(CH3)=CH2, -C(H)=C(H)C(O)OH, -C(H)=C(H)CH3, -C(=CH2)CH2C(O)OH, -CH2C(=CH2)C(O)OH OU un composé de formule (II) dans laquelle : - R 1 represents -C(H)=CH 2 , -C(CH 3 )=CH 2 , -C(H)=C(H)C(O)OH, -C(H)=C(H)CH 3 , -C(=CH 2 )CH 2 C(O)OH, -CH 2 C(=CH 2 )C(O)OH OR a compound of formula (II) in which:
- L1 représente CH2 monoalkoxylé ou CH2 polyalkoxylé, - L 1 represents monoalkoxylated CH 2 or polyalkoxylated CH 2 ,
- R1 représente Q1OQ2OC(O)C(CH3)=CH2 ou Q1OQ2OC(O)C(H)=CH2,- R 1 represents Q 1 OQ 2 OC(O)C(CH 3 )=CH 2 or Q 1 OQ 2 OC(O)C(H)=CH 2 ,
- Q1 représente un résidu divalent d’un composé diisocyanate dissymétrique, de préférence choisi parmi tolyl-l,3-diisocyanate (TDI) et isophorone-diisocyanate (IPDI), - Q 1 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
- Q2 représente CH2, CH2-CH2, CH2 monoalkoxylé, CH2-CH2 monoalkoxylé, CH2 polyalkoxylé ou CH2-CH2 polyalkoxylé ; - Q 2 represents CH 2 , CH 2 -CH 2 , monoalkoxylated CH 2 , monoalkoxylated CH 2 -CH 2 , polyalkoxylated CH 2 or polyalkoxylated CH 2 -CH 2 ;
• un composé de formule (III) :
dans laquelle : • a compound of formula (III): in which :
- L2 représente CH2, CH2 monoalkoxylé ou CH2 polyalkoxylé, - L 2 represents CH 2 , monoalkoxylated CH 2 or polyalkoxylated CH 2 ,
- R2 représente -C(H)=CH2, -C(CH3)=CH2, -C(H)=C(H)C(O)OH,- R 2 represents -C(H)=CH 2 , -C(CH 3 )=CH 2 , -C(H)=C(H)C(O)OH,
-C(H)=C(H)CH3, -C(=CH2)CH2C(O)OH, -CH2C(=CH2)C(O)OH,-C(H)=C(H)CH 3 , -C(=CH 2 )CH 2 C(O)OH, -CH 2 C(=CH 2 )C(O)OH,
Q3OQ4OC(O)C(CH3)=CH2 OU Q3OQ4OC(O)C(H)=CH2, Q 3 OQ 4 OC(O)C(CH 3 )=CH 2 OR Q 3 OQ 4 OC(O)C(H)=CH 2 ,
- Q3 représente un résidu divalent d’un composé diisocyanate dissymétrique, de préférence choisi parmi tolyl-l,3-diisocyanate (TDI) et isophorone-diisocyanate (IPDI),
- Q4 représente CH2, CH2-CH2, CH2 monoalkoxylé, CH2-CH2 monoalkoxylé, CH2 polyalkoxylé ou CH2-CH2 polyalkoxylé ; de préférence un composé de formule (III) dans laquelle : - Q 3 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI), - Q 4 represents CH2, CH2-CH2, monoalkoxylated CH2, monoalkoxylated CH2-CH2, polyalkoxylated CH2 or polyalkoxylated CH2-CH2; preferably a compound of formula (III) in which:
- L2 représente CH2, - L 2 represents CH2,
- R2 représente -C(H)=CH2, -C(CH3)=CH2, -C(H)=C(H)C(O)OH, -C(H)=C(H)CH3, -C(=CH2)CH2C(O)OH, -CH2C(=CH2)C(O)OH, OU un composé de formule (III) dans laquelle : - R 2 represents -C(H)=CH 2 , -C(CH 3 )=CH 2 , -C(H)=C(H)C(O)OH, -C(H)=C(H)CH 3 , -C(=CH 2 )CH 2 C(O)OH, -CH 2 C(=CH 2 )C(O)OH, OR a compound of formula (III) in which:
- L2 représente CH2 monoalkoxylé ou CH2 polyalkoxylé, - L 2 represents monoalkoxylated CH2 or polyalkoxylated CH2,
- R2 représente Q3OQ4OC(O)C(CH3)=CH2 ou Q3OQ4OC(O)C(H)=CH2,- R 2 represents Q 3 OQ 4 OC(O)C(CH 3 )=CH 2 or Q 3 OQ 4 OC(O)C(H)=CH 2 ,
- Q3 représente un résidu divalent d’un composé diisocyanate dissymétrique, de préférence choisi parmi tolyl-l,3-diisocyanate (TDI) et isophorone-diisocyanate (IPDI), - Q 3 represents a divalent residue of an asymmetrical diisocyanate compound, preferably chosen from tolyl-l,3-diisocyanate (TDI) and isophorone-diisocyanate (IPDI),
- Q4 représente CH2, CH2-CH2, CH2 monoalkoxylé, CH2-CH2 monoalkoxylé, CH2 polyalkoxylé ou CH2-CH2 polyalkoxylé ; - Q 4 represents CH2, CH2-CH2, monoalkoxylated CH2, monoalkoxylated CH2-CH2, polyalkoxylated CH2 or polyalkoxylated CH2-CH2;
• un composé de formule (IV) :
dans laquelle : • a compound of formula (IV): in which :
- R3 représente indépendamment H ou CH3, - R 3 independently represents H or CH 3 ,
- L3 représente indépendamment un groupement Ci-C2o-alkylène linéaire ou ramifié et - L 3 independently represents a linear or branched Ci-C2o-alkylene group and
- n représente indépendamment 0 ou un nombre entier allant de 1 à 30, par exemple de 1 à 20, en particulier de 1 à 15, notamment de 1 à 10 ; - n independently represents 0 or an integer ranging from 1 to 30, for example from 1 to 20, in particular from 1 to 15, in particular from 1 to 10;
• un composé choisi parmi les di(méth)acrylates comme le di(méth)acrylate de polyalkylène glycol, notamment le di(méth)acrylate de polypropylène glycol, le di(méth)acrylate d’éthylène glycol, le di(méth)acrylate de polyéthylène glycol, le di(méth)acrylate de triéthylène glycol, le di(méth)acrylate de 1,3-butylène glycol, le di(méth)acrylate de 1,6-butylène glycol, le di(méth)acrylate de 1,6-hexanediol, le di(méth)acrylate de néopentyl glycol, le di(méth)acrylate de 1,9-nonanediol, mais aussi le 2,2'-bis(4-(acryloxypropyloxy)-phényl)propane, le 2,2'-bis(4-(acryloxydiéthoxy)-phényl)propane ; les composés tri(méth)acrylates tels que le tri(méth)acrylate de triméthylolpropane et le tri(méth)acrylate de
triméthylolpropane éthoxylé, le tri(méth)acrylate triméthyloléthane, le tri(méth)acrylate pentaérythritol et le tri(méth)acrylate de tétraméthylolméthane ; les composés tétra(méth)acrylates tels que le tétra(méth)acrylate de ditriméthylolpropane, le tétra(méth)acrylate de tétraméthylolméthane et le tétra(méth)acrylate de pentaérythritol ; les composés hexa(méth)acrylates tels que l’hexa(méth)acrylate de dipentaérythritol ; les composés penta(méth)acrylates tels que le penta(méth)acrylate de dipentaérythritol ; les composés allyls tels que 1 ’ allyl (méth)acrylate, le diallylphthalate, l’itaconate de diallyl, le fumarate de diallyl, le maléate de diallyl ; les éthers polyallyls du sucrose ayant de 2 à 8 groupes par molécule, les éthers polyallyls du pentaérythritol tels que le pentaérythritol diallyl éther, le pentaérythritol triallyl éther et le pentaérythritol tetraallyl éther ; les éthers polyallyls du triméthylolpropane tels que l’éther diallyl triméthylolpropane et l’éther triallyl triméthylolpropane ; • a compound chosen from di(meth)acrylates such as polyalkylene glycol di(meth)acrylate, in particular polypropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, di(meth)acrylate polyethylene glycol, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-butylene glycol di(meth)acrylate, 1,6-butylene glycol di(meth)acrylate, ,6-hexanediol, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, but also 2,2'-bis(4-(acryloxypropyloxy)-phenyl)propane, 2 ,2'-bis(4-(acryloxydiethoxy)-phenyl)propane; tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and tri(meth)acrylate of ethoxylated trimethylolpropane, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate and tetramethylolmethane tri(meth)acrylate; tetra(meth)acrylate compounds such as ditrimethylolpropane tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate; hexa(meth)acrylate compounds such as dipentaerythritol hexa(meth)acrylate; penta(meth)acrylate compounds such as dipentaerythritol penta(meth)acrylate; allyl compounds such as 1 allyl (meth) acrylate, diallylphthalate, diallyl itaconate, diallyl fumarate, diallyl maleate; sucrose polyallyl ethers having 2 to 8 groups per molecule, pentaerythritol polyallyl ethers such as pentaerythritol diallyl ether, pentaerythritol triallyl ether and pentaerythritol tetraallyl ether; polyallyl ethers of trimethylolpropane such as diallyl trimethylolpropane ether and triallyl trimethylolpropane ether;
• un composé choisi parmi les composés polyinsaturés notamment divinyl glycol, divinyl benzène, divinylcyclohexyl et méthylènebisacrylamide ; • a compound chosen from polyunsaturated compounds in particular divinyl glycol, divinyl benzene, divinylcyclohexyl and methylenebisacrylamide;
• un composé choisi parmi les réticulants trifonctionnels, notamment tri(méth)acrylate de triméthylolpropane (TMPTA), du tri(méth)acrylate de triméthylolpropane éthoxylé tel que par exemple le TMPTA 3OE ; • a compound chosen from trifunctional crosslinkers, in particular trimethylolpropane tri(meth)acrylate (TMPTA), ethoxylated trimethylolpropane tri(meth)acrylate such as, for example, TMPTA 3OE;
• un composé choisi parmi di(méth)acrylate d’éthylène glycol, méthylènebisacrylamide, diallylphthalate, diallylmaléate ; • a compound chosen from ethylene glycol di(meth)acrylate, methylenebisacrylamide, diallylphthalate, diallylmaleate;
• un mélange de deux monomères distincts, par exemple EGDCPEA (éthylène glycol dicyclopentényl éther acrylate) et TMPTA ou encore EGDCPEA et TMPTA 3OE ; • a mixture of two distinct monomers, for example EGDCPEA (ethylene glycol dicyclopentenyl ether acrylate) and TMPTA or even EGDCPEA and TMPTA 3OE;
• un composé de formule (V) :
dans laquelle : • a compound of formula (V): in which :
- R4 représente indépendamment H ou CEE, - R 4 independently represents H or CEE,
R5 représente indépendamment -C(H)=CH2, -C(CH3)=CH2,R 5 independently represents -C(H)=CH2, -C(CH 3 )=CH2,
-C(H)=C(H)C(O)OH, -C(H)=C(H)CH3, -C(=CH2)CH2C(O)OH,-C(H)=C(H)C(O)OH, -C(H)=C(H)CH 3 , -C(=CH 2 )CH 2 C(O)OH,
-CH2C(=CH2)C(O)OH, -CH 2 C(=CH 2 )C(O)OH,
- L4 représente indépendamment un groupement éthylène, propylène ou butylène et
- p représente indépendamment 0 ou un nombre entier ou décimal allant de 1 à 30, de préférence p représente un nombre entier ou décimal allant de 1 à 18, de 1 à 15 ou de 2 à 16 ou encore de 2 à 12 ; plus préférentiellement un composé choisi parmi un composé (dl) de formule (V) dans laquelle R4 représente H, R5 représente -C(H)=CH2, L4 représente CH2-CH2 et p représente 10 (numéro CAS 99742-80-0) ; de manière également particulièrement préférée un composé (d2) de formule (V) dans laquelle R4 représente H, R5 représente -C(CH3)=CH2, L4 représente CFb-CFb et p représente 3,5 (numéro CAS 121826-50-4) ; de manière également particulièrement préférée un composé (d3) de formule (V) dans laquelle R4 représente H, L4 représente CH2-CH2, R5 représente -C(CH3)=CH2 et p représente 10 (numéro CAS 121826-50-4). - L 4 independently represents an ethylene, propylene or butylene group and - p independently represents 0 or an integer or decimal number ranging from 1 to 30, preferably p represents an integer or decimal number ranging from 1 to 18, from 1 to 15 or from 2 to 16 or even from 2 to 12; more preferably a compound chosen from a compound (dl) of formula (V) in which R 4 represents H, R 5 represents -C(H)=CH2, L 4 represents CH2-CH2 and p represents 10 (CAS number 99742-80 -0); also particularly preferably a compound (d2) of formula (V) in which R 4 represents H, R 5 represents -C(CH3)=CH2, L 4 represents CFb-CFb and p represents 3.5 (CAS number 121826- 50-4); also particularly preferably a compound (d3) of formula (V) in which R 4 represents H, L 4 represents CH2-CH2, R 5 represents -C(CH3)=CH2 and p represents 10 (CAS number 121826-50- 4).
Lors de la préparation du copolymère P, les quantités des composés utilisés peuvent varier. De manière préférée selon l’invention, le copolymère P comprend : During the preparation of the copolymer P, the amounts of the compounds used can vary. Preferably according to the invention, the copolymer P comprises:
- de 25 à 60 % en poids de monomère (a), - from 25 to 60% by weight of monomer (a),
- de 39,89 à 59 % en poids de monomère (b), - from 39.89 to 59% by weight of monomer (b),
- de 0, 1 à 8 % en poids de monomère (c) et - from 0.1 to 8% by weight of monomer (c) and
- de 0,01 à 8 % en poids de monomère (d). - from 0.01 to 8% by weight of monomer (d).
De manière également préférée selon l’invention, le copolymère P comprend : Also preferably according to the invention, the copolymer P comprises:
- de 25 à 60 % en poids de monomère (a), - from 25 to 60% by weight of monomer (a),
- de 44,89 à 59 % en poids de monomère (b), - from 44.89 to 59% by weight of monomer (b),
- de 0, 1 à 8 % en poids de monomère (c) et - from 0.1 to 8% by weight of monomer (c) and
- de 0,01 à 3 % en poids de monomère (d). - from 0.01 to 3% by weight of monomer (d).
De manière également préférée selon l’invention, le copolymère P comprend : Also preferably according to the invention, the copolymer P comprises:
- de 30 à 50 % en poids de monomère (a), - from 30 to 50% by weight of monomer (a),
- de 49,89 à 54 % en poids de monomère (b), - from 49.89 to 54% by weight of monomer (b),
- de 0, 1 à 8 % en poids de monomère (c) et - from 0.1 to 8% by weight of monomer (c) and
- de 0,01 à 8 % en poids de monomère (d). - from 0.01 to 8% by weight of monomer (d).
De manière également préférée selon l’invention, le copolymère P comprend : Also preferably according to the invention, the copolymer P comprises:
- de 25 à 45 % en poids de monomère (a), - from 25 to 45% by weight of monomer (a),
- de 54,89 à 59 % en poids de monomère (b), - from 54.89 to 59% by weight of monomer (b),
- de 0, 1 à 8 % en poids de monomère (c) et - from 0.1 to 8% by weight of monomer (c) and
- de 0,01 à 8 % en poids de monomère (d). - from 0.01 to 8% by weight of monomer (d).
De manière plus préférée selon l’invention, le copolymère P comprend de 39,89 à 59 % en poids de monomère (b) par rapport à la quantité en poids de monomères (a), (c) et (d).
Selon l’invention, le copolymère P est différent d’un copolymère préparé sans acide méthacrylique mais à partir de 30,0 % en poids d’acide acrylique, de 58,2 % en poids d’acrylate d’éthyl, de 7,5 % en poids de methacrylate de 2,2,2-trifluoroethyl, de 2,5 % en poids d’acide acrylamido-2-méthylpropane sulfonique et de 0,8 % en poids d ’ éthyl ènediméthacryl ate . More preferably according to the invention, the copolymer P comprises from 39.89 to 59% by weight of monomer (b) relative to the quantity by weight of monomers (a), (c) and (d). According to the invention, the copolymer P is different from a copolymer prepared without methacrylic acid but from 30.0% by weight of acrylic acid, from 58.2% by weight of ethyl acrylate, from 7, 5% by weight of 2,2,2-trifluoroethyl methacrylate, 2.5% by weight of acrylamido-2-methylpropane sulfonic acid and 0.8% by weight of ethyl enedimethacryl ate.
Le copolymère P selon l’invention possède de nombreuses propriétés particulièrement avantageuses. Notamment, le copolymère P possède une température de transition vitreuse (Tg) particulière. De manière préférée, le copolymère P selon l’invention possède une température de transition vitreuse (Tg), calculée au moyen de l’équation de Flory-Fox, inférieure à 60°C, de préférence inférieure à 30°C. L’équation de Flory-Fox permet de calculer la température de transition vitreuse du copolymère à partir des paramètres des monomères utilisés pour sa préparation, à l’exception des éventuels monomères (e) mis en œuvre. The copolymer P according to the invention has many particularly advantageous properties. In particular, the copolymer P has a particular glass transition temperature (Tg). Preferably, the copolymer P according to the invention has a glass transition temperature (Tg), calculated using the Flory-Fox equation, of less than 60° C., preferably less than 30° C. The Flory-Fox equation makes it possible to calculate the glass transition temperature of the copolymer from the parameters of the monomers used for its preparation, with the exception of any monomers (e) used.
De manière également préférée, le copolymère P selon l’invention est totalement ou partiellement neutralisé, de préférence au moyen d’un composé choisi parmi NaOH, KOH, LiOH, les dérivés ammonium, l’ammoniaque, les bases aminées, par exemple triéthanolamine, aminométhylpropanol ou 2-amino-2-méthyl-propanol (AMP) et leurs combinaisons. Also preferably, the copolymer P according to the invention is totally or partially neutralized, preferably by means of a compound chosen from NaOH, KOH, LiOH, ammonium derivatives, ammonia, amino bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and combinations thereof.
Outre les composés a, b, c et d, le copolymère P selon l’invention peut être préparé par une réaction de polymérisation qui met également en œuvre au moins un monomère (e) hydrophobe, notamment un monomère (e) hydrophobe associatif. De manière préférée selon l’invention, le monomère (e) comprend une insaturation oléfinique polymérisable, des groupements polyalkylèneglycols et un groupement terminal hydrophobe. De préférence selon l’invention, le groupement terminal hydrophobe est un groupement hydrocarboné linéaire, ramifié ou cyclique, saturé, insaturé ou aromatique, comprenant de 6 à 40 atomes de carbone. De manière préférée selon l’invention, le monomère (e) est un composé de formule (VI) : In addition to compounds a, b, c and d, the copolymer P according to the invention can be prepared by a polymerization reaction which also uses at least one hydrophobic monomer (e), in particular an associative hydrophobic monomer (e). Preferably according to the invention, the monomer (e) comprises a polymerizable olefinic unsaturation, polyalkylene glycol groups and a hydrophobic terminal group. Preferably according to the invention, the hydrophobic terminal group is a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group, comprising from 6 to 40 carbon atoms. Preferably according to the invention, the monomer (e) is a compound of formula (VI):
R6-(OE)q-(OP)r-R7 R 6 -(OE) q -(OP) r -R 7
(VI) dans laquelle : (VI) in which:
- q et r, identiques ou différents, représentent indépendamment 0 ou un nombre entier ou décimal, inférieur à 150, la somme q+r allant de 5 à 150, de préférence la somme q+r varie de 10 à 150, avantageusement de 10 à 100, plus avantageusement de
- OE représente un groupement CH2CH2O, - q and r, identical or different, independently represent 0 or an integer or decimal number, less than 150, the sum q+r ranging from 5 to 150, preferably the sum q+r varies from 10 to 150, advantageously from 10 to 100, more preferably to - OE represents a CH2CH2O group,
- OP représente indépendamment un groupement choisi parmi CH(CH3)CH2O et CH2CH(CH3)O, - OP independently represents a group chosen from CH(CH 3 )CH 2 O and CH 2 CH(CH 3 )O,
- R6 représente un groupement comprenant au moins une insaturation oléfinique polyméri sable, de préférence un groupement choisi parmi acrylate, méthacrylate, acryluréthane, méthacryluréthane, vinyl, allyl, méthallyl, isoprényl, un groupement uréthane insaturé, notamment acryluréthane, méthacryluréthane, a-a'-diméthyl-isopropenyl-benzyluréthane, allyluréthane, plus préférentiellement un groupement choisi parmi acrylate, méthacrylate, acryluréthane, méthacryluréthane, vinyl, allyl, méthallyl et isoprényl, encore plus préférentiellement un groupement méthacrylate, - R 6 represents a group comprising at least one polymerizable olefinic unsaturation, preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl, isoprenyl, an unsaturated urethane group, in particular acrylurethane, methacrylurethane, a-a '-dimethyl-isopropenyl-benzylurethane, allylurethane, more preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl and isoprenyl, even more preferably a methacrylate group,
- R7 représente indépendamment un groupement hydrocarboné linéaire, ramifié ou cyclique, saturé, insaturé ou aromatique comprenant de 6 à 40 atomes de carbone, de préférence un groupement hydrocarboné comprenant de 6 à 32 atomes de carbone, plus préférentiellement de 8 à 30 atomes de carbone. - R 7 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms, preferably a hydrocarbon group comprising from 6 to 32 carbon atoms, more preferably from 8 to 30 carbon atoms. carbon.
Préférentiellement, R7 représente un groupement alkyle issu d’un alcool de Guerbet de formule (VII) :
dans laquelle R8 et R9 représentent indépendamment un groupement Cô-C4o-alkyl, de préférence un groupement Cô-C32-alkyl. Preferably, R 7 represents an alkyl group derived from a Guerbet alcohol of formula (VII): in which R 8 and R 9 independently represent a Cô-C4o-alkyl group, preferably a Cô-C 3 2-alkyl group.
De manière également préférée selon l’invention, R7 représente un groupement alkyle ou alcényle, linéaire, comprenant de 6 à 40 atomes de carbone, notamment un groupement cyclohexyle. Selon l’invention, R7 peut également représenter un groupement alkyle issu d’un alcool obtenu par une réaction oxo. Also preferably according to the invention, R 7 represents a linear alkyl or alkenyl group comprising from 6 to 40 carbon atoms, in particular a cyclohexyl group. According to the invention, R 7 can also represent an alkyl group derived from an alcohol obtained by an oxo reaction.
Selon l’invention, R7 peut représenter un groupement aromatique comprenant de 6 à 40 atomes de carbone, préférentiellement de 6 à 32 atomes de carbone, plus préférentiellement de 6 à 30 atomes de carbone. According to the invention, R 7 can represent an aromatic group comprising from 6 to 40 carbon atoms, preferentially from 6 to 32 carbon atoms, more preferentially from 6 to 30 carbon atoms.
Selon l’invention, R7 peut représenter un groupement de formule (VIII) :
dans laquelle R10 représente un groupement hydrocarboné de formule C15H31-S dans laquelle s représente 0, 2, 4 ou 6 ; R10 pouvant ainsi comprendre 0, 1, 2 ou 3 insaturations éthyléniques (double liaison). Un tel groupement de formule (VIII) est avantageusement dérivé du cardanol, et ainsi d’origine bio-ressourcée. According to the invention, R 7 can represent a group of formula (VIII): in which R 10 represents a hydrocarbon group of formula C15H31-S in which s represents 0, 2, 4 or 6; R 10 can thus comprise 0, 1, 2 or 3 ethylenic unsaturations (double bond). Such a group of formula (VIII) is advantageously derived from cardanol, and thus of bio-resourced origin.
Selon l’invention, R7 peut représenter un groupement comprenant de 2 à 5 groupements phényles, tels qu’un groupement tristyrylphényle (TSP) de formule (IX) :
ou un groupement di styryl phényle (DSP) de formule (X) ou de formule (XI):
ou un groupement pentastyrylcumylphényl. According to the invention, R 7 can represent a group comprising from 2 to 5 phenyl groups, such as a tristyrylphenyl (TSP) group of formula (IX): or a distyryl phenyl (DSP) group of formula (X) or of formula (XI): or a pentastyrylcumylphenyl group.
En particulier, R7 représente indépendamment un groupement hydrocarboné linéaire, ramifié ou cyclique, saturé, insaturé ou aromatique comprenant de 6 à 40 atomes de carbone, de préférence un groupement Cô-C4o-alkyl, linéaire ou ramifié, de préférence un groupement Cs-Cso-alkyl, linéaire ou ramifié, un groupement Ce-C -aryl, de préférence un groupement Cs-Cso-aryl, préférentiellement comprenant de 2 à 5 groupements phényles, par exemple un groupement tristyrylphényle. In particular, R 7 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon-based group comprising from 6 to 40 carbon atoms, preferably a linear or branched Cô-C4o-alkyl group, preferably a Cs- Cso-alkyl, linear or branched, a Ce-C-aryl group, preferably a Cs-Cso-aryl group, preferably comprising from 2 to 5 phenyl groups, for example a tristyrylphenyl group.
De manière préférée selon l’invention, q représente un nombre entier ou décimal, avantageusement un nombre entier, supérieur ou égal à 10. Preferably according to the invention, q represents an integer or decimal number, advantageously an integer, greater than or equal to 10.
De manière préférée selon l’invention, la valeur de q est strictement supérieure à la valeur de r. De manière plus préférée selon l’invention, les quantités respectives en poids q et r vont de (q = 100 et r = 0) à (q= 70 et r = 30).
Selon une variante, r est nul et q représente un nombre entier ou décimal, avantageusement un nombre allant de 10 à 100, avantageusement allant de 10 à 60, plus avantageusement allant de 20 à 60, encore plus avantageusement allant de 20 à 40. Preferably according to the invention, the value of q is strictly greater than the value of r. More preferably according to the invention, the respective quantities by weight q and r range from (q=100 and r=0) to (q=70 and r=30). According to a variant, r is zero and q represents an integer or decimal number, advantageously a number ranging from 10 to 100, advantageously ranging from 10 to 60, more advantageously ranging from 20 to 60, even more advantageously ranging from 20 to 40.
Selon une autre variante, chacun de r et de q est différent de 0. En particulier q et r, identiques ou différents, représentent indépendamment un nombre entier ou décimal, avantageusement un nombre allant de 5 à 100, la somme q+r variant de 10 à 150, avantageusement de 10 à 100, plus avantageusement de 10 à 60. De manière préférée selon l’invention, la valeur de q est strictement supérieure à la valeur de r. Dans ce cas et de manière préférée selon l’invention, les quantités respectives en poids q et r vont de (q = 90 et r = 10) à (q= 70 et r = 30). According to another variant, each of r and q is different from 0. In particular q and r, which are identical or different, independently represent an integer or decimal number, advantageously a number ranging from 5 to 100, the sum q+r varying from 10 to 150, advantageously from 10 to 100, more advantageously from 10 to 60. Preferably according to the invention, the value of q is strictly greater than the value of r. In this case and preferably according to the invention, the respective quantities by weight q and r range from (q=90 and r=10) to (q=70 and r=30).
De manière plus préférée selon l’invention, r représente 0. More preferably according to the invention, r represents 0.
De manière avantageuse selon l’invention, le copolymère P peut comprendre de 0,4 à 30 % en poids de monomère (e) par rapport à la quantité totale de monomères. Advantageously according to the invention, the copolymer P can comprise from 0.4 to 30% by weight of monomer (e) relative to the total quantity of monomers.
Le copolymère P selon l’invention peut être préparé selon des méthodes connues en tant que telles. De manière spécifique, le copolymère P selon l’invention est préparé par une réaction de polymérisation mettant en œuvre les différents composés a, b, c et d, éventuellement le composé e, par une réaction de polymérisation radicalaire, par exemple une réaction de polymérisation en émulsion, en dispersion ou en solution. De manière avantageuse, le copolymère P est préparé dans l’eau, de préférence en présence d’au moins un composé tensio-actif, par exemple sodium dodecyl sulfate ou sodium dodecyl laurate. La préparation du copolymère P selon l’invention peut également mettre en œuvre un ou plusieurs composés, notamment au moins un composé initiateur, seul ou en combinaison avec au moins un agent de transfert de chaîne. Comme exemples de composés initiateurs, on peut utiliser un composé choisi parmi les composés initiateurs azoïques (par exemple azo-bis-isobutyronitrile), un composé peroxyde, de préférence peroxyde d’hydrogène, peroxyde de benzoyle, hydroperoxyde de benzoyle et leurs mélanges. On peut également citer les persulfates de métaux alcalins, en particulier le persulfate de sodium et le persulfate de potassium, le persulfate d’ammonium, les peroxydes partiellement hydrosolubles, en particulier le peracide succinique, l’ hydroperoxyde de t-butyle, l’hydroperoxyde de cumyle, les persulfates associés à un ion cuivreux, à un ion ferreux, à un ion sulfite ou à un ion bisulfite et leurs mélanges. Comme exemples d’agents de transfert de chaîne, on peut utiliser les composés mercaptans, en particulier les composés mercaptans comprenant au moins 4 atomes de carbone tels que le butylmercaptan, le
n-octylmercaptan, le n-dodécylmercaptan, le tert-dodécylmercaptan, l’isooctyl 3 -mercaptopropionate. The copolymer P according to the invention can be prepared according to methods known as such. Specifically, the copolymer P according to the invention is prepared by a polymerization reaction implementing the various compounds a, b, c and d, optionally the compound e, by a radical polymerization reaction, for example a polymerization reaction in emulsion, in dispersion or in solution. Advantageously, the copolymer P is prepared in water, preferably in the presence of at least one surfactant compound, for example sodium dodecyl sulphate or sodium dodecyl laurate. The preparation of the copolymer P according to the invention can also implement one or more compounds, in particular at least one initiator compound, alone or in combination with at least one chain transfer agent. As examples of initiator compounds, use may be made of a compound chosen from azo initiator compounds (for example azo-bis-isobutyronitrile), a peroxide compound, preferably hydrogen peroxide, benzoyl peroxide, benzoyl hydroperoxide and mixtures thereof. Mention may also be made of alkali metal persulfates, in particular sodium persulfate and potassium persulfate, ammonium persulfate, partially water-soluble peroxides, in particular succinic peracid, t-butyl hydroperoxide, hydroperoxide cumyl, persulfates associated with a cuprous ion, a ferrous ion, a sulfite ion or a bisulfite ion and mixtures thereof. As examples of chain transfer agents, use may be made of mercaptan compounds, in particular mercaptan compounds comprising at least 4 carbon atoms such as butyl mercaptan, n-octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan, isooctyl 3-mercaptopropionate.
Selon l’invention, le composé initiateur ou générateur de radicaux peut donc être associé à au moins un agent de transfert de polymérisation radicalaire contrôlée, notamment un agent de transfert de type RAFT (reversible addition-fragmentation chain transfer ou polymérisation radicalaire contrôlée par transfert de chaîne réversible par addition-fragmentation). De préférence, la réaction est une réaction de polymérisation radicalaire en émulsion. According to the invention, the radical initiator or generator compound can therefore be associated with at least one controlled radical polymerization transfer agent, in particular a transfer agent of the RAFT type (reversible addition-fragmentation chain transfer or radical polymerization controlled by transfer of reversible chain by addition-fragmentation). Preferably, the reaction is a free radical emulsion polymerization reaction.
Ainsi, de manière préférée selon l’invention, la préparation dans l’eau du copolymère P permet d’obtenir une composition aqueuse polymérique sous la forme d’une émulsion.Thus, preferably according to the invention, the preparation in water of the copolymer P makes it possible to obtain an aqueous polymeric composition in the form of an emulsion.
Les propriétés particulièrement avantageuses du copolymère P selon l’invention permettent de l’utiliser dans de nombreux domaines techniques. En particulier, le copolymère P selon l’invention peut être utilisé pour améliorer les propriétés viscoélastiques et les propriétés suspensives d’une composition, notamment d’une composition aqueuse, de préférence d’une composition aqueuse comprenant des particules. Ainsi, outre le copolymère P, l’invention fournit une composition aqueuse C comprenant au moins un copolymère P selon l’invention. De manière préférée, la composition aqueuse C selon l’invention comprend au moins un copolymère P selon l’invention et des particules solides, liquides ou gazeuses, et éventuellement un composé liant. The particularly advantageous properties of the copolymer P according to the invention allow it to be used in many technical fields. In particular, the copolymer P according to the invention can be used to improve the viscoelastic properties and the suspensive properties of a composition, in particular of an aqueous composition, preferably of an aqueous composition comprising particles. Thus, in addition to the copolymer P, the invention provides an aqueous composition C comprising at least one copolymer P according to the invention. Preferably, the aqueous composition C according to the invention comprises at least one copolymer P according to the invention and solid, liquid or gaseous particles, and optionally a binder compound.
De manière préférée, la composition C selon l’invention comprend de 0,1 à 5 % en poids de copolymère P. De manière plus préférée, la composition C selon l’invention comprend de 0,5 à 3 % en poids de copolymère P. Preferably, composition C according to the invention comprises from 0.1 to 5% by weight of copolymer P. More preferably, composition C according to the invention comprises from 0.5 to 3% by weight of copolymer P .
De manière préférée pour la composition C selon l’invention, les particules sont des particules d’un produit choisi parmi un produit cosmétique, un produit phytosanitaire, un engrais, un produit de recouvrement. De manière plus préférée pour la composition C selon l’invention, la composition aqueuse C est une composition de vernis comprenant un copolymère P, des particules d’un pigment et un composé liant sous forme de latex, éventuellement un composé dispersant de pigment. De préférence selon l’invention, le composé liant possède une température de transition vitreuse, calculée au moyen de l’équation de Flory-Fox, qui est la même +/-10°C que la température de transition vitreuse du copolymère P. De manière également préférée selon l’invention, le composé liant possède une température de transition vitreuse, calculée au moyen de l’équation de Flory-Fox, qui est la même +/-5°C que la température de transition vitreuse du copolymère P. Selon l’invention, le composé liant préféré est un composé acrylique, un composé alkyde
ou un composé alkyde-uréthane ou encore un composé styrène-acrylique ou un composé styrène-butadiène. Preferably for composition C according to the invention, the particles are particles of a product chosen from a cosmetic product, a phytosanitary product, a fertilizer, a coating product. More preferably for composition C according to the invention, aqueous composition C is a varnish composition comprising a copolymer P, particles of a pigment and a binder compound in latex form, optionally a pigment-dispersing compound. Preferably according to the invention, the binder compound has a glass transition temperature, calculated using the Flory-Fox equation, which is the same +/-10° C. as the glass transition temperature of the copolymer P. also preferably according to the invention, the binder compound has a glass transition temperature, calculated using the Flory-Fox equation, which is the same +/- 5° C. as the glass transition temperature of the copolymer P. According to the invention, the preferred binder compound is an acrylic compound, an alkyd compound or an alkyd-urethane compound or a styrene-acrylic compound or a styrene-butadiene compound.
Les propriétés du copolymère P selon l’invention permettent de l’utiliser dans des conditions qui peuvent varier de manière importante. En particulier, les propriétés du copolymère P peuvent être mises en œuvre à des valeurs de pH variables. De manière préférée, la composition aqueuse C selon l’invention a un pH allant de 3 à 13, de préférence un pH allant de 5 à 13. De manière également préférée, le pH de la composition aqueuse C va de 4 à 8 ou de 5 à 7. The properties of the copolymer P according to the invention allow it to be used under conditions which can vary significantly. In particular, the properties of the copolymer P can be implemented at variable pH values. Preferably, the aqueous composition C according to the invention has a pH ranging from 3 to 13, preferably a pH ranging from 5 to 13. Also preferably, the pH of the aqueous composition C ranges from 4 to 8 or from 5 to 7.
L’invention concerne également une méthode de préparation d’une composition aqueuse C, viscoél asti que et suspensive comprenant l’introduction d’au moins un copolymère P selon l’invention et l’agitation de la composition C. Le copolymère P permet d’améliorer les propriétés de la composition C selon l’invention. En particulier, le copolymère P permet d’améliorer la stabilité de cette composition, notamment pour une composition C de vernis. Ainsi, l’invention concerne également une méthode de stabilisation d’une composition C de vernis comprenant l’introduction dans une composition aqueuse C de base de vernis d’au moins un copolymère P selon l’invention. De manière préférée, la composition C de base de vernis comprend un composé liant sous la forme d’un latex dont la température de transition vitreuse est la même +/-10°C que la température de transition vitreuse du copolymère P, calculée au moyen de l’équation de Flory-Fox. De manière également préférée pour cette méthode, le composé liant possède une température de transition vitreuse, calculée au moyen de l’équation de Flory-Fox, qui est la même +/-5°C que la température de transition vitreuse du copolymère P. The invention also relates to a method for preparing an aqueous composition C, viscoelastic and suspending, comprising the introduction of at least one copolymer P according to the invention and the stirring of the composition C. The copolymer P makes it possible to improve the properties of composition C according to the invention. In particular, the copolymer P makes it possible to improve the stability of this composition, in particular for a varnish composition C. Thus, the invention also relates to a method for stabilizing a varnish composition C comprising the introduction into an aqueous varnish base composition C of at least one copolymer P according to the invention. Preferably, the varnish base composition C comprises a binder compound in the form of a latex, the glass transition temperature of which is the same +/-10° C. as the glass transition temperature of the copolymer P, calculated by means of of the Flory-Fox equation. Also preferably for this method, the binder compound has a glass transition temperature, calculated using the Flory-Fox equation, which is the same +/-5°C as the glass transition temperature of the copolymer P.
Le copolymère P selon l’invention possède des propriétés particulièrement avantageuses pour contrôler différentes composantes de la rhéologie d’une composition aqueuse. En particulier, le copolymère P selon l’invention permet de contrôler le seuil d’écoulement d’une composition aqueuse. The copolymer P according to the invention has particularly advantageous properties for controlling various components of the rheology of an aqueous composition. In particular, the copolymer P according to the invention makes it possible to control the flow threshold of an aqueous composition.
Le seuil d’écoulement correspond à la valeur de la contrainte de cisaillement appliquée à une composition aqueuse qui entraîne un écoulement de cette composition. En l’absence de contrainte suffisante, la viscosité de cette composition aqueuse empêche son écoulement spontané à une échelle de temps acceptable. The yield stress corresponds to the value of the shear stress applied to an aqueous composition which causes this composition to flow. In the absence of sufficient constraint, the viscosity of this aqueous composition prevents its spontaneous flow on an acceptable time scale.
Ainsi, l’invention fournit également une méthode de contrôle du seuil d’écoulement d’une composition aqueuse comprenant l’introduction dans la composition aqueuse d’au moins un copolymère P selon l’invention. De manière préférée, le seuil d’écoulement de cette composition aqueuse, mesuré selon la méthode décrite dans les exemples, est supérieur à
0,1 Pa, plus préférentiellement supérieur à 0,5 Pa ou bien supérieur à 2 Pa, de préférence supérieur 4 Pa. Thus, the invention also provides a method for controlling the yield point of an aqueous composition comprising the introduction into the aqueous composition of at least one copolymer P according to the invention. Preferably, the yield point of this aqueous composition, measured according to the method described in the examples, is greater than 0.1 Pa, more preferably greater than 0.5 Pa or else greater than 2 Pa, preferably greater than 4 Pa.
De manière plus préférée, la composition C selon l’invention comprend de 0,1 à 5 % en poids de copolymère P et possède un seuil d’écoulement supérieur à 0,1 Pa, plus préférentiellement supérieur à 0,5 Pa, ou bien supérieur à 2 Pa, de préférence supérieur à 4 Pa. De manière également plus préférée, la composition C selon l’invention comprend de 0,5 à 3 % en poids de copolymère P et possède un seuil d’écoulement supérieur à 0, 1 Pa, plus préférentiellement supérieur à 0,5 Pa, ou bien supérieur à 2 Pa, de préférence supérieur à 4 Pa. More preferably, composition C according to the invention comprises from 0.1 to 5% by weight of copolymer P and has a yield point greater than 0.1 Pa, more preferably greater than 0.5 Pa, or else greater than 2 Pa, preferably greater than 4 Pa. Also more preferably, composition C according to the invention comprises from 0.5 to 3% by weight of copolymer P and has a yield point greater than 0.1 Pa, more preferably greater than 0.5 Pa, or else greater than 2 Pa, preferably greater than 4 Pa.
Selon l’invention, les caractéristiques particulières, avantageuses ou préférées du copolymère P selon l’invention définissent des compositions selon l’invention et des méthodes selon l’invention qui sont des compositions et des méthodes particulières, avantageuses ou préférées selon l’invention. According to the invention, the particular, advantageous or preferred characteristics of the copolymer P according to the invention define compositions according to the invention and methods according to the invention which are particular, advantageous or preferred compositions and methods according to the invention.
Les exemples qui suivent permettent d’illustrer les différents aspects de l’invention. The following examples illustrate the different aspects of the invention.
EXEMPLES EXAMPLES
Exemple 1 : préparation et caractérisation de copolymères selon l’invention Example 1: preparation and characterization of copolymers according to the invention
Les réactions de préparation de copolymères P selon l’invention ont été réalisées dans un réacteur cylindrique en verre d’un volume utile de 1 L équipé d’une agitation mécanique de type ancre et d’un système de chauffage par bain d’huile. Une agitation est maintenue pendant toute la durée de la préparation. The reactions for the preparation of copolymers P according to the invention were carried out in a cylindrical glass reactor with a working volume of 1 L equipped with an anchor-type mechanical stirrer and an oil bath heating system. Stirring is maintained throughout the duration of the preparation.
Les monomères suivants ont été mis en œuvre : The following monomers were used:
- monomère a : - monomer a:
• composé (al), acide acrylique (AA), • compound (al), acrylic acid (AA),
• composé (a2), acide méthacrylique (AMA), • compound (a2), methacrylic acid (AMA),
- monomère b : composé (bl), acrylate d’éthyle (AE), - monomer b: compound (bl), ethyl acrylate (AE),
- composé c : composé (cl), sel de sodium de l’acide 2-acrylamido-2-méthylpropane sulfonique (AMPS), - compound c: compound (cl), sodium salt of 2-acrylamido-2-methylpropane sulphonic acid (AMPS),
- composé réticulant d : - cross-linking compound d:
• composé (dl), éthylène glycol diméthacrylate (EDMA), • compound (dl), ethylene glycol dimethacrylate (EDMA),
• composé (d2), diallyl phthalate (DAP), • compound (d2), diallyl phthalate (DAP),
• composé (d3), composé de formule IV dans laquelle R3 représente H, L3
représente un groupement CH2CH2 et n représente 1, • compound (d3), compound of formula IV in which R 3 represents H, L 3 represents a CH2CH2 group and n represents 1,
• composé (d4), triallyl pentaerythritol (APE), • compound (d4), triallyl pentaerythritol (APE),
• composé (d5), triacrylate de triméthylolpropane (TMPTA), • compound (d5), trimethylolpropane triacrylate (TMPTA),
- monomère hydrophobe e : composé (el) de formule VI dans laquelle R6 représente un groupement méthacrylate, q représente 25, OE représente un groupement CH2CH2O, r représente 0 et R7 représente un groupement de formule VII dans laquelle R8 représente un groupement Cô-alkyl linéaire et R9 représente un groupement Cio-alkyl linéaire. - hydrophobic monomer e: compound (el) of formula VI in which R 6 represents a methacrylate group, q represents 25, OE represents a CH2CH2O group, r represents 0 and R 7 represents a group of formula VII in which R 8 represents a group Linear C6-alkyl and R 9 represents a linear Cio-alkyl group.
Préparation et caractérisation du copolymère (PI) selon l’invention Preparation and characterization of the copolymer (PI) according to the invention
Dans le réacteur, on introduit 460 g d’eau désionisée et 6,48 g de sodium dodecyl sulfate. Dans un premier bêcher en verre et selon les proportions présentées dans le tableau 1, on pèse 102,14 g de monomère (al), 160,20 g de monomère (bl), 4,57 g de composé (dl), 20,05 g de monomère (el), 3,38 g de sodium dodecyl sulfate et 124 g d’eau désionisée. Dans un second bêcher en verre, on pèse 0,914 g de persulfate d’ammonium que l’on dissout dans 10 g d’eau désionisée. Dans un troisième bêcher en verre, on pèse 0,100 g de métabisulfite de sodium que l’on dissout dans 10 g d’eau désionisée. Dans un quatrième récipient, de type seringue jetable, on pèse 5,27 g de composé (cl) à 50 % en poids dans l’eau. 460 g of deionized water and 6.48 g of sodium dodecyl sulphate are introduced into the reactor. In a first glass beaker and according to the proportions presented in Table 1, 102.14 g of monomer (al), 160.20 g of monomer (bl), 4.57 g of compound (dl), 20, 05 g of monomer (el), 3.38 g of sodium dodecyl sulphate and 124 g of deionized water. In a second glass beaker, 0.914 g of ammonium persulfate is weighed and dissolved in 10 g of deionized water. In a third glass beaker, weigh 0.100 g of sodium metabisulphite and dissolve it in 10 g of deionized water. In a fourth container, of the disposable syringe type, 5.27 g of compound (cl) at 50% by weight in water are weighed.
On chauffe le contenu du réacteur à une température de 76°C ± 2°C. The contents of the reactor are heated to a temperature of 76°C ± 2°C.
En 2 heures et 30 minutes, les réactifs des 4 récipients sont introduits dans le réacteur de polymérisation à une température de 76°C ± 2°C. Les pompes sont rincées avec de l’eau désionisée. Ensuite, 0,3 g de persulfate d’ammonium dissout dans 20 g d’eau désionisée sont introduits dans le réacteur en 1 heure. In 2 hours and 30 minutes, the reagents from the 4 containers are introduced into the polymerization reactor at a temperature of 76°C ± 2°C. The pumps are flushed with deionized water. Then, 0.3 g of ammonium persulfate dissolved in 20 g of deionized water are introduced into the reactor over 1 hour.
Puis, on cuit pendant 1 heure avant de laisser le milieu refroidir puis de le filtrer. Then, it is cooked for 1 hour before allowing the medium to cool and then filtering it.
On obtient un copolymère (PI) à 30,6 % en poids d’extrait sec (ES, mesuré avec une balance à micro-ondes). Sa température de transition vitreuse (Tg) est calculée grâce à l’équation de Flory-Fox. La composition et les caractéristiques du copolymère (PI) sont présentées dans le tableau 1. A copolymer (PI) with 30.6% by weight of solids content (SD, measured with a microwave balance) is obtained. Its glass transition temperature (Tg) is calculated using the Flory-Fox equation. The composition and characteristics of the copolymer (PI) are shown in Table 1.
Préparation et caractérisation des copolymères (P2) à (P I 4) selon l’invention Preparation and characterization of the copolymers (P2) to (P I 4) according to the invention
Ces polymères sont préparés de manière analogue au copolymère (PI). Leurs compositions et leurs caractéristiques sont présentées dans le tableau 1.
These polymers are prepared analogously to the copolymer (PI). Their compositions and characteristics are shown in Table 1.
Tableau 1 Table 1
Exemple 2 : Préparation et caractérisation des propriétés de compositions aqueuses Cl à C3 selon l’invention Example 2: Preparation and characterization of the properties of aqueous compositions C1 to C3 according to the invention
Le copolymère PI préparé selon l’exemple 1 est mélangé à de l’eau désionisée en une quantité en poids sec de 1 % puis on ajoute une solution aqueuse de soude (50 % en poids) afin de neutraliser totalement la composition. On obtient la composition aqueuse Cl selon l’invention. Les compositions aqueuses C2 et C3 selon l’invention sont préparées de manière analogue à partir des copolymères P2 et P3 selon l’invention. The PI copolymer prepared according to example 1 is mixed with deionized water in an amount by dry weight of 1% then an aqueous solution of sodium hydroxide (50% by weight) is added in order to completely neutralize the composition. The aqueous composition C1 according to the invention is obtained. The aqueous compositions C2 and C3 according to the invention are prepared analogously from the copolymers P2 and P3 according to the invention.
On mesure ensuite la viscosité Brookfield à 25°C et à 100 tour/min de ces compositions au moyen d’un viscosimètre Brookfield DV1 équipé d’un mobile adapté à la plage de viscosité de la composition. On mesure également le seuil d’écoulement de ces compositions qui est la contrainte appliquée qui entraîne l’écoulement de la composition aqueuse. On met œuvre une rampe de contrainte variant de 0,01 à 1 000 Pa durant une période de 3 000 secondes avec un temps d’équilibrage de 30 secondes entre chaque mesure. La mesure de la contrainte de seuil d’écoulement a été réalisée à 25°C au moyen d’un rhéomètre à contrainte imposée Haake Mars III (ThermoFisher Scientific) équipé d’une géométrie de type cône-plan CP60-1/S (diamètre de 60 mm, angle de troncature de 1°) puis en utilisant le traitement par le logiciel RheoWin Data Manager. Les résultats obtenus sont présentés dans le tableau 2.
The Brookfield viscosity is then measured at 25° C. and at 100 revolutions/min of these compositions by means of a Brookfield DV1 viscometer equipped with a rotor adapted to the viscosity range of the composition. The flow threshold of these compositions is also measured, which is the applied stress which causes the flow of the aqueous composition. A stress ramp varying from 0.01 to 1000 Pa is implemented over a period of 3000 seconds with an equilibration time of 30 seconds between each measurement. Yield stress was measured at 25°C using a Haake Mars III imposed stress rheometer (ThermoFisher Scientific) equipped with a CP60-1/S cone-plane type geometry (diameter of 60 mm, truncation angle of 1°) then using processing by the RheoWin Data Manager software. The results obtained are shown in Table 2.
Tableau 2 Table 2
On détermine également la viscoélasticité des compositions aqueuses Cl, Cl et C3 selon l’invention en fonction de la fréquence à faibles déformations. La déformation imposée est sinusoïdale de forme y = yO sin(cot) avec yO fixé à 1 %. La fréquence co suit une variation logarithmique des hautes fréquences aux basses fréquences (de 100 à 0,01 Hz). La réponse en contrainte mesurée est de type o = oO sin(cot+ô) avec ô le décalage de phase. Le cas échéant, le signal de la contrainte peut également être décomposé en partie en phase (réponse solide) et la part en opposition de phase (réponse liquide). Ces deux contributions sont exprimées dans la formule G = yOG’sin(cot) + yOG”cos(cot) dans laquelle G’ représente le module de stockage (ou module élastique) et G” représente le module de perte (ou module visqueux). The viscoelasticity of the aqueous compositions Cl, Cl and C3 according to the invention is also determined as a function of the frequency at low deformations. The strain imposed is sinusoidal of form y = yO sin(cot) with yO fixed at 1%. The frequency co follows a logarithmic variation from high frequencies to low frequencies (from 100 to 0.01 Hz). The stress response measured is of the type o=oO sin(cot+δ) with δ the phase shift. If necessary, the stress signal can also be broken down into the phase part (solid response) and the phase opposition part (liquid response). These two contributions are expressed in the formula G = yOG'sin(cot) + yOG”cos(cot) in which G' represents the storage modulus (or elastic modulus) and G” represents the loss modulus (or viscous modulus) .
On détermine ainsi le caractère solide ou liquide de l’échantillon de composition aqueuse. Lorsque G’ > G”, alors l’échantillon est solide. Lorsque G” > G’, alors l’échantillon est liquide. On peut définir tan ô = G” / G’ qui est l’angle de perte. Si tan ô = 0, le comportement est solide-élastique, si tan ô = 1, le comportement est visqueux. Lorsque 0 < tan ô < 1, la composition évaluée possède un comportement viscoélastique. Les résultats obtenus sont présentés dans le tableau 3.
The solid or liquid character of the sample of aqueous composition is thus determined. When G'> G”, then the sample is solid. When G” >G', then the sample is liquid. We can define tan ô = G” / G' which is the loss angle. If tan ô = 0, the behavior is solid-elastic, if tan ô = 1, the behavior is viscous. When 0 < tan δ < 1, the composition evaluated has a viscoelastic behavior. The results obtained are shown in Table 3.
Tableau 3 Table 3
Les copolymères selon l’invention permettent donc d’épaissir des compositions aqueuses de manière importante. Les compositions aqueuses obtenues possèdent un seuil d’écoulement élevé. De plus, la valeur de tangente ô de ces compositions aqueuses selon l’invention se situe systématiquement entre 0 et 1 démontrant ainsi leur caractère viscoélastique. Ces propriétés sont obtenues en l’absence d’acide méthacrylique lors de la préparation des copolymères selon l’invention.
The copolymers according to the invention therefore make it possible to thicken aqueous compositions significantly. The aqueous compositions obtained have a high flow threshold. In addition, the tangent value δ of these aqueous compositions according to the invention is systematically between 0 and 1, thus demonstrating their viscoelastic character. These properties are obtained in the absence of methacrylic acid during the preparation of the copolymers according to the invention.
Claims
1. Copolymère P préparé en l’absence d’acide méthacrylique, par au moins une réaction de polymérisation : a. d'au moins un monomère (a) anionique choisi parmi l’acide acrylique, un sel d’acide acrylique, les oligomères de l’acide acrylique, les sels d’oligomères de l’acide acrylique et leurs combinaisons ; b. d’au moins un monomère (b) non-ionique choisi parmi le styrène, les esters en Ci- Cs d’un acide choisi parmi acide acrylique, acide méthacrylique et leurs combinaisons ; c. d’au moins un composé (c) choisi parmi acide 2-acrylamido-2-méthylpropane sulfonique, méthacrylate de 2-sulfoéthyl, méthallyl sulfonate de sodium, styrène sulfonate, leurs sels et leurs combinaisons ; d. d’au moins un composé (d) réticulant ou comprenant au moins deux insaturations oléfiniques polymérisables. 1. Copolymer P prepared in the absence of methacrylic acid, by at least one polymerization reaction: a. at least one anionic monomer (a) chosen from acrylic acid, a salt of acrylic acid, oligomers of acrylic acid, salts of oligomers of acrylic acid and combinations thereof; b. at least one nonionic monomer (b) chosen from styrene, Ci-Cs esters of an acid chosen from acrylic acid, methacrylic acid and combinations thereof; vs. at least one compound (c) chosen from 2-acrylamido-2-methylpropane sulphonic acid, 2-sulphoethyl methacrylate, sodium methallyl sulphonate, styrene sulphonate, their salts and their combinations; d. of at least one compound (d) crosslinking or comprising at least two polymerizable olefinic unsaturations.
2. Copolymère P selon la revendication 1 pour lequel le monomère (a) est l’acide acrylique ou un mélange d’oligomères de l’acide acrylique de formule (I) :
dans laquelle m est un nombre entier ou décimal allant de 1 à 10, de préférence allant de 2 à 4. 2. Copolymer P according to claim 1 for which the monomer (a) is acrylic acid or a mixture of oligomers of acrylic acid of formula (I): in which m is an integer or decimal number ranging from 1 to 10, preferably ranging from 2 to 4.
3. Copolymère P selon l’une des revendications 1 ou 2 pour lequel le monomère (b) est choisi parmi : 3. Copolymer P according to one of claims 1 or 2 for which the monomer (b) is chosen from:
- acrylate d’ alkyl e, en particulier acrylate de Ci-Cs-alkyl, préférentiellement acrylate de Ci-C4-alkyl, plus préférentiellement acrylate de méthyle, acrylate d’éthyle, acrylate de propyle, acrylate d’isobutyle, acrylate de n-butyle, méthacrylate d’alkyle, en particulier méthacrylate de Ci-Cs-alkyl, préférentiellement méthacrylate de Ci-C4-alkyl, plus préférentiellement méthacrylate de méthyle, méthacrylate d’éthyle, méthacrylate de propyle, méthacrylate d’isobutyle, méthacrylate de n-butyle,
acrylate d’aryle, de préférence phényl acrylate, benzyl acrylate, phénoxy éthyl acryl ate, - alkyl acrylate, in particular Ci-Cs-alkyl acrylate, preferably Ci-C4-alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n- butyl, alkyl methacrylate, in particular Ci-Cs-alkyl methacrylate, preferably Ci-C4-alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, n- butyl, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxy ethyl acryl ate,
- méthacrylate d’aryle, de préférence phénylméthacrylate, benzylméthacrylate, phénoxyéthylméthacrylate et - aryl methacrylate, preferably phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate and
- leurs combinaisons. - their combinations.
4. Copolymère P selon l’une des revendications 1 à 3 pour lequel le monomère (c) est choisi parmi l’acide 2-acrylamido-2-méthylpropane sulfonique (AMPS) et ses sels de sodium ou d’ammonium. 4. Copolymer P according to one of claims 1 to 3 for which the monomer (c) is chosen from 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its sodium or ammonium salts.
5. Copolymère P selon l’une des revendications 1 à 4 pour lequel le composé (d) est choisi parmi les monomères aromatiques polyinsaturés comme divinylbenzene, divinyl naphthalène et trivinylbenzene, les monomères alicycliques polyinsaturés par exemple 1, 2, 4-trivinyl cyclohexane, esters d’acide phthalique difonctionnels comme diallyl phthalate, éthers polyalkenyl tels que triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose et triméthylolpropane diallyl éther, esters polyinsaturés de polyalcohols ou de polyacides comme 1,6-hexanediol di(méth)acrylate, tétraméthylène tri(méth)acrylate, allyl acrylate, diallyl itaconate, diallyl fumarate, diallyl maléate, triméthylolpropane tri(méth)acrylate, triméthylolpropane di(méth)acrylate, poly(alkylèneoxy) glycol di(méth)acrylate et polyéthylène glycol di(méth)acrylate, alkylène bisacrylamides comme méthylènebisacrylamide et propylène bisacrylamide, dérivés hydroxy ou carboxy de méthylène bis-acrylamide comme N,N'-bisméthylol méthylène bisacrylamide, polyalkylèneglycol di(méth)acrylates comme éthylèneglycol di(méth)acrylate, diéthylèneglycol di(méth)acrylate, triéthylèneglycol di(méth)acrylate, allyl méthacrylate, éthylène glycol diméthacrylate, butylène glycol diméthacrylate, pentaerythritol di-, tri- et tetra-acrylates, poly(alkylèneoxy)glycol di(méth)acrylates tels que polyéthylène glycol diacrylate, bisphenol A diacrylate, butanediol diméthacrylate, 2,2-diméthylpropanediol diméthacrylate, phénylène diacrylate, un composé réticulant dissymétrique et leurs combinaisons. 5. Copolymer P according to one of claims 1 to 4 for which compound (d) is chosen from polyunsaturated aromatic monomers such as divinylbenzene, divinyl naphthalene and trivinylbenzene, polyunsaturated alicyclic monomers, for example 1, 2, 4-trivinyl cyclohexane, difunctional phthalic acid esters such as diallyl phthalate, polyalkenyl ethers such as triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose and trimethylolpropane diallyl ether, polyunsaturated esters of polyalcohols or polyacids such as 1,6-hexanediol di(meth)acrylate, tetramethylene tri(meth)acrylate, allyl acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, poly(alkyleneoxy) glycol di(meth)acrylate and polyethylene glycol di(meth)acrylate , alkylene bisacrylamides such as methylenebisacrylamide and propylene bisacrylamide, hydroxy or carboxy derivatives of methylene bisacrylamide such as N,N' -bismethylol methylene bisacrylamide, polyalkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, pentaerythritol di-, tri- and tetra-acrylates, poly(alkyleneoxy)glycol di(meth)acrylates such as polyethylene glycol diacrylate, bisphenol A diacrylate, butanediol dimethacrylate, 2,2-dimethylpropanediol dimethacrylate, phenylene diacrylate, an unsymmetrical crosslinking compound and combinations thereof.
6. Copolymère P selon l’une des revendications 1 à 5 comprenant : 6. Copolymer P according to one of claims 1 to 5 comprising:
- de 25 à 60 % en poids de monomère (a), - from 25 to 60% by weight of monomer (a),
- de 39,89 à 59 % en poids de monomère (b), - from 39.89 to 59% by weight of monomer (b),
- de 0, 1 à 8 % en poids de monomère (c) et
- de 0,01 à 8 % en poids de monomère (d). - from 0.1 to 8% by weight of monomer (c) and - from 0.01 to 8% by weight of monomer (d).
7. Copolymère P selon l’une des revendications 1 à 6 ayant une température de transition vitreuse (Tg), calculée au moyen de l’équation de Flory-Fox, inférieure à 60°C, de préférence inférieure à 30°C. 7. Copolymer P according to one of claims 1 to 6 having a glass transition temperature (Tg), calculated using the Flory-Fox equation, of less than 60°C, preferably less than 30°C.
8. Copolymère P selon l’une des revendications 1 à 7 totalement ou partiellement neutralisé, de préférence au moyen d’un composé choisi parmi NaOH, KOH, LiOH, les dérivés ammonium, l’ammoniaque, les bases aminées, par exemple triéthanolamine, aminométhylpropanol ou 2-amino-2-méthyl-propanol (AMP) et leurs combinaisons. 8. Copolymer P according to one of claims 1 to 7 totally or partially neutralized, preferably by means of a compound chosen from NaOH, KOH, LiOH, ammonium derivatives, ammonia, amino bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and combinations thereof.
9. Copolymère P selon l’une des revendications 1 à 8 préparé par une réaction de polymérisation mettant également en œuvre au moins un monomère (e) hydrophobe comprenant une insaturation oléfinique polymérisable, des groupements polyalkylèneglycols et un groupement terminal hydrophobe, de préférence un groupement hydrocarboné linéaire, ramifié ou cyclique, saturé, insaturé ou aromatique, comprenant de 6 à 40 atomes de carbone. 9. Copolymer P according to one of claims 1 to 8 prepared by a polymerization reaction also using at least one hydrophobic monomer (e) comprising polymerizable olefinic unsaturation, polyalkylene glycol groups and a hydrophobic terminal group, preferably a group linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon, comprising from 6 to 40 carbon atoms.
10. Copolymère P selon la revendication 9 pour lequel le monomère (e) est un composé de formule (VI) : 10. Copolymer P according to claim 9 for which the monomer (e) is a compound of formula (VI):
R6-(OE)q-(OP)r-R7 R 6 -(OE) q -(OP) r -R 7
(VI) dans laquelle : (VI) in which:
- q et r, identiques ou différents, représentent indépendamment 0 ou un nombre entier ou décimal, inférieur à 150, la somme q+r allant de 5 à 150, de préférence la somme q+r varie de 10 à 150, avantageusement de 10 à 100, plus avantageusement de 10 à 60, - q and r, identical or different, independently represent 0 or an integer or decimal number, less than 150, the sum q+r ranging from 5 to 150, preferably the sum q+r varies from 10 to 150, advantageously from 10 to 100, more preferably from 10 to 60,
- OE représente un groupement CH2CH2O, - OE represents a CH2CH2O group,
- OP représente indépendamment un groupement choisi parmi CH(CH3)CH2O et CH2CH(CH3)O, - OP independently represents a group chosen from CH(CH3)CH2O and CH 2 CH(CH 3 )O,
- R6 représente un groupement comprenant au moins une insaturation oléfinique polymérisable, de préférence un groupement choisi parmi acrylate, méthacrylate, acryluréthane, méthacryluréthane, vinyl, allyl, méthallyl, isoprényl, un groupement uréthane insaturé, notamment acryluréthane, méthacryluréthane,
22 a-a'-diméthyl-isopropenyl-benzyluréthane, allyluréthane, plus préférentiellement un groupement choisi parmi acrylate, méthacrylate, acryluréthane, méthacryluréthane, vinyl, allyl, méthallyl et isoprényl, encore plus préférentiellement un groupement méthacrylate,- R 6 represents a group comprising at least one polymerizable olefinic unsaturation, preferably a group chosen from acrylate, methacrylate, acryl urethane, methacryl urethane, vinyl, allyl, methallyl, isoprenyl, an unsaturated urethane group, in particular acryl urethane, methacryl urethane, 22 a-a'-dimethyl-isopropenyl-benzylurethane, allylurethane, more preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl and isoprenyl, even more preferably a methacrylate group,
- R7 représente indépendamment un groupement hydrocarboné linéaire, ramifié ou cyclique, saturé, insaturé ou aromatique comprenant de 6 à 40 atomes de carbone, de préférence un groupement hydrocarboné comprenant de 6 à 32 atomes de carbone, plus préférentiellement de 8 à 30 atomes de carbone. - R 7 independently represents a linear, branched or cyclic, saturated, unsaturated or aromatic hydrocarbon group comprising from 6 to 40 carbon atoms, preferably a hydrocarbon group comprising from 6 to 32 carbon atoms, more preferably from 8 to 30 carbon atoms. carbon.
11. Copolymère P selon l’une des revendications 1 à 10 comprenant de 0,4 à 30 % en poids de monomère (e) par rapport à la quantité totale de monomères. 11. Copolymer P according to one of claims 1 to 10 comprising from 0.4 to 30% by weight of monomer (e) relative to the total amount of monomers.
12. Composition aqueuse C comprenant au moins un copolymère P selon l’une des revendications 1 à 11 et des particules solides, liquides ou gazeuses, et éventuellement un composé liant. 12. Aqueous composition C comprising at least one copolymer P according to one of claims 1 to 11 and solid, liquid or gaseous particles, and optionally a binder compound.
13. Composition C selon la revendication 12 comprenant de 0,1 à 5 % en poids, de préférence de 0,5 à 3 % en poids, de copolymère P. 13. Composition C according to claim 12 comprising from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight, of copolymer P.
14. Composition C selon l’une des revendications 12 ou 13 pour laquelle les particules sont des particules d’un produit choisi parmi un produit cosmétique, un produit phytosanitaire, un engrais, un produit de recouvrement. 14. Composition C according to one of claims 12 or 13 for which the particles are particles of a product chosen from a cosmetic product, a phytosanitary product, a fertilizer, a covering product.
15. Composition C selon l’une des revendications 12 à 14 qui est une composition aqueuse C de vernis comprenant un copolymère P selon l’une des revendications 1 à 11, des particules d’un pigment et un composé liant sous forme de latex, éventuellement un composé dispersant de pigment ; de préférence un composé liant dont la température de transition vitreuse, calculée au moyen de l’équation de Flory-Fox, est la même +/-10°C que la température de transition vitreuse du copolymère P. 15. Composition C according to one of Claims 12 to 14, which is an aqueous varnish composition C comprising a copolymer P according to one of Claims 1 to 11, particles of a pigment and a binder compound in latex form, optionally a pigment dispersing compound; preferably a binder compound whose glass transition temperature, calculated using the Flory-Fox equation, is the same +/-10°C as the glass transition temperature of the copolymer P.
16. Composition C selon l’une des revendications 12 à 15 qui a un pH allant de 3 à 13, de préférence un pH allant de 5 à 13 ou un pH allant de 4 à 8 ou encore un pH allant de 5 à 7.
23 16. Composition C according to one of claims 12 to 15 which has a pH ranging from 3 to 13, preferably a pH ranging from 5 to 13 or a pH ranging from 4 to 8 or else a pH ranging from 5 to 7. 23
17. Méthode de préparation d’une composition aqueuse C, viscoél asti que et suspensive comprenant l’introduction d’au moins un copolymère P selon l’une des revendications 1 à 11 et l’agitation de la composition C. 17. Method for preparing an aqueous composition C, viscoelastic and suspending, comprising the introduction of at least one copolymer P according to one of claims 1 to 11 and the stirring of composition C.
18. Méthode de stabilisation d’une composition C de vernis comprenant l’introduction dans une composition aqueuse C de base de vernis d’au moins un copolymère P selon l’une des revendications 1 à 11, de préférence dans une composition C de base de vernis comprenant un composé liant sous la forme d’un latex dont la température de transition vitreuse est la même +/-10°C que la température de transition vitreuse du copolymère P, calculée au moyen de l’équation de Flory-Fox. 18. Method for stabilizing a varnish composition C comprising the introduction into an aqueous varnish base composition C of at least one copolymer P according to one of claims 1 to 11, preferably in a base composition C varnish comprising a binder compound in the form of a latex whose glass transition temperature is the same +/-10° C. as the glass transition temperature of the copolymer P, calculated using the Flory-Fox equation.
19. Méthode de contrôle du seuil d’écoulement d’une composition aqueuse comprenant l’introduction dans la composition aqueuse d’au moins un copolymère P selon l’une des revendications 1 à 11, de préférence le seuil d’écoulement de cette composition aqueuse, mesuré selon la méthode comprenant la mesure de la contrainte de seuil d’écoulement qui est réalisée à 25°C au moyen d’un rhéomètre à contrainte imposée Haake Mars III (ThermoFisher Scientific) équipé d’une géométrie de type cône-plan CP60-1/S (diamètre de 60 mm, angle de troncature de 1°) puis en utilisant le traitement par le logiciel RheoWin Data Manager, est supérieur à 0,1 Pa, plus préférentiellement supérieur à 0,5 Pa ou bien supérieur à 2 Pa, de préférence supérieur à 4 Pa.
19. Method for controlling the yield point of an aqueous composition comprising the introduction into the aqueous composition of at least one copolymer P according to one of claims 1 to 11, preferably the yield point of this composition aqueous, measured according to the method comprising the measurement of the yield point stress which is carried out at 25° C. by means of a Haake Mars III imposed stress rheometer (ThermoFisher Scientific) equipped with a cone-plane type geometry CP60-1/S (60 mm diameter, 1° truncation angle) then using RheoWin Data Manager software processing, is greater than 0.1 Pa, more preferably greater than 0.5 Pa or better than 2 Pa, preferably greater than 4 Pa.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2012936A FR3117116B1 (en) | 2020-12-09 | 2020-12-09 | VISCOELASTIC AND SUSPENSIVE COPOLYMER |
| PCT/FR2021/000143 WO2022123127A1 (en) | 2020-12-09 | 2021-12-07 | Copolymer having viscoelastic and suspensive properties |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4259671A1 true EP4259671A1 (en) | 2023-10-18 |
Family
ID=74860077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP21835343.1A Pending EP4259671A1 (en) | 2020-12-09 | 2021-12-07 | Copolymer having viscoelastic and suspensive properties |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20240010775A1 (en) |
| EP (1) | EP4259671A1 (en) |
| KR (1) | KR20230117748A (en) |
| CN (1) | CN116635493A (en) |
| FR (1) | FR3117116B1 (en) |
| MX (1) | MX2023005400A (en) |
| WO (1) | WO2022123127A1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0607038A2 (en) * | 2005-01-28 | 2009-12-01 | Basf Ag | use of polymers cosmetic compositions for hair and skin and dermatological composition |
| KR102188318B1 (en) * | 2013-05-14 | 2020-12-08 | 제온 코포레이션 | Binder composition for lithium ion secondary battery, slurry composition for lithium ion secondary battery, electrode for lithium ion secondary battery, lithium ion secondary battery, and method for producing binder composition for lithium ion secondary battery |
| US20170003717A1 (en) | 2014-03-20 | 2017-01-05 | Intel Corporation | Memory card connector for electronic devices |
| EP2933280B1 (en) * | 2014-04-18 | 2016-10-12 | Rhodia Opérations | Rheology modifier polymer |
-
2020
- 2020-12-09 FR FR2012936A patent/FR3117116B1/en active Active
-
2021
- 2021-12-07 CN CN202180082246.6A patent/CN116635493A/en active Pending
- 2021-12-07 EP EP21835343.1A patent/EP4259671A1/en active Pending
- 2021-12-07 US US18/253,992 patent/US20240010775A1/en active Pending
- 2021-12-07 KR KR1020237023228A patent/KR20230117748A/en unknown
- 2021-12-07 WO PCT/FR2021/000143 patent/WO2022123127A1/en active Application Filing
- 2021-12-07 MX MX2023005400A patent/MX2023005400A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR3117116B1 (en) | 2023-12-29 |
| CN116635493A (en) | 2023-08-22 |
| KR20230117748A (en) | 2023-08-09 |
| US20240010775A1 (en) | 2024-01-11 |
| MX2023005400A (en) | 2023-05-19 |
| FR3117116A1 (en) | 2022-06-10 |
| WO2022123127A1 (en) | 2022-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2096083C (en) | Partially or entirely water-soluble acrylic copolymer, cross-linked or not, and the use thereof | |
| DK2475694T3 (en) | Polycosanol associative monomers, associated associative thickeners and uses thereof | |
| CA2767173A1 (en) | Aqueous self-crosslinkable polymer dispersion made from hard-core, soft-shell structured polymer particles, and coating or treatment compositions | |
| FR2956862A1 (en) | ASSOCIATIVE MONOMER BASED ON OXO ALCOHOLS, ACRYLIC POLYMER CONTAINING THIS MONOMER, USE OF SAID POLYMER AS THICKENING IN AQUEOUS FORMULATION, FORMULATION OBTAINED | |
| EP2585503A1 (en) | Alkali-swellable acrylic emulsions comprising acrylic acid, use thereof in aqueous formulations and formulations containing same | |
| CA2211164C (en) | Finely particulate composite latices and use thereof in solvent-free paints | |
| FR2767327A1 (en) | NOVEL ASSOCIATIVE POLYMERS AND THEIR REVERSE EMULSION PREPARATION PROCESS | |
| EP1129117A1 (en) | Polymers fluorinated by polymerisation in mini-emulsion | |
| FR3056983A1 (en) | ANIONIC COPOLYMER THICKENING | |
| EP0690882B1 (en) | Latex for solvent-free paints having improved washability | |
| EP0783530B1 (en) | Nail varnish containing microgels | |
| EP4259671A1 (en) | Copolymer having viscoelastic and suspensive properties | |
| FR3052165A1 (en) | COPOLYMER THICKENING AND SUSPENSIVE | |
| EP3313907A1 (en) | Polymer as thickener and suspending agent | |
| EP3784706B1 (en) | Preparation of an active polymer emulsion | |
| WO2002081581A1 (en) | Liquid concentrate of mineral fillers containing grafted polymers and their use for preparing paints in aqueous and/or organic medium | |
| WO2017207945A1 (en) | Copolymer having thickening and suspension properties | |
| FR3127494A1 (en) | PREPARATION OF A COMPOSITION WITHOUT SULFATED SURFACTANT | |
| FR3098822A1 (en) | AQUEOUS COATING COMPOSITION |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 20230613 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| DAV | Request for validation of the european patent (deleted) | ||
| DAX | Request for extension of the european patent (deleted) |