EP3877426A1 - Verfahren zur synthese von polymeren durch kontrollierte radikalische inverse emulsionspolymerisation - Google Patents
Verfahren zur synthese von polymeren durch kontrollierte radikalische inverse emulsionspolymerisationInfo
- Publication number
- EP3877426A1 EP3877426A1 EP19818209.9A EP19818209A EP3877426A1 EP 3877426 A1 EP3877426 A1 EP 3877426A1 EP 19818209 A EP19818209 A EP 19818209A EP 3877426 A1 EP3877426 A1 EP 3877426A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- monomer
- group
- water
- carbon atoms
- monomers
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 239000000839 emulsion Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 86
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 239000008346 aqueous phase Substances 0.000 claims abstract description 14
- 239000012074 organic phase Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- -1 alkylarylcarbonyl Chemical group 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 230000002441 reversible effect Effects 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 125000000129 anionic group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 150000001447 alkali salts Chemical class 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 3
- 125000005099 aryl alkyl carbonyl group Chemical group 0.000 claims description 3
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 3
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000005544 phthalimido group Chemical group 0.000 claims description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000007870 radical polymerization initiator Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical compound C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 claims description 2
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- 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 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
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical class CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 claims description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 2
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 2
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 claims description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 2
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 125000004426 substituted alkynyl group Chemical group 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000010526 radical polymerization reaction Methods 0.000 description 12
- 230000007704 transition Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 5
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Chemical group 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011557 critical solution Substances 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002270 exclusion chromatography Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012690 ionic polymerization Methods 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229940080818 propionamide Drugs 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LDQYWNUWKVADJV-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanamide;dihydrate Chemical compound O.O.NC(=O)C(C)(C)N=NC(C)(C)C(N)=O LDQYWNUWKVADJV-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- ZQRNRKASNNVFAJ-UHFFFAOYSA-N 3-[dimethyl(2-prop-2-enoyloxyethyl)azaniumyl]propane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCC[N+](C)(C)CCOC(=O)C=C ZQRNRKASNNVFAJ-UHFFFAOYSA-N 0.000 description 1
- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 description 1
- OIETYYKGJGVJFT-UHFFFAOYSA-N 3-[dimethyl-[3-(2-methylprop-2-enoylamino)propyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)NCCC[N+](C)(C)CCCS([O-])(=O)=O OIETYYKGJGVJFT-UHFFFAOYSA-N 0.000 description 1
- GPVILMAFGAKQPP-UHFFFAOYSA-N 4-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]butane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCCS([O-])(=O)=O GPVILMAFGAKQPP-UHFFFAOYSA-N 0.000 description 1
- YVECQSLRWYXZTR-UHFFFAOYSA-N 4-[dimethyl-[3-(2-methylprop-2-enoylamino)propyl]azaniumyl]butane-1-sulfonate Chemical compound CC(=C)C(=O)NCCC[N+](C)(C)CCCCS([O-])(=O)=O YVECQSLRWYXZTR-UHFFFAOYSA-N 0.000 description 1
- PGFZYOCLSPEKSN-UHFFFAOYSA-N 5,5-dimethyl-1,3-diazabicyclo[2.2.0]hex-3-ene dihydrochloride Chemical compound Cl.Cl.CC1(C)CN2CN=C12 PGFZYOCLSPEKSN-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 239000004908 Emulsion polymer Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-M butane-1-sulfonate Chemical compound CCCCS([O-])(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-M 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000004680 hydrogen peroxides Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000569 multi-angle light scattering Methods 0.000 description 1
- MVVMETRGWFSULN-UHFFFAOYSA-N n',n',2-trimethyl-n-propylprop-2-enehydrazide Chemical class CCCN(N(C)C)C(=O)C(C)=C MVVMETRGWFSULN-UHFFFAOYSA-N 0.000 description 1
- MCJSBJWFBJVOFV-UHFFFAOYSA-N n',n'-dimethyl-2-methylidenepentanehydrazide Chemical class CCCC(=C)C(=O)NN(C)C MCJSBJWFBJVOFV-UHFFFAOYSA-N 0.000 description 1
- VXRNYQMFDGOGSI-UHFFFAOYSA-N n-(1,3-dihydroxy-2-methylpropan-2-yl)-2-[[1-[(1,3-dihydroxy-2-methylpropan-2-yl)amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCC(C)(CO)NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC(C)(CO)CO VXRNYQMFDGOGSI-UHFFFAOYSA-N 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- BUGISVZCMXHOHO-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]-2-[[1-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCC(CO)(CO)NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC(CO)(CO)CO BUGISVZCMXHOHO-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 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
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- CAAIULQYGCAMCD-UHFFFAOYSA-L zinc;hydroxymethanesulfinate Chemical compound [Zn+2].OCS([O-])=O.OCS([O-])=O CAAIULQYGCAMCD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2400/00—Characteristics for processes of polymerization
- C08F2400/02—Control or adjustment of polymerization parameters
Definitions
- the present invention relates to a new radical polymerization process in reverse emulsion.
- Reversible deactivation (PRDR) radical polymerizations combine both the ease of carrying out conventional radical polymerization and the living nature of ionic polymerization.
- PRDR brings together techniques such as iodine transfer polymerization (ITP), nitroxide-controlled polymerization, NMP (Nitroxide Mediated Polymerization), by atom transfer, ATRP (Atom Transfer Radical Polymerization), by reversible addition-fragmentation chain transfer, RAFT (Reversible Addition Fragmentation chain Transfer Polymerization), which includes MADIX technology (MAcromolecular Design by Interchange of Xanthates), various variations of polymerizations with organometallic compounds, OMRP (Organometallic Mediated Radical Polymerization), radical polymerization controlled by heteroatomic compounds (OrganoHeteroatom-mediated Radical Polymerization (OHRP).
- This activation-deactivation process allows the chains to grow at the same rate, until the total consumption of the monomer is made, making it possible to control the molecular weights of the polymers and obtain narrow molecular weight distributions. This will also make it possible to minimize the heterogeneity of the composition.
- Reversible deactivation of growing chains is responsible for minimizing irreversible termination reactions.
- the vast majority of polymer chains remain in dormant form and are therefore reactivable. It is then possible to functionalize the chain ends in order to initiate other modes of polymerization or to make chain extensions. This is the key to accessing high molecular weights, compositions and controlled architectures.
- Controlled radical polymerization therefore has the following distinctive aspects:
- the average molecular weight is controlled by the monomer / precursor molar ratio.
- Patent EP 991 683 describes a controlled radical polymerization in direct emulsion. This mode of polymerization requires a step of recovering the polymer, such as for example evaporation under vacuum. The polymers described in patent EP 991 683 are obtained by polymerization of lipophilic monomers. Thus, in the case of an emulsion polymerization, the emulsion is a direct emulsion and the monomers are polymerized in the dispersed phase, namely the organic phase. The technique presented leads to low molecular weight block polymers.
- Patent application WO 2012/042167 uses the gel polymerization route. Although using water-soluble precursors, this technique does not make it possible to obtain polymers of high molecular weights.
- the problem which the applicant proposes to solve is to obtain water-soluble polymers of high molecular weight while having a low polydispersity index, advantageously less than 2.
- the invention relates to a process for the preparation of a polymer by reverse emulsion polymerization comprising the following steps:
- o Z O, S or N
- R 1 and R 2 identical or different, represent:
- a heterocycle (iii), saturated or not, optionally substituted or aromatic, these groups and rings (i), (ii) and (iii) possibly being substituted by substituted aromatic groups or alkoxycarbonyl or aryloxycarbonyl (- COOR), carboxy (-COOH), acyloxy (-0 2 CR), carbamoyl ( -CONR2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, male ⁇ mido, succinimido, amidino, guanidimo, hydroxy (-OH), amino (-NR2), halogen, allyl, epoxy, alkoxy (-OR ), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as the alkali salts of carboxylic acids, the alkali salts of sulfonic acid, the polyalkylene oxide chains (POE
- R representing an alkyl or aryl group
- o A is a linear or structured polymer chain comprising n identical or different monomers
- n is an integer between 1 and 500, advantageously between 2 and 500,
- R 1 and R 2 are identical or different and advantageously represent a group (i) (alkyl, acyl, alkenyl or alkynyl), more advantageously a group chosen from a linear or branched alkyl group comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms; a linear or branched acyl group comprising from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms; a linear or branched alkenyl group comprising from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms; or a linear or branched alkynyl group comprising from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms; these groups being optionally substituted by one or more substituted aromatic groups which may comprise 4 to 7 carbon atoms or alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxy (- COOH), acyloxy (-O2CR), carbamoyl
- R advantageously represents a linear or branched alkyl group comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, or aryl comprising from 6 to 10 carbon atoms.
- a carbon ring (ii) comprises from 6 to 10 carbon atoms.
- a heterocycle (iii) advantageously comprises from 5 to 9 carbon atoms.
- a group comprising carbon atoms is a hydrocarbon group which may optionally include heteroatoms.
- a heterocyclic comprises 1 or more heteroatoms, advantageously N, O, S or P.
- the term monomer also denotes the monomer in its polymerized form.
- the two R groups can be identical or different from each other.
- Step d) makes it possible to obtain a water-soluble polymer. It is a homopolymer or a copolymer.
- reverse emulsion refers to both reverse emulsions and reverse microemulsions. These are water-in-oil type emulsions in which the aqueous phase is dispersed in the organic phase in the form of drops or droplets.
- water-soluble precursor designates a water-soluble precursor, at a temperature of 25 ° C., in a proportion of at least 50 g / l. This definition also relates to the other water-soluble compounds mentioned (polymer, monomer %)
- the polymer chain A comprises at least one nonionic monomer and / or at least one anionic monomer and / or at least one cationic monomer.
- A comprises at least two identical monomers.
- the following different types of monomers can be used as monomers of the aqueous phase or in the polymer chain A of the precursor.
- the nonionic monomer or monomers which can be used within the framework of the invention can be chosen, in particular, from the group comprising vinyl monomers soluble in water.
- Preferred monomers belonging to this class are, for example, acrylamide, methacrylamide; N-isopropylacrylamide; N, N-dimethylacrylamide; N, N diethylacrylamide; N-methylolacrylamide; N-vinylformamide; N-vinyl acetamide; N-vinylpyridine; N-vinylpyrrolidone; acryloyl morpholine (ACMO), glycidyl methacrylate, glyceryl methacrylate and diacetone acrylamide.
- a preferred nonionic monomer is acrylamide.
- the anionic monomer (s) are preferably chosen from acrylic acid; methacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; 2-acrylamido 2-methylpropane sulfonic acid; vinyl sulfonic acid; vinylphosphonic acid; allylsulfonic acid; allylphosphonic acid; styrene sulfonic acid, said anionic monomer being unsalted, partially or fully salified, and the salts of 3-sulfopropyl methacrylate.
- the salified form advantageously corresponds to the salts of alkali metals (Li, Na, K, etc.), of alkaline earth metals (Ca, Mg, etc.) or of ammonium, in particular quaternary ammoniums.
- the cationic monomer or monomers which can be used within the framework of the invention can be chosen, in particular from the monomers of the acrylamide, acrylic, vinyl, allyl or maleic type having a quaternary ammonium function by salification or quaternization.
- AD AME dimethylaminoethyl acrylate
- MADAME dimethylaminoethyl methacrylate
- DADMAC dimethyldiallylammonium chloride
- ATAC acrylamide propyltrimethyl chloride ammonium
- MATAC methacrylamido propyltrimethyl ammonium chloride
- the cationic monomer (s) can also be chosen from associative cationic monomers as described in patent FR 2 868 783.
- the monomer can optionally be a zwitterionic monomer of the acrylamide, acrylic, vinyl, allylic or maleic type having an amine or quaternary ammonium function and an acid function of the carboxylic, sulfonic or phosphoric type.
- dimethylammonio dimethylamino propyl methylacrylamide derivatives such as 2 - ((3-methacrylamidopropyl) dimethylammonio) ethane-1-sulfonate, 3 - ((3-methacrylamidopropyl) dimethylammonio) propane-1-sulfonate, 4- ((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate and [3- (methacryloyloxy) propyl)] (dimethylammonio) acetate.
- the monomer can optionally have an LCST group or a UCST group.
- an LCST group corresponds to a group whose solubility in water for a determined concentration is modified beyond a certain temperature and according to the salinity. It is a group having a transition temperature by heating defining its lack of affinity with the solvent medium. The lack of affinity with the solvent results in an opacification or a loss of transparency which may be due to precipitation, aggregation, gelling or viscosification of the medium.
- the minimum transition temperature is called “LCST” (lower critical solubility temperature, from the acronym “Lower Critical Solution Temperature”).
- LCST lower critical solubility temperature
- the measurement of the LCST can be done visually: the temperature at which the lack of affinity with the solvent appears, that is to say the cloud point, is determined.
- the cloud point corresponds to the clouding of the solution or loss of transparency.
- the LCST can also be determined according to the type of phase transition, for example by DSC (differential scanning calorimetry, from the English acronym “Differential scanning calorimetry”), by a transmittance measurement or by a viscosity measurement.
- DSC differential scanning calorimetry, from the English acronym "Differential scanning calorimetry”
- the LCST is determined by determining the cloud point by transmittance according to the following protocol.
- the transition temperature is measured for an LCST compound for a solution having a concentration by weight in deionized water of 1% by weight of said compound.
- the cloud point corresponds to the temperature at which the solution has a transmittance equal to 85% of light rays having a wavelength between 400 and 800 nm.
- the temperature at which the solution has a transmittance equal to 85% corresponds to the minimum transition temperature LCST of the compound, in this case from the macromonomer to LCST.
- a transparent composition has a maximum light transmittance value, whatever the wavelength between 400 and 800 nm, through a sample of 1 cm thickness, of at least 85 %, preferably at least 90%. This is the reason why, the cloud point corresponds to a transmittance of 85%.
- a group with UCST corresponds to a group whose solubility in water for a determined concentration is modified below a certain temperature and according to the salinity. It is a group having a transition temperature by cooling defining its lack of affinity with the solvent medium. The lack of affinity with the solvent results in an opacification or a loss of transparency which can be due to precipitation, aggregation, gelling or viscosification of the medium.
- the maximum transition temperature is called “UCST” (upper critical solubility temperature, from the acronym “Upper Critical Solution Temperature”).
- UCST upper critical solubility temperature
- Upper Critical Solution Temperature Upper Critical Solution Temperature
- the precursor is of formula (I) in which:
- the precursor is of formula (I) in which:
- o A is a linear or structured polymer chain obtained from 1 to 100 (advantageously 2 to 100) monomers comprising at least one nonionic monomer and / or at least one anionic monomer and / or at least one cationic monomer.
- the precursor is of formula (I) in which:
- A is a linear or structured polymer chain obtained from 1 to 100 (advantageously 2 to 100) monomers comprising at least one nonionic monomer and / or at least one anionic monomer and / or at least one associative cationic monomer.
- the precursor is of formula (I) in which:
- o A is a linear or structured polymer chain obtained from 1 to 100 (advantageously 2 to 100) monomers comprising at least one nonionic monomer and / or at least one anionic monomer and / or at least one monomer comprising an LCST group.
- A consists of n identical nonionic monomers. More advantageously, A is a polyacrylamide.
- the precursor has the following formula (II):
- n denotes an integer between 1 and 100, preferably between 1 and 50.
- n denotes an integer between 2 and 100, preferably between 3 and 100, more preferably between 4 and 50.
- the amount of precursor in the emulsion can be between 5. 10 7 % and 5% relative to the weight of the emulsion, preferably between 5.10 4 and 5.10
- the molar ratio of water-soluble monomer / precursor in the aqueous phase is advantageously between 12,500: 1 and 300,000: 1, preferably between 27,500: 1 and 250,000: 1, more preferably between 27,500: 1 and 10,000: 1.
- the radical polymerization initiator can be chosen from the initiators conventionally used in radical polymerization. It can for example be one of the following initiators:
- hydrogen peroxides such as those selected from the group comprising tertiary butyl hydroperoxide, cumene hydroperoxide, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyoctoate, t-butylperoxyneodecanoate, t -butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, and ammonium persulfate, azo compounds such as those selected from the group including 2-2'- azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 4,4'-azobis (4-pentanoic acid), l, l'-azobis (cyclohexane-carbonitrile), 2- (t -butyl
- alkali metal persulfates in combination with an arylphosphinic acid, such as benzene phosphonic acid and the like, and reducing sugars.
- the different monomers used in the aqueous phase can be chosen from the respective lists mentioned above in the description also concerning the polymer chain A of the precursor.
- the monomer is chosen from the group comprising nonionic monomers; anionic monomers; and mixtures of nonionic monomers and anionic monomers.
- the polymer obtained according to the invention has a molecular weight of between 1,250,000 and 30,000,000 (30 million) g / mol, and preferably between 2,750,000 and 25,000,000 g / mol. Molecular weight is understood as weight average molecular weight.
- the polydispersity index (Ip) of the polymer obtained according to the invention is advantageously at most 2 ( ⁇ 2), preferably at most 1.5 ( ⁇ 1.5).
- the index of polydispersity is determined according to the following formula:
- Mw is the weight average molecular weight
- Mn is the number average molecular weight
- the determination of the average molecular weights in weight (Mw) and in number (Mn) is carried out in a conventional manner, advantageously by steric exclusion chromatography (CES) coupled to a multi-angle light scattering detector of the Dawn Heleos II type. , 18 angles (Wyatt technology).
- the invention relates to the use of the polymers obtained according to the polymerization process described above in the oil and gas industry, hydraulic fracturing, paper, water treatment, construction, mining, cosmetics, textiles or detergents.
- the polymers are used in the field of enhanced oil and gas recovery.
- Figure 1 illustrates the reversible balance between a dormant species and an active species in a radical polymerization process by reversible deactivation.
- FIG. 2 illustrates the nuclear magnetic resonance spectrum of the proton (3 ⁇ 4 NMR) of the water-soluble precursor of formula (I) of Example 1.
- R 1 CH2-CH3
- This precursor was notably characterized by its 1 H NMR spectrum (300.13 MHz) in D 2 0 (FIG. 2).
- Preparation of the aqueous phase 400 g of acrylamide (50% by weight in water), 90 g of acrylic acid, 150 g of water and 0.0015% by weight relative to the emulsion were mixed , of the water-soluble precursor of Example 1.
- the aqueous phase was neutralized with 90 g of sodium hydroxide (50% by weight in water).
- the aqueous phase and the organic phase were mixed and emulsified.
- the emulsion was then degassed for 60 minutes before polymerization was initiated by the addition of a reducing agent, sodium metabisulfite (MBS).
- MBS sodium metabisulfite
- the polymer obtained is recovered by precipitation in acetone.
- Polymer P2 is synthesized as in Example 2, replacing the water-soluble precursor with sodium hypophosphite.
- the three polymers P1, P2 and P3 were analyzed by steric exclusion chromatography (CES), the conditions of which are as follows: a Shodex SB807- G precolumn and two Shodex OHpak columns in series (SB-807 HQ and SB-805 HQ ) coupled with a refractive index detector (Optilab T-rEX, Wyatt Technology, and Dawn Heleos II 18 angles, Wyatt Technology).
- CES steric exclusion chromatography
- Table 1 values of the molecular weights in number and in weight and the polydispersity index of PL P 2 and P 3
- the molecular weight in number of the polymer P3 was difficult to control because the precursor used is not soluble in water which is equivalent to a polymerization without precursor.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
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FR1860202A FR3088067B1 (fr) | 2018-11-06 | 2018-11-06 | Procede de synthese de polymeres par polymerisation radicalaire controlee en emulsion inverse |
PCT/FR2019/052609 WO2020094963A1 (fr) | 2018-11-06 | 2019-11-04 | Procede de synthese de polymeres par polymerisation radicalaire controlee en emulsion inverse |
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US (1) | US20210380729A1 (de) |
EP (1) | EP3877426A1 (de) |
JP (1) | JP2022506667A (de) |
KR (1) | KR20210088634A (de) |
CN (1) | CN112969721A (de) |
AR (1) | AR116985A1 (de) |
AU (1) | AU2019376489A1 (de) |
CA (1) | CA3118202A1 (de) |
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FR2965564B1 (fr) | 2010-09-30 | 2012-10-26 | Rhodia Operations | Preparation de polymeres hydrophiles de haute masse par polymerisation radicalaire controlee |
CN102492092B (zh) * | 2011-12-21 | 2014-05-07 | 浙江大学 | 反相乳液聚合制备超支化离子型酰胺类聚合物的方法 |
CN104693385B (zh) * | 2015-02-12 | 2017-03-01 | 浙江理工大学 | 含定量硫酸酯乙基砜基团的三硫代酯化合物及其合成方法和应用 |
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Publication number | Publication date |
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WO2020094963A1 (fr) | 2020-05-14 |
FR3088067B1 (fr) | 2020-11-06 |
AU2019376489A8 (en) | 2021-06-17 |
FR3088067A1 (fr) | 2020-05-08 |
US20210380729A1 (en) | 2021-12-09 |
AU2019376489A1 (en) | 2021-05-27 |
CA3118202A1 (en) | 2020-05-14 |
JP2022506667A (ja) | 2022-01-17 |
CN112969721A (zh) | 2021-06-15 |
KR20210088634A (ko) | 2021-07-14 |
AR116985A1 (es) | 2021-06-30 |
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