EP3658597A1 - Composition polymérique aqueuse et copolymère - Google Patents
Composition polymérique aqueuse et copolymèreInfo
- Publication number
- EP3658597A1 EP3658597A1 EP18782779.5A EP18782779A EP3658597A1 EP 3658597 A1 EP3658597 A1 EP 3658597A1 EP 18782779 A EP18782779 A EP 18782779A EP 3658597 A1 EP3658597 A1 EP 3658597A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- monomer
- copolymer
- less
- acid
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 180
- 229920001577 copolymer Polymers 0.000 title claims abstract description 104
- 229920000642 polymer Polymers 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 117
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 125000000129 anionic group Chemical group 0.000 claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 84
- 238000009472 formulation Methods 0.000 claims description 46
- 239000011230 binding agent Substances 0.000 claims description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- -1 alkali metal persulfate Chemical class 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000010526 radical polymerization reaction Methods 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000002671 adjuvant Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 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 4
- 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 4
- 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 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 238000000518 rheometry Methods 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
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 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 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-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
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- 150000002689 maleic acids Chemical class 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-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
- 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
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- 239000008030 superplasticizer Substances 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000243 solution Substances 0.000 description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 22
- 239000004568 cement Substances 0.000 description 17
- 239000010949 copper Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000004567 concrete Substances 0.000 description 13
- 239000004570 mortar (masonry) Substances 0.000 description 13
- 238000007792 addition Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 7
- 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 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- 239000005569 Iron sulphate Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011505 plaster Substances 0.000 description 3
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 3
- 229940099427 potassium bisulfite Drugs 0.000 description 3
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 3
- 239000012989 trithiocarbonate Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000002270 exclusion chromatography Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011440 grout Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910002476 CuII Inorganic materials 0.000 description 1
- DXXYTBCIXZGERI-UHFFFAOYSA-N O.O.O.O.O.O.O.[Fe] Chemical compound O.O.O.O.O.O.O.[Fe] DXXYTBCIXZGERI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- CGPVLUCOFNAVGV-UHFFFAOYSA-N copper;pentahydrate Chemical compound O.O.O.O.O.[Cu] CGPVLUCOFNAVGV-UHFFFAOYSA-N 0.000 description 1
- FFHWGQQFANVOHV-UHFFFAOYSA-N dimethyldioxirane Chemical compound CC1(C)OO1 FFHWGQQFANVOHV-UHFFFAOYSA-N 0.000 description 1
- GQZXNSPRSGFJLY-UHFFFAOYSA-M dioxidophosphate(1-) Chemical compound [O-]P=O GQZXNSPRSGFJLY-UHFFFAOYSA-M 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 239000011178 precast concrete Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Classifications
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
-
- 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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
- C08F216/1425—Monomers containing side chains of polyether groups
- C08F216/1433—Monomers containing side chains of polyethylene oxide groups
-
- 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
- C08F220/288—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 polypropylene-co-ethylene oxide in the alcohol moiety
-
- 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
- C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
-
- 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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Definitions
- the invention relates to an aqueous composition
- the invention also relates to this copolymer as such and a process for its preparation as well as its use as a superplasticizer.
- composition according to the invention is advantageously used in the technical field of mortars, concretes, plasters or other compositions based on hydraulic compounds or binders, especially cement or plaster.
- Such compositions may advantageously be used in the fields of construction, public works or the exploitation of hydrocarbons.
- Dispersant compounds of hydraulic binders are usually used for their ability to modify the rheology of the medium in which they are present, in particular for their ability to control the workability of this medium.
- Workability is generally defined as the property of a composition comprising a hydraulic binder, in particular a slag or a grout of cement or mortar or else a concrete, for example a ready-to-use concrete or a precast concrete, to remain manageable for as long as possible.
- controlling the workability makes it possible to transport or move the aqueous composition comprising the hydraulic binder, for example during transport or displacement from a reservoir to another reservoir.
- Maneuverability also makes it possible to control the storage conditions of such an aqueous composition. It also makes it possible to pump or even pump easily, this composition. Controlling the maneuverability of such a composition therefore makes it possible to improve the conditions of use thereof, in particular to increase its duration of use under satisfactory or effective conditions.
- an aqueous composition comprising a hydraulic binder can be evaluated by measuring the flow time of the hydraulic binder.
- the hydraulic binder or the superplasticizing agent should make it possible to obtain a composition having a controlled and stable viscosity and, preferably, a stable viscosity over a prolonged period.
- aqueous hydraulic compositions comprising a hydraulic binder
- compositions comprising a small amount of water.
- an important aspect of the invention is the provision of an aqueous composition comprising a hydraulic binder having improved workability time. Handling control should not lead to alteration of other properties, including mechanical properties, especially at younger ages.
- the workability of the aqueous compositions comprising a hydraulic binder can be evaluated by measuring the slump, for example according to the EN 12350-2 standard. Indeed, sagging and handling are proportional.
- the retention of fluidity is also a property to be controlled for aqueous compositions comprising a hydraulic binder.
- Another aspect of the invention relates to obtaining an aqueous composition comprising a hydraulic binder for limiting or reducing shrinkage during drying.
- the improvement of the properties of the aqueous compositions comprising a hydraulic binder should be obtained without modifying the setting of the composition, in particular without delaying this setting.
- aqueous compositions comprising a hydraulic binder should also have a weight ratio water / hydraulic binder, usually water / cement or E / C, the lowest possible, without impairing their properties.
- aqueous compositions comprising a hydraulic binder should make it possible to improve the mechanical properties of the materials obtained, in particular their mechanical properties at young ages, properties which can be evaluated by measuring the evolution over time of the resistance to the compression.
- the compounds used for the preparation of aqueous compositions comprising a hydraulic binder should be used in reduced doses.
- aqueous compositions comprising a hydraulic binder, in particular being miscible in all proportions with these other components, in order to avoid or limit the risks of segregation of the components of the aqueous composition. comprising a hydraulic binder.
- the application US 2011 0186773 describes the preparation of polymers using dipropionate trithiocarbonate disodium without making any mention of improving the workability of a concrete composition or the reduction of water within such a composition.
- the application US 2014 0343240 describes a polymeric additive for hydraulic composition; it is prepared by means of a chain transfer agent which is a thiol.
- the application US 2014 0088250 relates to a method for preparing a polymer using dipropionate trithiocarbonate disodium.
- the application US 2016 0289120 discloses a workability retaining agent for a concrete composition.
- Dispersant compounds or superplasticizing agents which can be used in aqueous compositions comprising a hydraulic binder are known.
- these compounds do not provide a solution to the problems encountered.
- these compounds do not make it possible to maintain a good degree of initial fluidity of the aqueous compositions comprising a hydraulic binder in which they are incorporated, while maintaining their workability and without altering their mechanical properties, nor can they cause segregation phenomena.
- the invention makes it possible to provide a solution to all or some of the problems encountered with the polymeric compositions of the state of the art.
- the invention makes it possible to obtain copolymers by a particularly efficient preparation method, for example as regards the control of the temperature of the polymerization reaction.
- it is essential to have available preparation processes that make it possible to overcome the low temperature maintenance of the reaction medium used in the polymerization reactions known from the state of the art.
- the copolymers prepared may comprise residues of the comonomers in proportions that are identical or close to the proportions of the monomers used.
- the invention provides an aqueous composition
- aqueous composition comprising at least one copolymer whose polymolecularity index Ip is less than 3, obtained by at least one radical polymerization reaction in water and at a temperature ranging from 10 to 90 ° C. ,
- - RI and R2 identical or different, independently represent H or CH3,
- L independently represents a group chosen from (CH 2 -CH 2 O) x, (CH 2 CH (CH 3) O) y, (CH (CH 3) CH 2 O) and their combinations and
- - x, y and z identical or different, independently represent an integer or decimal number between 0 and 150 and the sum x + y + z is between 10 and 150;
- X independently represents H, Na or K
- R is independently a Cl-C5-alkyl group
- At least one radical-generating compound selected from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, mixtures thereof or combinations thereof with an alkali metal bisulfite or with an ion selected from Fe 11 , Fe 111 , Cu 1 , Cu 11 .
- the invention also provides an aqueous composition comprising at least one copolymer chosen from:
- - RI and R2 identical or different, independently represent H or CH3,
- L independently represents a group selected from (CH 2 -CH 2 O) x, (CH 2 CH (CH 3 ) O) y , (CH (CH 3 ) CH 2 0) z and combinations thereof and
- - x, y and z identical or different, independently represent an integer or decimal number between 0 and 150 and the sum x + y + z is between 10 and 150;
- X independently represents H, Na or K
- R is independently a Cl-C5-alkyl group
- At least one radical generating compound selected from hydrogen peroxide, an alkali metal persulfate, mixtures thereof or combinations thereof with an alkali metal bisulfite or with an ion selected from Fe 11 , Fe 111 , Cu 1 , Cu 11 , and
- - RI and R2 identical or different, independently represent H or CH3,
- L is independently a group selected from (CH 2 -CH 2 O) x combined with (CH (CH 3) CH 2 O) and (CH 2 CH (CH 3) O) combined with (CH (CH 3) CH 2 O) and combinations thereof, and
- - x, y and z identical or different, independently represent an integer or decimal number between 0 and 150 and the sum x + y + z is between 10 and 150;
- X independently represents H, Na or K
- R is independently a Cl-C5-alkyl group
- At least one radical-generating compound selected from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, mixtures thereof or combinations thereof with an alkali metal bisulfite or with an ion selected from Fe 11 , Fe 111 , Cu 1 , Cu 11 .
- the conditions of preparation of the composition according to the invention are particularly advantageous. Indeed, these conditions of preparation of the composition according to the invention make it possible to reduce or avoid the formation of homopolymer of the monomer (a).
- the composition according to the invention does not comprise homopolymer of the monomer (a) relative to the amount by dry weight of copolymer.
- the composition according to the invention comprises a quantity by weight reduced, low or very low homopolymer of the monomer (a) relative to the amount by dry weight of copolymer. In the same way, the invention makes it possible to avoid or strongly limit the formation of copolymers of different monomers (a).
- the absence or the presence of a reduced, low or very small amount of homopolymer of the monomer (a) within the composition according to the invention makes it possible to avoid or limit the risk of inhibition. Crystallization of the concrete when the composition according to the invention is used for its plasticizing properties within a concrete formulation.
- a homopolymer of the monomer (a) has dispersant properties of mineral material particles and can therefore disrupt or inhibit crystallization within a concrete formulation. The properties of the concrete formulation or the final material prepared from the concrete formulation can then be modified or altered.
- the invention makes it possible to prepare a copolymer from monomers (a) and (b) while controlling the polymerization reaction of monomers (a) and (b).
- the invention thus makes it possible to obtain an aqueous composition comprising a very small amount of residual monomer (a) relative to the amount by dry weight of copolymer.
- the aqueous composition according to the invention comprises less than 2000 ppm by weight or less than 1500 ppm by weight of residual monomer (a) relative to the amount by dry weight of copolymer.
- the aqueous composition according to the invention comprises less than 1000 ppm by weight or less than 500 ppm by weight of residual monomer (a) relative to the amount by dry weight of copolymer.
- the aqueous composition according to the invention may comprise less than 200 ppm by weight or less than 100 ppm by weight of residual monomer (a) relative to the amount by dry weight of copolymer.
- the aqueous composition according to the invention comprises at least one copolymer whose polymolecularity index Ip is less than 3.
- the polymolecularity index Ip ranges from 1.5 to 3, more preferably from 1 to , 8 to 2.8 or 1.8 to 2.5, more preferably 2 to 2.8 or 2 to 2.5.
- the copolymer of the aqueous composition according to the invention is obtained by at least one radical polymerization reaction in water and at a temperature ranging from 10 to 90.degree. C., preferably from 30 to 85.degree. temperature ranging from 40 to 75 ° C or from 50 to 70 ° C. More preferably, a single polymerization reaction radical is implemented.
- the preparation of the aqueous composition according to the invention implements a radical polymerization reaction which is carried out in water in the presence of 0.05 to 5% by weight of at least one compound of formula (II) with respect to the amount of monomers.
- this compound (i) is of formula (II) in which R represents a C 1 -C 3 -alkyl group, preferably a methyl group.
- the preferred compound of formula (II) according to the invention is dipropionate trithiocarbonate disodium (DPTTC - CAS No. 86470-33-2).
- the polymerization reaction uses the compound of formula (II) in an amount of 0.05 to 4% by weight, of 0.05 to 3% by weight, of 0.05 at 2% by weight, 0.5 to 4% by weight, 0.5 to 3% by weight, 0.5 to 2% by weight, 1 to 4% by weight, 1 to 3% by weight, weight, from 1 to 2% by weight relative to the amount of monomers.
- the preparation of the aqueous composition according to the invention also implements at least one compound (ii) generating radicals which is particular. It is preferably chosen from hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, their mixtures or their combinations with sodium bisulfite or with potassium bisulfite or with an ion chosen from Fe 11 , Fe 111 , Cu 1 , Cu 11 . It is more preferentially selected from hydrogen peroxide, sodium persulfate, potassium persulfate, their mixtures or their combinations with sodium bisulfite or with potassium bisulfite or with an ion selected from Fe 11 , Fe 111 , Cu 1 , Cu 11 .
- the Fe 11 , Fe 111 , Cu 1 or Cu 11 ions can be used by means of at least one compound chosen from iron sulphate, hydrated iron sulphate, hemihydrated iron sulphate and sulphate. of iron heptahydrate, iron carbonate, hydrated iron carbonate, hemihydrated iron carbonate, iron chloride, copper carbonate, hydrated copper carbonate, hemihydrated copper carbonate, copper acetate, copper sulphate, sulphate of copper pentahydrate, copper hydroxide, copper halide.
- the particular radical generating compound is more preferably selected from hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, sodium bisulfite and potassium bisulfite, especially sodium persulfate or bisulphite. sodium.
- the particular radical generating compound is even more preferentially selected from hydrogen peroxide, sodium persulfate and potassium persulfate.
- the polymerization reaction is carried out in the absence of a compound comprising phosphorus at the oxidation state I, especially in the absence of hypophosphorous acid (H3PO2) or a derivative of hypophosphorous acid (H3PO2), such as compounds comprising at least one hypophosphite ion (H2PO2), in particular in the absence of a compound selected from sodium hypophosphite (H 2 PO 2 Na), potassium hypophosphite (H2PO2K), hypophosphite of calcium ([H 2 PO 2 ] 2 Ca).
- hypophosphorous acid H3PO2
- H3PO2K a derivative of hypophosphorous acid
- H2PO2K hypophosphite of calcium
- the amounts of monomers (a) and (b) used can vary quite widely.
- the polymerization reaction uses:
- the polymerization reaction uses:
- the polymerization reaction uses:
- the polymerization reaction uses:
- the polymerization reaction uses:
- the invention comprises the implementation of a radical polymerization reaction in water of at least one anionic monomer (a) comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or a salt thereof .
- the composition according to the invention comprises a copolymer prepared by a polymerization reaction using an anionic monomer (a) comprising a polymerizable olefinic unsaturation and a carboxylic acid functional group or one of its salts.
- the monomer (a) used is selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, an acrylic acid salt, a methacrylic acid salt, an itaconic acid salt, a maleic acid salt and mixtures thereof.
- the monomer (a) used is chosen from acrylic acid, methacrylic acid, an acrylic acid salt, a methacrylic acid salt and mixtures thereof, especially acrylic acid or an acid salt. acrylic, especially a sodium salt of acrylic acid.
- the invention also comprises the use of at least one monomer (b) of formula (I).
- the compound (b) of formula (I) is a compound for which:
- x represents an integer or decimal number between 15 and 140
- y + z represents an integer or decimal number between 10 and 135
- x is strictly greater than y + z and the sum x + y + z is between 10 and 150 .
- the compound (b) of formula (I) is a compound for which:
- x represents an integer or decimal number between 15 and 140
- y + z represents an integer or decimal number between 1 and 135 and x is strictly greater than y + z and the sum x + y + z is between 10 and 150 .
- the compound (b) is a compound of formula (I) for which x represents an integer or decimal number between 10 and 150 or between 30 and 120, y + z represents an integer or decimal number of between 10 and 150. and 135, x is strictly greater than y + z and the sum x + y + z is between 10 and 150.
- the compound (b) is a compound of formula (I) for which x represents an integer or decimal number between 15 and 80 and y + z represents an integer or decimal number between 10 and 65, of preferably a compound of formula (I) for which x represents an integer or decimal number between 30 and 65 and y + z represents an integer or decimal number between 15 and 40 or between 10 and 25, in particular a compound of formula ( I) for which x represents an integer or decimal number between 40 and 60 and y + z represents an integer or decimal number between 20 and 30 or between 10 and 20.
- the monomer (b) is a compound of formula (I) for which x is strictly greater than y + z.
- a preferred compound (b) is a compound (b1) of formula (I) for which: R1 and R2 represent H,
- L represents a (CH 2 -CH 2 O) x group
- x represents an integer or decimal number between 10 and 150.
- a preferred compound (b) is a compound (b2) of formula (I) for which:
- R1 and R2 are H
- L independently represents a group selected from (CH 2 CH (CH 3) O) y and (CH (CH 3) CH 2 O) z and
- y and z identical or different, independently represent an integer or decimal number between 1 and 150 and the sum y + z is between 10 and 150.
- a preferred compound (b) is a compound (b3) of formula (I) for which:
- R1 and R2 are H
- L independently represents a group selected from (CH 2 -CH 2 O) x, (CH 2 CH (CH 3) O) y, (CH (CH 3) CH 2 O) and
- x, y and z identical or different, independently represent an integer or decimal number between 1 and 150 and the sum x + y + z is between 10 and 150.
- a preferred compound (b) is a compound (b4) of formula (I) for which:
- L represents a (CH 2 -CH 2 O) x group
- x represents an integer or decimal number between 10 and 150.
- a preferred compound (b) is a compound (b5) of formula (I) for which:
- R1 and R2 represent CH3
- L independently represents a group chosen from
- y and z identical or different, independently represent an integer or decimal number between 1 and 150 and the sum y + z is between 10 and 150.
- a preferred compound (b) is a compound (b6) of formula (I) for which:
- R1 and R2 represent CH3
- L independently represents a group selected from (CH 2 -CH 2 O) x, (CH 2 CH (CH 3) O) y, (CH (CH 3) CH 2 O) and
- x, y and z identical or different, independently represent a number integer or decimal number between 1 and 150 and the sum x + y + z is between 10 and 150.
- a preferred compound (b) is a compound (b7) of formula (I) for which:
- RI H
- R2 represents CH3
- L represents a (CH 2 -CH 2 O) x group
- x represents an integer or decimal number between 10 and 150.
- a preferred compound (b) is a compound (b8) of formula (I) for which:
- RI H
- R2 represents CH3
- L independently represents a group selected from (CH 2 CH (CH 3) O) y and (CH (CH 3) CH 2 O) z and
- y and z identical or different, independently represent an integer or decimal number between 1 and 150 and the sum y + z is between 10 and 150.
- a preferred compound (b) is a compound (b9) of formula (I) for which:
- R2 represents CH3
- L independently represents a group selected from (CH 2 -CH 2 O) x, (CH 2 CH (CH 3) O) y, (CH (CH 3) CH 2 O) and
- x, y and z identical or different, independently represent an integer or decimal number between 1 and 150 and the sum x + y + z is between 10 and 150.
- a preferred compound (b) is a compound (blO) of formula (I) for which:
- RI CH3
- R2 represents H
- L represents a (CH 2 -CH 2 O) x group
- x represents an integer or decimal number between 10 and 150.
- a preferred compound (b) is a compound (b1) of formula (I) for which:
- RI CH3
- R2 represents H
- L independently represents a group selected from (CH 2 CH (CH 3) O) y and (CH (CH 3) CH 2 O) z and
- y and z identical or different, independently represent an integer or decimal number between 1 and 150 and the sum y + z is between 10 and 150.
- a preferred compound (b) is a compound (b1) of formula (I) for which:
- RI CH3
- R2 represents H
- L independently represents a group selected from (CH 2 -CH 2 O) x, (CH 2 CH (CH 3) O) y, (CH (CH 3) CH 2 O) and
- the aqueous composition according to the invention comprises at least one copolymer obtained by at least one radical polymerization reaction in water of at least one monomer (a) and at least one monomer (b) of formula (I).
- the polymerization reaction may also employ one or more other monomers.
- the polymerization reaction then also implements at least one other monomer chosen from: ⁇ another anionic monomer, preferably chosen from acrylic acid, methacrylic acid, itaconic acid, maleic acid, their salts and mixtures thereof;
- a nonionic monomer comprising at least one polymerizable olefinic unsaturation, preferably at least one polymerizable ethylenic unsaturation and in particular a polymerizable vinyl function, more preferably a nonionic monomer chosen from esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid selected from acrylic acid, methacrylic acid, and mixtures thereof, for example hydroxyethylacrylate, hydroxypropylacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate, styrene, vinylcaprolactam, alkyl acrylate, in particular C 1 -C 10 alkyl acrylate, preferably C 1 -C 4 -alkyl acrylate, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, alkyl methacrylate, in particular
- Ql represents a polymerizable acrylate group or a polymerizable methacrylate group
- Q2 represents an H group or a CH3 group
- L1 and L2 which may be identical or different, independently represent an ethylenoxy group or a propylenoxy group and m and n, which are identical or different, and of which at least one is different from 0, represent a number less than or equal to 150 and their sum m + n is less than 150;
- - RI and R2 identical or different, independently represent H or CH3,
- L represents a group chosen from (CH 2 -CH 2 O) x
- - RI and R2 identical or different, independently represent H or CH3,
- L independently represents a group selected from (CH 2 CH (CH 3) O) y (CH (CH 3) CH 2 O) and combinations thereof,
- 2-acrylamido-2-methylpropanesulphonic acid a salt of 2-acrylamido-2-methylpropanesulphonic acid, 2- (methacryloyloxy) ethanesulphonic acid, a salt of 2- (methacryloyloxy) ethanesulphonic acid, methallyl sulfonate, sodium, styrene sulfonate and mixtures thereof.
- the polymerization reaction may also employ a monomer of formula (IV):
- T1 and T2 identical or different, independently represent H or CH3,
- VI independently represents a group chosen from CH 2, CH 2 -CH 2, O-CH 2 -CH 2 -CH 2 -CH 2,
- V 2 independently represents a group chosen from (CH 2 -CH 2 O) p, (CH 2 CH (CH 3) O) q, (CH (CH 3) CH 2 O) and their combinations and
- - p, q and r identical or different, independently represent an integer or decimal number between 0 and 150, preferably p is strictly greater than q + r and the sum p + q + r is between 10 and 150.
- this additional monomer is a compound of formula (IV) in which:
- T1 and T2 represent H or CH3 or
- VI represents a group selected from CH2 or
- V2 represents a combination group (CH2-CH20) p and
- p represents an integer or decimal number between 10 and 140 or q + r represents an integer or decimal number between 10 and 140 where p is strictly greater than q + r and the sum p + q + r is between 10 and 150 .
- a more preferred compound of formula (IV) is a compound for which T 1 and T 2 represent H, V 1 represents CH 2 , V 2 represents a combination group (CH 2 -CH 2 O) P and CH 2 CH (CH 3 ) O) q or (CH (CH 3 ) CH 2 0) r , p represents an integer or decimal number between 10 and 140, q + r represents an integer or decimal number between 10 and 140 and p is strictly greater than q + r and the sum p + q + r is between 10 and 150.
- a compound of formula (IV) which is also more preferred is a compound for which T 1 represents CH 3 , T 2 represents H, V 1 represents CH 2 , V 2 represents a combination group (CH 2 -CH 2 0 ) and P (CH 2 CH (CH 3) 0) q or (CH (CH 3) CH 2 0) r, p represents an integer or decimal number between 10 and 140, q + r is an integer or decimal number between 10 and 140 and p is strictly greater than q + r and the sum p + q + r is between 10 and 150.
- a compound of formula (IV) which is also more preferred is a compound for which T 1 represents CH 3 , T 2 represents H, V 1 represents CH 2 , V 2 represents (CH 2 -CH 2 O) p , p represents an integer or decimal number between 10 and 140.
- a compound of formula (IV) that is also more preferred is a compound for which T 1 and T 2 represent H, V 1 represents O-CH 2 -CH 2 -CH 2 -CH 2 , V 2 represents (CH 2) 2 -CH 2 0) p , p represents an integer or decimal number between 10 and 140.
- a compound of formula (IV) which is also more preferred is a compound for which T 1 represents CH 3 , T 2 represents H, V 1 represents CH 2 -CH 2 , V 2 represents (CH 2 -CH 2 O ) p , p represents an integer or decimal number between 10 and 140.
- a particular copolymer according to the invention is a non-crosslinked copolymer.
- the invention provides an aqueous composition comprising at least one copolymer obtained by at least one radical polymerization reaction in water of at least one anionic monomer (a) comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts and at least one monomer (b) of formula (I).
- the invention also relates to such a copolymer as such, in particular such a copolymer obtained from an aqueous composition according to the invention and then separation of the copolymer according to the invention, in particular separation of water from the aqueous composition according to the invention. 'invention.
- the invention therefore provides a copolymer whose polymolecularity index Ip is less than 3, obtained at least one radical polymerization reaction in water and at a temperature ranging from 10 to 90 ° C.
- - RI and R2 identical or different, independently represent H or CH3,
- L independently represents a group chosen from (CH 2 -CH 2 O) x, (CH 2 CH (CH 3) O) y, (CH (CH 3) CH 2 O) and their combinations and
- - x, y and z identical or different, independently represent an integer or decimal number between 0 and 150 and the sum x + y + z is between 10 and 150;
- X independently represents H, Na or K
- R is independently a Cl-C5-alkyl group
- At least one radical generating compound selected from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, mixtures thereof or combinations thereof with an alkali metal bisulfite or with an ion selected from Fell, FelII , Ass, Cuil.
- the invention also provides a copolymer selected from:
- - RI and R2 identical or different, independently represent H or CH3,
- L independently represents a group chosen from (CH 2 -CH 2 O) x, (CH 2 CH (CH 3) O) y, (CH (CH 3) CH 2 O) and their combinations and
- - x, y and z identical or different, independently represent an integer or decimal number between 0 and 150 and the sum x + y + z is between 10 and 150;
- X independently represents H, Na or K
- R is independently a Cl-C5-alkyl group
- At least one radical-generating compound selected from hydrogen peroxide, an alkali metal persulfate, mixtures thereof or combinations thereof with an alkali metal bisulfite or with an ion selected from Fell, FelII, Cul, CuII and
- - RI and R2 identical or different, independently represent H or CH3,
- L independently represents a group selected from (CH 2 -CH 2 O) x combined with (CH (CH 3) CH 2 O) and (CH 2 CH (CH 3) O) combined with
- - x, y and z identical or different, independently represent an integer or decimal number between 0 and 150 and the sum x + y + z is between 10 and 150;
- X independently represents H, Na or K
- R is independently a C 1 -C 6 -alkyl group
- At least one radical-generating compound selected from hydrogen peroxide, ammonium persulfate, an alkali metal persulfate, mixtures thereof or combinations thereof with an alkali metal bisulfite or with an ion selected from Fe 11 , Fe 111 , Cu 1 , Cu 11 .
- the copolymer according to the invention comprises:
- the copolymer according to the invention comprises
- the copolymer according to the invention comprises
- the copolymer according to the invention comprises from 3 to 10% by weight of monomer (a) and
- the copolymer according to the invention comprises:
- the copolymer according to the invention may also be characterized by its weight-average molecular mass (Mw). Preferably, it has a weight-average molecular weight ranging from 8,000 g / mol to 600,000 g / mol or from 10,000 g / mol to 500,000 g / mol or from 12,000 g / mol to 200,000 g / mol. mol.
- it has a molecular weight in weight ranging from 15,000 g / mol to 150,000 g / mol or from 15,000 g / mol to 90,000 g / mol or from 15,000 g / mol to 90,000 g / mol or 25,000 g / mol to 75,000 g / mol.
- the molecular weight and the polymolecularity index of the copolymers is determined by Steric Exclusion Chromatography (SEC) or in English “Steric Exclusion Chromatography” (SEC).
- SEC Steric Exclusion Chromatography
- This technique uses a Waters liquid chromatography apparatus equipped with a detector. This detector is a Waters refractometric concentration detector.
- This liquid chromatography apparatus is provided with a steric exclusion column in order to separate the different molecular weights of the copolymers studied.
- the liquid elution phase is an aqueous phase adjusted to pH 9.00 using 1 N sodium hydroxide containing 0.05 M NaHCO 3 , 0.1 M NaNO, 0.02 M triethanolamine and 0.03% of Nope .
- the copolymer solution is diluted to 0.9% dry in the solubilization solvent of the CES, which corresponds to the liquid phase of elution of the CES, to which 0.04% of dimethylformamide which is added is added. the role of flow marker or internal standard. Then, it is filtered at 0.2 ⁇ . 100 ⁇ ⁇ are then injected into the chromatograph (eluent: an aqueous phase adjusted to pH 9.00 by N sodium hydroxide containing 0.05 M NaHC0, 0.1 M NaN0, 0.02 M triethanolamine and 0.03% NaN 3 ).
- the liquid chromatography apparatus contains an isocratic pump (Waters 515) with a flow rate of 0.8 mL / min.
- the chromatography apparatus also comprises an oven which itself comprises in series the following column system: a precolumn of the Guard Column Ultrahydrogel Waters type, 6 cm long and 40 mm inside diameter, and a linear column of the Ultrahydrogel Waters type. 30 cm in length and 7.8 mm inside diameter.
- the detection system consists of a type RI Waters 410 refractometric detector. The oven is heated to a temperature of 60 ° C and the refractometer is heated to a temperature of 45 ° C.
- Molecular weights are evaluated by dynamic light scattering detection by means of a Viscotek Dual 270 detector whereby the molecular weight is determined from the hydrodynamic volume of the copolymer.
- copolymers according to the invention which are also particular, advantageous or preferred.
- the aqueous composition and the copolymer according to the invention have particularly advantageous properties in many technical fields.
- the aqueous composition or the copolymer according to the invention can take different forms. They can in particular be implemented in different formulations.
- the invention therefore provides a formulation (Fl) comprising:
- the invention also provides a formulation (F2) comprising:
- formulations (Fl) and (F2) according to the invention comprise:
- copolymer from 0.01 to 5% by dry weight of copolymer, respectively in the form of at least one aqueous composition according to the invention or of at least one copolymer according to the invention as such;
- the formulations (F1) and (F2) according to the invention comprise: from 0.01 to 4% by dry weight or from 0.01 to 3% by dry weight of copolymer, respectively in the form of at least one aqueous composition according to the invention or of at least one copolymer according to the invention as such ; from 96 to 99.9% by dry weight or from 97 to 99.9% by dry weight of at least one hydraulic binder.
- formulations (F1) and (F2) according to the invention comprise:
- formulations (F1) and (F2) according to the invention comprise:
- the formulations (Fl) and (F2) according to the invention comprise water in an amount by weight relative to the amount by weight of hydraulic binder less than 0.7, less than 0.65 or less at 0.6, preferably less than 0.5 or less than 0.4 or even less than 0.3 or less than 0.2.
- Preferred ranges of amount of water by weight relative to the amount by weight of hydraulic binder in the formulations (F1) and (F2) are from 0.2 to 0.65 or from 0.2 to 0.6 or from 0.2 to 0.5 or 0.3 to 0.65 or 0.3 to 0.6 or 0.3 to 0.5.
- the hydraulic binder or hydrolite can be selected from cement, mortar, plaster, grout, concrete.
- the cement may be selected from Portland cement, white Portland cement, artificial cement, blast furnace cement, high strength cement, alumina cement, fast cement, magnesium phosphate cement, incineration cement, fly ash cement and mixtures thereof.
- Other hydraulic binders may be selected from latent hydraulic binders, pozzolanic binders, ash, slag, slag.
- the plaster may be selected from gypsum, calcium sulfate dihydrate, calcium sulfate, calcium sulfate hemihydrate, calcium sulfate anhydride and mixtures thereof.
- the aggregate may be selected from sand, coarse aggregate, gravel, crushed stone, slag, recycled aggregate.
- the aggregates are classified into several categories known as such by those skilled in the art, for example according to the French standard XP P 18-540. According to this standard, defining in particular the values d and D, the families of aggregates comprise:
- the adjuvant of the formulations (Fl) or (F2) may be chosen from an antifoaming agent, a plasticizer or superplasticizer, a workability improving agent, a sludge reducing agent, an air-reducing agent, a coloring agent, a pigment, a water-reducing agent, a setting-retarding agent, a hygroscopic control agent, an anti-corrosion agent, an anti-corrosion agent, removal, an agent inhibiting silico-alkaline reactions, a water-repellent agent, a foaming agent.
- the invention provides a method for modifying the rheology of a hydraulic formulation comprising the addition of at least one aqueous composition according to the invention or at least one copolymer according to the invention in the hydraulic formulation comprising water and a hydraulic binder.
- composition according to the invention and of the copolymer are particularly useful in the field of hydraulic formulations.
- the invention therefore provides a method for controlling the workability of a hydraulic formulation comprising the addition of at least one aqueous composition according to the invention or at least one copolymer according to the invention in a hydraulic formulation.
- the invention provides a workability control method for which the workability of the hydraulic formulation is kept constant for a period of at least 1 hour, preferably at least 2 hours, more preferably at least 3 h, still more preferably at least 3.5 h or at least 4 h.
- the invention also provides a method for reducing the setting time of a hydraulic formulation comprising the addition of at least one aqueous composition according to the invention or at least one copolymer according to the invention in a hydraulic formulation comprising water and a hydraulic binder.
- the hydraulic formulation is chosen from a hydraulic formulation (F1) and a hydraulic formulation (F2).
- the particular, advantageous or preferred characteristics of the hydraulic formulations (F1) and (F2) according to the invention define the methods for controlling the workability of a hydraulic formulation or for reducing the setting time of a hydraulic formulation according to the invention. which are also particular, advantageous or preferred.
- Example 1 Preparation of Copolymers According to the Invention and a Comparative Copolymer
- Example 1.1 Copolymer (PI) according to the invention
- the reactor is kept at a temperature of 65 ⁇ 2 ° C. for 1 hour.
- the product is cooled and then partially neutralized by addition of a 50% aqueous solution of sodium hydroxide (7.8 g).
- the aqueous polymeric solution comprises less than 220 ppm of dry residual acrylic acid relative to the total amount of dry copolymer.
- a copolymer (PI) comprising 12.8% by weight of acrylic acid and 87.2% by weight of monomer (bl2) is obtained. Its molecular weight Mw is 71,900 g / mol and its polymolecularity index Ip is 2.
- Example 1.2 Copolymer (P2) According to the Invention
- the reactor is kept at a temperature of 65 ⁇ 2 ° C. for 1 hour.
- the product is cooled and then partially neutralized by addition of a 50% aqueous solution of sodium hydroxide (1.6 g).
- the aqueous polymeric solution comprises less than
- a copolymer (P2) comprising 12.8% by weight of acrylic acid and 87.2% by weight of monomer (b 12) is obtained. Its molecular weight Mw is 207,000 g / mol and its polymolecularity index Ip is 2.2.
- Example 1.3 Copolymer (P3) According to the Invention
- water (400 g), iron sulfate heptahydrate (0.11 g) and DPTTC in solution at 20% by weight in water (3.18 g) are introduced.
- the reactor is heated to 65 ⁇ 2 ° C. 35% by weight aqueous hydrogen peroxide (22.4 g) is introduced.
- the reactor is kept at a temperature of 65 ⁇ 2 ° C. for 1 hour.
- the product is cooled and then partially neutralized by addition of a 50% aqueous solution of sodium hydroxide (6.7 g).
- the aqueous polymeric solution comprises less than 25 ppm of residual methacrylic acid.
- a copolymer (P3) comprising 7.4% by weight of methacrylic acid and 92.6% by weight of monomer (bl2) is obtained. Its molecular weight Mw is 168,600 g / mol and its polymolecularity index Ip is 2.
- Example 1.4 Copolymer (P4) According to the Invention
- the reactor is kept at a temperature of 65 ⁇ 2 ° C. for 30 minutes.
- the product is cooled and then partially neutralized by addition of a 50% aqueous solution of sodium hydroxide (1.1 g).
- the aqueous polymeric solution comprises less than
- a copolymer (P4) comprising 7.4% by weight of methacrylic acid and
- Example 1.5 Copolymer (P5) According to the Invention
- water 100 g
- iron sulphate heptahydrate (0.11 g)
- a monomer bl2 with a molecular mass of 3000 g / mol (114.23 g)
- a comonomer are introduced.
- T 1 represents C3 ⁇ 4
- T 2 represents H
- V 1 represents CH 2
- V 2 represents (CH 2 -CH 2 -0) p with a molecular weight of 2,400 g / mol, in solution at 60% mass in water (152.31 g), DPTTC in solution at 20% by weight in water (2.54 g).
- the reactor is heated to 65 ⁇ 2 ° C. 35% by weight aqueous hydrogen peroxide (5.6 g) is introduced.
- the product is cooled and then partially neutralized by addition of a 50% aqueous solution of sodium hydroxide (35 g).
- the aqueous polymeric solution comprises less than 55 ppm of residual acrylic acid.
- a copolymer (P5) comprising 13.6% by weight of acrylic acid, 38.4% by weight of comonomer of formula (IV) and 48.0% by weight of monomer (bl2) is obtained. Its molecular weight Mw is 238,000 g / mol and its polymolecularity index Ip is 2.9.
- Example 1.6 Copolymer (P6) According to the Invention
- the reactor is kept at a temperature of 65 ⁇ 2 ° C. for 1 hour.
- the product is cooled and then neutralized by adding an aqueous solution of 50% sodium hydroxide to pH 7.5.
- the aqueous polymeric solution comprises less than 1500 ppm of dry residual methacrylic acid relative to the total amount of dry copolymer.
- a copolymer (P6) comprising 7.44% by weight of methacrylic acid and 92.56% by weight of monomer (bl2) is obtained. Its molecular weight Mw is 194 560 g / mol and its polymolecularity index Ip is 1.6.
- the reactor is kept at a temperature of 65 ⁇ 2 ° C. for 1 hour.
- the product is cooled and then neutralized by addition of a 50% aqueous sodium hydroxide solution to pH 7.2.
- the aqueous polymeric solution comprises less than 2 ppm of dry residual methacrylic acid relative to the total amount of dry copolymer.
- a copolymer (P7) comprising 7.44% by weight of methacrylic acid and 92.56% by weight of monomer (bl2) is obtained. Its molecular weight Mw is 202 755 g / mol and its polymolecularity index I p is 1.6.
- the product is cooled and then partially neutralized by addition of a 50% aqueous solution of sodium hydroxide (4.1 g).
- the aqueous polymer solution comprises more than 4930 ppm of dry residual acrylic acid based on the total amount of dry copolymer.
- Mortar formulations are prepared whose composition is shown in the table
- a comparative formulation (FC) of mortar not comprising a copolymer is prepared.
- the water-reducing power of the copolymers according to the invention is evaluated from mortar formulations.
- the workability T0 of the mortars formulated with the copolymers according to the invention was evaluated by measuring the spreading diameter (slump flow in English) according to the EN 12350-2 standard adapted to the mortar (mini-cone of Abrams).
- the mortar filled cone is raised perpendicular to a horizontal plate while making a quarter turn.
- the spread is measured after 5 minutes in two diameters at 90 ° with a ruler.
- the result of the spread measurement is the average of the 2 values at ⁇ 1 mm.
- the tests are carried out at 20 ° C.
- the adjuvant dosage is determined so as to achieve a target spread of 220 mm ⁇ 5 mm.
- the dosage is expressed in% by dry weight relative to the weight of the hydraulic binder or the mixture of hydraulic binders. The results are shown in Table 1.
- the implementation of the copolymers according to the invention makes it possible to reduce the quantity of water by 25% in the hydraulic formulation, while maintaining an initial fluidity (handling) similar to that of the comparative formulation comprising no copolymer.
- copolymers according to the invention can therefore be qualified as high water reducing agents according to the standard ADJUVANT NF EN 934-2. Indeed, they allow a reduction of water for the adjuvanted mortar by at least 12% compared to the control mortar.
- copolymers according to the invention would make it possible to obtain similar results within the adjuvanted concrete by reducing the amount of water by at least 12% compared with a control concrete not comprising a copolymer according to the invention. invention.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1757218A FR3069546B1 (fr) | 2017-07-28 | 2017-07-28 | Composition polymerique aqueuse et copolymere |
PCT/FR2018/051900 WO2019020934A1 (fr) | 2017-07-28 | 2018-07-25 | Composition polymérique aqueuse et copolymère |
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EP18782779.5A Withdrawn EP3658597A1 (fr) | 2017-07-28 | 2018-07-25 | Composition polymérique aqueuse et copolymère |
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EP (1) | EP3658597A1 (fr) |
KR (1) | KR20200037145A (fr) |
CN (1) | CN110831988A (fr) |
FR (1) | FR3069546B1 (fr) |
WO (1) | WO2019020934A1 (fr) |
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FR3097865B1 (fr) * | 2019-06-26 | 2022-01-21 | Coatex Sas | Copolymère et composition de liant hydraulique |
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FR2868068B1 (fr) * | 2004-03-29 | 2006-07-14 | Coatex Soc Par Actions Simplif | Nouveaux composes soufres : utilisation comme agent de transfert pour la polymerisation radicalaire controlee de l'acide acrylique, polymeres obtenus et leurs applications |
US20060293417A1 (en) * | 2005-06-16 | 2006-12-28 | Kao Corporation | Hydraulic composition dispersant |
KR101899627B1 (ko) * | 2011-09-12 | 2018-09-17 | 가부시키가이샤 닛폰 쇼쿠바이 | 수경성 재료 첨가제용 폴리카르복실산계 중합체 |
KR101539350B1 (ko) * | 2012-08-21 | 2015-07-24 | 주식회사 엘지화학 | 폴리카르본산계 공중합체를 포함하는 시멘트 조성물의 첨가제 및 이를 포함하는 시멘트 조성물 |
FR2995899B1 (fr) * | 2012-09-26 | 2014-10-03 | Coatex Sas | Procede de polymerisation de l'acide (meth)acrylique en solution, solutions de polymeres obtenues et leurs utilisations. |
FR3013350B1 (fr) * | 2013-11-15 | 2016-09-02 | Coatex Sas | Agent retenteur de fluidite pour composition hydraulique compatible avec agent reducteur d'eau de type polymere peigne |
CN104031190A (zh) * | 2014-06-12 | 2014-09-10 | 东升新材料(山东)有限公司 | 光引发室温raft聚合制备高效重钙研磨分散剂 |
JP2018504508A (ja) * | 2014-12-08 | 2018-02-15 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | 分岐した反応性ブロックポリマーを製造する方法 |
CN105153375B (zh) * | 2015-09-21 | 2018-06-22 | 华南理工大学 | 一种用raft法合成聚羧酸减水剂的方法 |
CN106749872A (zh) * | 2016-12-22 | 2017-05-31 | 东升新材料(山东)有限公司 | 一种马丙共聚物的raft制备方法及其产品与应用 |
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- 2017-07-28 FR FR1757218A patent/FR3069546B1/fr not_active Expired - Fee Related
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2018
- 2018-07-25 EP EP18782779.5A patent/EP3658597A1/fr not_active Withdrawn
- 2018-07-25 KR KR1020197038299A patent/KR20200037145A/ko not_active Application Discontinuation
- 2018-07-25 WO PCT/FR2018/051900 patent/WO2019020934A1/fr active Application Filing
- 2018-07-25 CN CN201880042698.XA patent/CN110831988A/zh active Pending
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FR3069546B1 (fr) | 2020-09-25 |
FR3069546A1 (fr) | 2019-02-01 |
CN110831988A (zh) | 2020-02-21 |
WO2019020934A1 (fr) | 2019-01-31 |
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