WO2023187261A1 - Continuous preparation of a hydrophobic polyether compound - Google Patents
Continuous preparation of a hydrophobic polyether compound Download PDFInfo
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- WO2023187261A1 WO2023187261A1 PCT/FR2023/000028 FR2023000028W WO2023187261A1 WO 2023187261 A1 WO2023187261 A1 WO 2023187261A1 FR 2023000028 W FR2023000028 W FR 2023000028W WO 2023187261 A1 WO2023187261 A1 WO 2023187261A1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 19
- 229920000570 polyether Polymers 0.000 title claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 title description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000001125 extrusion Methods 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003973 paint Substances 0.000 claims description 29
- 238000009472 formulation Methods 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- -1 oxyethylene, oxyethylene-oxypropylene Chemical group 0.000 claims description 11
- 239000002562 thickening agent Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000003139 biocide Substances 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 3
- 239000013011 aqueous formulation Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 3
- 239000002966 varnish Substances 0.000 claims description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 229930182478 glucoside Natural products 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 230000003165 hydrotropic effect Effects 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013980 iron oxide Nutrition 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 235000020094 liqueur Nutrition 0.000 claims 1
- 230000008719 thickening Effects 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000010923 batch production Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000518 rheometry Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
Definitions
- the invention relates to a thickening copolymer and its continuous preparation method by reactive extrusion.
- the preparation method first comprises a polymerization reaction of a dihalogenated compound and a polyhydroxylated monomer and then the reaction with a monohalogenated hydrophobic compound.
- This copolymer makes it possible to control the viscosity of an aqueous composition.
- thickening agents which are generally water-soluble polymers comprising hydrophobic groups that are often insoluble in water.
- Such macromolecules have an associating character: once introduced into water, the hydrophobic groups are likely to assemble in the form of micellar aggregates. These aggregates are linked together by the hydrophilic parts of the polymers. A three-dimensional network is then formed which causes the viscosity of the medium to increase.
- compositions also comprising a latex-type binder compound
- the thickening agents generally make it possible to develop interactions with the particles of these binder compounds. Such interactions generally make it possible to increase the thickening effect.
- Compositions comprising a thickening polymer are usually prepared by prior synthesis of the thickening polymer by a discontinuous process, called a batch process.
- a thickening composition comprising a hydrophilic polymer, advantageously water-soluble, which are flexible and reproducible.
- water-soluble polymer means a polymer that is completely miscible with water at a temperature higher than the melting temperature of this polymer.
- aqueous coating compositions and in particular for aqueous paint or varnish compositions, it is necessary to control the viscosity both for low or medium shear gradients and for high shear gradients. Indeed, during its preparation, storage, application or drying, a paint formulation undergoes numerous constraints requiring particularly complex rheological properties.
- pigment particles tend to settle out due to gravity. Stabilizing the dispersion of these pigment particles then requires having a paint formulation whose viscosity is high at very low shear gradients corresponding to the limiting speed of the particles.
- Paint hold is the amount of paint carried away using an application tool, such as a paintbrush, brush or roller for example.
- the tool dipped and then removed from the paint pot carrying a high quantity of paint will avoid having to be refilled more frequently.
- Paint setting is an increasing function of viscosity.
- the calculation of the equivalent shear rate is a function of the paint flow speed for a particular thickness of paint on the tool.
- the paint formulation should therefore also have a high viscosity at low or medium shear gradients.
- a high filling power of the paint must be sought so that when it is applied to a substrate, a significant quantity of paint is deposited during each pass.
- a high filling power then makes it possible to obtain a greater wet film during each pass of the tool.
- High viscosity of the paint formulation must therefore be sought at high shear gradients.
- High viscosity at high shear gradients will also reduce or eliminate the risk of splashes or droplets forming during paint application.
- Hydrophobic compounds particularly hydrophobically modified compounds such as associative nonionic thickeners, are known as rheology modifying agents.
- known compounds do not always provide a satisfactory solution.
- the preparation of polymers by polymerization of polyethylene glycol often produces a reaction mixture whose viscosity increases significantly during the reaction, which can lead to a sharp increase in stirring energy consumption or to heating of the reaction medium.
- Document WO 9631550 describes a method for the batch preparation of polyether compounds from dihalides and a,co-difunctional polyethers.
- Document WO 2021022153 describes the batch preparation of polyacetal-poly ether polymers.
- Document WO 0034361 describes the discontinuous preparation of comb polymers from dibromomethane, polyethylene glycol and polyethoxylated amine, then cetyl bromide.
- Document WO 2020084200 describes the preparation of polyurethanes by reactive extrusion.
- the invention provides a method for the continuous preparation of a copolymer P by reactive extrusion comprising:
- the presence of a base is essential to allow the reaction of the polyhydroxylated monomer b with the dihalogenated compound a.
- the base is used in a molar excess relative to the molar quantity of OH groups of monomer b. More preferably, the base is used in a molar quantity of 1.05 to 10, preferably 1.1 to 6, molar equivalents relative to the molar quantity of OH groups of monomer b.
- the base implemented leads to an increase in the pH during the implementation of the method according to the invention.
- the polymerization is carried out at a pH greater than 10 or greater than 12.
- the base is a strong mineral base or a strong organic base. More preferably, the base is chosen from sodium hydride, potassium hydride, NaOH, KOH, sodium methanolate, potassium methanolate, sodium ethanolate, potassium ethanolate, sodium terZ-butanolate, potassium terZ-butanolate. Soda is the preferred base.
- the base makes it possible to obtain the alkoxide derivative of compound b.
- the treatment, total or partial using the base, of compound b, prior to carrying out the reactive extrusion can make it possible to directly introduce this alkoxide derivative of compound b.
- the alkoxide derivative of compound b can optionally be stored separately then introduced during the implementation of reactive extrusion in the presence of compound a.
- the method according to the invention comprises the polymerization of the polyhydroxylated monomer b and the dihalogenated compound a.
- the method according to the invention uses a single dihalogenated a compound or 2 or 3 different dihalogenated a compounds.
- the dihalogenated compound a is an al compound of formula I: LX x 2 (I) in which:
- - L independently represents a divalent hydrocarbon group, preferably a Ci-Cio-alkylene group, more preferably a Ci-C2-alkylene group, much more preferably CH2;
- - X 1 independently represents Br, Cl or I, preferably Br.
- the method according to the invention uses a single polyhydroxy compound b or 2 or 3 different polyhydroxy compounds b. More preferably according to the invention, the polyhydroxy compound b is a compound comprising 2, 3 or 4 hydroxyl groups.
- the polyhydroxy compound b is a compound b1 of formula II: HO-Q11-OH (II) in which:
- - Q independently represents an oxyalkylene group, preferably chosen from oxyethylene, oxyethylene-oxypropylene comprising at most 40 mole % of oxypropylene, oxyethylene-oxybutylene comprising at most 20 mole % of oxybutylene, and their combinations,
- - n independently represents a number ranging from 20 to 800.
- oxyethylene-oxypropylene copolymer In order for the oxyethylene-oxypropylene copolymer to retain its water-soluble character, its oxypropylene content is less than 40 molar%, advantageously less than 35 molar%. In order for the oxyethylene-oxybutylene copolymer to retain its water-soluble nature, its oxybutylene content is less than 20 molar%, advantageously less than 15 molar%.
- the preferred polyhydroxy compound b1 of formula II comprises Q oxyethylene groups.
- the polyhydroxy compound has a molar mass by mass (Mw) ranging from 800 to 40,000 g/mol, preferably from 2,000 to 20,000 g/mol, more preferably from 2,000 to 15,000 g/mol.
- Mw molar mass by mass
- the molar mass of compound b is determined by Size Exclusion Chromatography (CES).
- the method according to the invention uses a single monohalogenated hydrophobic compound c or 2 or 3 different monohalogenated hydrophobic compounds c.
- the monohalogenated hydrophobic compound is a cl compound of formula III:
- - R independently represents a hydrophobic hydrocarbon group, preferably a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic, or comprising from 6 to 40 carbon atoms;
- - X 2 independently represents Br, Cl or I, preferably Br.
- the hydrocarbon group R advantageously represents an alkyl or alkenyl group, linear, branched or cyclic, advantageously linear or branched, comprising from 6 to 40 carbon atoms, preferably from 6 to 32 carbon atoms.
- the hydrocarbon group R can also represent an aromatic group comprising from 6 to 40 carbon atoms, preferably from 7 to 32 carbon atoms.
- the hydrocarbon group R can also comprise a tristyrylphenyl group (TSP) of formula: or a distyrylphenyl group (DSP) of formula:
- TSP tristyrylphenyl group
- DSP distyrylphenyl group
- the copolymer P is advantageously prepared by reactive extrusion, relative to the total molar quantity of compounds a, b and c, by means of:
- the copolymer P can also be prepared by reactive extrusion, relative to the total molar quantity of compounds a, b and c, by means of:
- copolymer P can be prepared by reactive extrusion, relative to the total molar quantity of compounds a, b and c, using 20 mole % of dihalogenated compound a, 30 mole % of polyhydroxylated monomer b and 50 Mole % of monohalogenated hydrophobic compound c.
- the method according to the invention can be implemented with or without a solvent, for example in a solvent chosen from water, an organic solvent and their combinations, preferably water.
- the preparation method can be carried out in the absence of solvent.
- the preparation method according to the invention may also comprise a final acid treatment of the copolymer P leading to a pH less than 8, preferably to a pH greater than 6, for example by means of an acid, in particular a carboxylic acid such as acetic acid or lactic acid.
- a final acid treatment of the copolymer P leading to a pH less than 8, preferably to a pH greater than 6, for example by means of an acid, in particular a carboxylic acid such as acetic acid or lactic acid.
- the preparation method according to the invention comprises the reaction in a continuous process by reactive extrusion.
- Reactive extrusion is a generally known method for the preparation of thermoplastic polymers that have high glass transition or melting temperatures. Reactive extrusion generally allows all steps (mixing, polymerization and purification or devolatilization) to be carried out in the extruder. Although polyhydroxy compound b may be heat sensitive, no degradation is generally observed.
- Different types of extruder can allow the mixing of reagents: single-screw, two-stage or co-kneader, twin-screw, planetary gear, ring extruder. Twin-screw extruders are generally preferred.
- the L/D ratio (length/diameter) of the extruder is adapted according to the polymerization or polycondensation or polyaddition time, depending on the flow rate and the residence time.
- the L/D ratio can for example be greater than or equal to 20, more advantageously greater than or equal to 30.
- the implementation parameters can be adapted, in particular the rotation speed of the screws of the extruder, its design in the zones mixing, for example depending on the desired mixture.
- the extruder may include one or more feed zones. It is possible to pre-mix the components before introducing them into the extruder. It can also be envisaged to provide in the extruder a zone for melting some of the compounds before adding the other compounds, in particular compound b.
- the extruder may include one or more heating zones. Advantageously, it includes several heating zones. The polymerization or polycondensation or even polyaddition reaction is advantageously carried out at a temperature ranging from 50°C to 350°C, more advantageously ranging from 70°C to 300°C. Pressure can vary by 50 mbar (5,103 Pa) up to 50 bar (5 MPa).
- the polymerization or polycondensation or even polyaddition reaction is advantageously carried out under an inert atmosphere, for example by sweeping with nitrogen or argon.
- the method according to the invention may comprise one or more steps of evaporation of unreacted volatile components.
- the method according to the invention makes it possible to obtain the copolymer P with high conversion rates, in times compatible with industrial use.
- the method according to the invention compared to a batch process in a reactor, allows more rapid homogenization of the compounds with an increase in the speed of diffusion of the compounds and thus an improvement in mixing.
- the reagents are generally pumped to the reactor at a temperature between 70°C and 120°C.
- Hot water or steam can be used as the heat transfer fluid to control the reactor temperature in the range of 70°C to 120°C.
- the reactor may include distinct heating zones such that different zones may be maintained at different temperatures depending on the preparation requirements of the prepared P copolymer.
- the residence time in the reactor can be controlled, for example from less than one hour to more than six hours.
- a twin screw extruder can be fitted to the end of the reactor.
- the preparation method according to the invention is particularly advantageous as such but also for making it possible to obtain a particular copolymer P.
- the invention also relates to a copolymer P obtained according to the continuous preparation method by reactive extrusion defined according to the invention.
- the copolymer P is in solid form at 25°C.
- the preparation method according to the invention also makes it possible to improve the viscosifying properties of the copolymer P according to the invention.
- the same quantity of copolymer P obtained by the method according to the invention will be thicker than an identical quantity of polymer obtained by reaction of the same compounds, in the same proportions, but according to a batch process in a reactor.
- the method according to the invention makes it possible to obtain copolymers P having molar masses (Mw) higher than those of polymers which can be obtained in a batch process in a reactor while the increase in viscosity would impose a maximum molar mass limit. Reactive extrusion is particularly advantageous for the preparation of copolymer P despite the sensitivity of compound b to heat.
- Reactive extrusion saves time, with shorter cycle times compared to a batch reactor process. It is then possible to implement higher temperatures, for example when using polyalkylene glycol. The risk of thermal degradation of these compounds is then reduced, in particular thanks to reduced residence times.
- the molar mass (Mw) of the copolymer P may go up to 500,000 g/mol, advantageously it may vary from 10,000 to 500,000 g/mol, preferably from 60,000 to 500,000 g/mol. mol.
- the method according to the invention makes it possible to achieve polymers (P) of high molar mass (Mw), advantageously varying from 120,000 to 500,000 g/mol, preferably from 150,000 to 500,000 g/mol, preferably from 150,000 to 500,000 g/mol. 300,000 g/mol.
- the method according to the invention also makes it possible to prepare copolymers P of lower molar mass (Mw), advantageously varying from 10,000 to 150,000 g/mol, preferably from 60,000 to 150,000 g/mol, more preferably from 60,000 to 120,000. g/mol.
- the molecular mass of the copolymer P or of the compound b is determined by Size Exclusion Chromatography (CES) or in English “Gel Permeation Chromatography” (GPC).
- This technique uses a “Waters” brand liquid chromatography device equipped with a detector.
- This detector is a “Waters” 2414 type refractometric concentration detector.
- This liquid chromatography equipment is equipped with two steric exclusion columns in order to separate the different molecular weights of the polymers or compounds studied.
- the elution liquid phase is an organic phase composed of THF (HPLC grade, unstabilized).
- a first step approximately 25 mg of copolymer or compound is dissolved in 5 mL of THF, to which 0.1 mole % of water is added, used as an internal flow marker. Then, the solution is filtered to 0.2 ⁇ m. 50 ⁇ L are then injected into the chromatography apparatus (eluent: THF, HPLC grade, unstabilized).
- the liquid chromatography apparatus contains an isocratic pump (“Waters” 515) whose flow rate is set at 0.3 mL/min.
- the chromatography apparatus also includes an oven which includes a system of columns in series: an “Agilent” PLgel MiniMIX-A type column of 250 mm in length and 4.6 mm in diameter followed by an “Agilent” PLgel MiniMIX-B type column of 250 mm in length and 4.6 mm in diameter.
- the detection system consists of an RI “Waters” 2414 type refractometric detector. The columns are maintained at a temperature of 35°C and the refractometer is brought to a temperature of 35°C.
- the chromatography device is calibrated using polymethyl methacrylate standards certified by the supplier “Agilent” (“EasiVial” PMMA).
- copolymer P according to the invention can be used directly or it can be combined with other substances in a composition.
- the copolymer P according to the invention can be in the molten state, in particular at a temperature higher than its melting point and compatible with the intended use. It can also be used directly after cooling, especially after cooling to a temperature below its melting point. It can then be used in different solid forms, for example in a form chosen from pellet, flake, ground material, chip, powder and their combinations.
- the invention provides a rheological control composition
- a rheological control composition comprising at least one copolymer P according to the invention.
- the composition according to the invention can optionally be treated in an acidic manner leading to a pH less than 8, preferably a pH greater than 6, for example by means of an acid, in particular a carboxylic acid such as acetic acid. or lactic acid.
- the copolymer P according to the invention is combined with at least one solvent, in particular water or a coalescence solvent, for example glycol, butyl glycol, butyl diglycol, monopropylene glycol , ethyleneglycol, ethylenediglycol, “Dowanol” products whose CAS number is 34590-94-8, “Texanol” products whose CAS number is 25265-77-4; or combined with at least one additive chosen from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxy surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl glucosides; a hydrotropic compound, an anti-foam agent, a biocidal
- the invention also provides an aqueous formulation which can be used in many technical fields.
- the aqueous formulation according to the invention comprises:
- organic or mineral pigment or organic, organo-metallic or mineral particles for example calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides; and eventually
- At least one agent chosen from a particle spacer, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, an opacifying agent, a coloring agent, a solvent, a coalescing agent, an anti-foaming agent, a preservative, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof.
- the formulation according to the invention can be implemented in numerous technical fields.
- the formulation according to the invention can be a coating formulation.
- the formulation according to the invention is an ink formulation, an adhesive formulation, a varnish formulation, a paint formulation, for example decorative paint or industrial paint.
- the invention also provides a concentrated aqueous pigment paste comprising at least one copolymer P and at least one organic or mineral colored pigment.
- the copolymer P and the formulation according to the invention have properties allowing them to be used to modify or control the rheology of the medium comprising them.
- the invention also provides a method for controlling the viscosity of an aqueous composition.
- This method of controlling viscosity according to the invention comprises the addition of at least one copolymer P, obtained according to the invention, in an aqueous composition.
- the viscosity control method according to the invention is implemented for an aqueous composition which is a formulation according to the invention.
- the advantageous, particular or preferred characteristics of the preparation method according to the invention define copolymers P, aqueous compositions, formulations, pigment pastes as well as methods of controlling the viscosity according to the invention which are also advantageous, particular or preferred.
- Example 1 preparation of PI to Pl i copolymers according to the invention:
- the twin-screw extruder has 16 zones whose temperature is independently controlled. They can be heated electrically and cooled by circulating water.
- zone 16 corresponds to the die.
- the other zones are numbered 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, in that order between zone 1 and zone 16.
- Each zone has a length equal to 5 screw elements.
- the reagents can be stored in heated, stirred tanks under nitrogen, equipped with pumps allowing direct injection of the reagents into the extruder.
- the flow rates of each pump can be controlled independently in order to control the ratios between the different reagents as well as the overall flow rate. It is thus possible to adjust the residence time in the extruder.
- the residence time can be measured by adding a colored tracer.
- the compound bl is placed in a sealed tank heated to 90°C, under vacuum and dehydrated until a water content of less than 800 ppm is obtained. This tank is then purged with nitrogen. Compound bl is injected into zone 1 heated to 80°C of the extruder. Sodium hydroxide is added to zone 1 as well. Zones 2, 3, 4 and 5 of the extruder are respectively brought to 100°C, 100°C, 150°C and 150°C. The compound al is added in zone 6 of the extruder. Zones 6 to 9 are heated to 200°C to produce a copolymer of compounds al and bl. Then, the compound cl is introduced into zone 10, the temperature of which is 160°C. Zones 11 to 14 are maintained at this temperature. Zone 15 is cooled to 80°C. The residence time of the reaction medium in the extruder is approximately 9 minutes for a flow rate of 3 kg/h.
- the PI copolymer obtained at the extruder exit is in molten form.
- the PI copolymer is introduced directly at the outlet of the extruder die into an aqueous composition whose final pH is adjusted to approximately 7 by means of an aqueous acid solution.
- acetic and which also includes a surfactant compound (alcohol ethoxylate - “Emulan” HE 51 from “Basf”).
- the CRI composition comprises 30% by weight of PI copolymer, 20% by weight of surfactant compound and 50% by weight of aqueous solution comprising acetic acid.
- copolymers P2 to Pl i are prepared and characterized as well as the rheological control composition CR2 according to the invention comprising the copolymer P2.
- Example 2 preparation and characterization of aqueous paint formulations comprising the copolymers PI and P2 according to the invention:
- the CRI and CR2 compositions of PI and P2 copolymers according to the invention are used as a thickening agent for a solvent-free matt paint formulation.
- the CRI and CR2 compositions respectively comprising the thickening copolymers PI and P2 have a dry extract of 30% by weight of active material.
- Each paint formulation is prepared by mixing the different ingredients. The ingredients and quantities (in g) of the paint formulations are detailed in Table 2.
- copolymers according to the invention make it possible to effectively thicken a matt paint without solvent at different shear gradients. These copolymers can be used effectively as pseudoplastic additives.
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Abstract
The invention relates to a thickening copolymer and a method for continuously preparing the same by reactive extrusion. The preparation method first involves a polymerization reaction between a dihalogenated compound and a polyhydroxylated monomer, followed by a reaction with a monohalogenated hydrophobic compound. Said copolymer makes it possible to control the viscosity of an aqueous composition.
Description
PRÉPARATION CONTINUE DE COMPOSÉ POLYÉTHER HYDROPHOBE CONTINUOUS PREPARATION OF HYDROPHOBIC POLYETHER COMPOUND
L’invention concerne un copolymère épaississant et sa méthode de préparation continue par extrusion réactive. La méthode de préparation comprend d’abord une réaction de polymérisation d’un composé dihalogéné et d’un monomère polyhydroxylé puis la réaction avec un composé hydrophobe monohalogéné. Ce copolymère permet de contrôler la viscosité d’une composition aqueuse. The invention relates to a thickening copolymer and its continuous preparation method by reactive extrusion. The preparation method first comprises a polymerization reaction of a dihalogenated compound and a polyhydroxylated monomer and then the reaction with a monohalogenated hydrophobic compound. This copolymer makes it possible to control the viscosity of an aqueous composition.
De nombreux domaines techniques nécessitent de contrôler la rhéologie des compositions utilisées, en particulier de contrôler la rhéologie de compositions aqueuses. Disposer d’agents épaississants variés et efficaces est donc très utile. Many technical fields require controlling the rheology of the compositions used, in particular controlling the rheology of aqueous compositions. Having a variety of effective thickening agents is therefore very useful.
Parmi les agents épaississants, on distingue les épaississants associatifs qui sont généralement des polymères hydrosolubles comprenant des groupements hydrophobes souvent insolubles dans l’eau. De telles macromolécules ont un caractère associant : une fois introduits dans l'eau, les groupements hydrophobes sont susceptibles de s'assembler sous forme d'agrégats micellaires. Ces agrégats sont reliés entre eux par les parties hydrophiles des polymères. Il y a alors formation d'un réseau tridimensionnel qui provoque l'augmentation de la viscosité du milieu. Among the thickening agents, we distinguish associative thickeners which are generally water-soluble polymers comprising hydrophobic groups that are often insoluble in water. Such macromolecules have an associating character: once introduced into water, the hydrophobic groups are likely to assemble in the form of micellar aggregates. These aggregates are linked together by the hydrophilic parts of the polymers. A three-dimensional network is then formed which causes the viscosity of the medium to increase.
Au sein de compositions comprenant également un composé liant de type latex, les agents épaississants permettent généralement de développer des interactions avec les particules de ces composés liants. De telles interactions permettent alors généralement d’augmenter l’effet épaississant. Les compositions comprenant un polymère épaississant sont usuellement préparées par synthèse au préalable du polymère épaississant par un procédé discontinu, dit procédé batch. Within compositions also comprising a latex-type binder compound, the thickening agents generally make it possible to develop interactions with the particles of these binder compounds. Such interactions generally make it possible to increase the thickening effect. Compositions comprising a thickening polymer are usually prepared by prior synthesis of the thickening polymer by a discontinuous process, called a batch process.
Généralement, on recherche des méthodes de préparation de composition épaississante, comprenant un polymère hydrophile, avantageusement hydrosoluble, qui soient flexibles et reproductibles. On recherche également à améliorer l’efficacité d’épaississement de l’agent épaississant obtenu. Selon l’invention, on entend par polymère hydrosoluble un polymère totalement miscible à l’eau à une température supérieure à la température de fusion de ce polymère.
De manière générale pour les compositions aqueuses de revêtement, et en particulier pour les compositions aqueuses de peinture ou de vernis, il est nécessaire de contrôler la viscosité tant pour de faibles ou moyens gradients de cisaillement que pour des gradients de cisaillement élevés. En effet, au cours de sa préparation, de son stockage, de son application ou de son séchage, une formulation de peinture subit de nombreuses contraintes nécessitant des propriétés rhéologiques particulièrement complexes. Generally, we are looking for methods of preparing a thickening composition, comprising a hydrophilic polymer, advantageously water-soluble, which are flexible and reproducible. We also seek to improve the thickening efficiency of the thickening agent obtained. According to the invention, the term water-soluble polymer means a polymer that is completely miscible with water at a temperature higher than the melting temperature of this polymer. In general for aqueous coating compositions, and in particular for aqueous paint or varnish compositions, it is necessary to control the viscosity both for low or medium shear gradients and for high shear gradients. Indeed, during its preparation, storage, application or drying, a paint formulation undergoes numerous constraints requiring particularly complex rheological properties.
Lors du stockage de la peinture, les particules de pigment tendent à sédimenter par gravité. Stabiliser la dispersion de ces particules de pigment nécessite alors de disposer d’une formulation de peinture dont la viscosité est élevée à de très faibles gradients de cisaillement correspondant à la vitesse limite des particules. When storing paint, pigment particles tend to settle out due to gravity. Stabilizing the dispersion of these pigment particles then requires having a paint formulation whose viscosity is high at very low shear gradients corresponding to the limiting speed of the particles.
La prise de peinture est la quantité de peinture emportée au moyen d’un outil d’application, tel qu’un pinceau, une brosse ou un rouleau par exemple. L’outil plongé puis retiré du pot de peinture emportant une quantité élevée de peinture évitera de devoir être rechargé plus fréquemment. La prise de peinture est fonction croissante de la viscosité. Le calcul du gradient de cisaillement équivalent est fonction de la vitesse d’écoulement de la peinture pour une épaisseur particulière de peinture sur l’outil. La formulation de peinture devrait donc également avoir une viscosité élevée à des gradients de cisaillement faibles ou moyens. Paint hold is the amount of paint carried away using an application tool, such as a paintbrush, brush or roller for example. The tool dipped and then removed from the paint pot carrying a high quantity of paint will avoid having to be refilled more frequently. Paint setting is an increasing function of viscosity. The calculation of the equivalent shear rate is a function of the paint flow speed for a particular thickness of paint on the tool. The paint formulation should therefore also have a high viscosity at low or medium shear gradients.
De plus, un pouvoir garnissant élevé de la peinture doit être recherché afin que lors de son application sur un subjectile, une quantité importante de peinture soit déposée lors de chaque passage. Un pouvoir garnissant élevé permet alors d’obtenir un feuil humide plus important lors de chaque passage de l’outil. Une viscosité élevée de la formulation de peinture doit donc être recherchée à des gradients de cisaillement élevés. In addition, a high filling power of the paint must be sought so that when it is applied to a substrate, a significant quantity of paint is deposited during each pass. A high filling power then makes it possible to obtain a greater wet film during each pass of the tool. High viscosity of the paint formulation must therefore be sought at high shear gradients.
Une viscosité élevée à des gradients de cisaillement élevés permettra également de réduire ou d’éliminer le risque de formation d’éclaboussures ou de gouttelettes lors de l’application de la peinture. High viscosity at high shear gradients will also reduce or eliminate the risk of splashes or droplets forming during paint application.
Des composés hydrophobes, notamment des composés modifiés hydrophobiquement tels que les agents épaississants non-ioniques associatifs, sont connus comme agents modificateurs de rhéologie. Toutefois, les composés connus ne permettent pas toujours d’apporter de solution satisfaisante.
Par ailleurs, il est également important de pouvoir disposer de méthodes de préparation de copolymère améliorées. En effet, les méthodes connues, notamment les méthodes de préparation discontinue ou par batch, génèrent de nombreux problèmes les rendant difficiles à mettre en œuvre. Il peut s’avérer impossible de mettre en œuvre efficacement certaines méthodes de préparation d’agent épaississant tant les problèmes rencontrés peuvent être difficiles à surmonter, en particulier les problèmes de dérive de viscosité du milieu réactionnel de préparation d’agents épaississants. Par exemple, la préparation de polymères par polymérisation de polyéthylène glycol produit souvent un mélange réactionnel dont la viscosité augmente significativement au cours de la réaction, pouvant conduire à une forte augmentation de la consommation d’énergie d’agitation ou à un échauffement du milieu réactionnel du fait de l’exothermie due à l’agitation, voire à un blocage en cas de dérive trop importante de la viscosité. La préparation de tels polymères empêche alors l’utilisation de réacteurs agités. La préparation de ces polymères peut également nécessiter une importante dilution du milieu réactionnel au moyen d’un solvant devant ensuite être séparé. Néanmoins, l’utilisation de solvant devrait toujours être limitée ou éliminée. Hydrophobic compounds, particularly hydrophobically modified compounds such as associative nonionic thickeners, are known as rheology modifying agents. However, known compounds do not always provide a satisfactory solution. Furthermore, it is also important to have improved copolymer preparation methods. Indeed, known methods, in particular discontinuous or batch preparation methods, generate numerous problems making them difficult to implement. It may prove impossible to effectively implement certain methods of preparing thickening agents as the problems encountered may be difficult to overcome, in particular the problems of viscosity drift of the reaction medium for preparing thickening agents. For example, the preparation of polymers by polymerization of polyethylene glycol often produces a reaction mixture whose viscosity increases significantly during the reaction, which can lead to a sharp increase in stirring energy consumption or to heating of the reaction medium. due to exotherm due to agitation, or even to blockage in the event of excessive viscosity drift. The preparation of such polymers then prevents the use of stirred reactors. The preparation of these polymers may also require significant dilution of the reaction medium using a solvent which must then be separated. However, solvent use should always be limited or eliminated.
Il est également important de pouvoir disposer de méthodes de préparation flexibles, notamment de méthodes permettant de faire varier en cours de synthèse les réactifs introduits (nature, quantité) dans les zones d’alimentation. Améliorer la reproductibilité des méthodes de préparation de copolymère doit également être recherché. It is also important to be able to have flexible preparation methods, in particular methods allowing the reagents introduced (nature, quantity) to be varied during the synthesis in the feed zones. Improving the reproducibility of copolymer preparation methods must also be sought.
Le document WO 9631550 décrit une méthode de préparation discontinue de composés polyéthers à partir de dihalogénures et de polyéthers a,co-difonctionnels. Le document WO 2021022153 décrit la préparation discontinue de polymères polyacétal-poly éthers. Le document WO 0034361 décrit la préparation discontinue de polymères peigne à partir de de dibromométhane, de polyéthylèneglycol et d’amine polyéthoxylée, puis de bromure de cétyl. Le document WO 2020084200 décrit la préparation de polyuréthanes par extrusion réactive. Document WO 9631550 describes a method for the batch preparation of polyether compounds from dihalides and a,co-difunctional polyethers. Document WO 2021022153 describes the batch preparation of polyacetal-poly ether polymers. Document WO 0034361 describes the discontinuous preparation of comb polymers from dibromomethane, polyethylene glycol and polyethoxylated amine, then cetyl bromide. Document WO 2020084200 describes the preparation of polyurethanes by reactive extrusion.
Il existe donc un besoin de disposer d’une méthode de préparation de copolymère épaississant qui permette d’apporter une solution à tout ou partie des problèmes des méthodes connues.
Ainsi, l’invention fournit une méthode de préparation continue d’un copolymère P par extrusion réactive comprenant : There is therefore a need to have a method of preparing a thickening copolymer which makes it possible to provide a solution to all or part of the problems of known methods. Thus, the invention provides a method for the continuous preparation of a copolymer P by reactive extrusion comprising:
* la réaction de polymérisation en présence d’une base : a) d'au moins un composé dihalogéné a ; b) d’au moins un monomère polyhydroxylé b mis en œuvre en une quantité molaire apportant un nombre de groupements hydroxyles (OH) supérieur au nombre d’halogénures apportés par le composé a ; puis * the polymerization reaction in the presence of a base: a) of at least one dihalogenated compound a; b) at least one polyhydroxylated monomer b used in a molar quantity providing a number of hydroxyl groups (OH) greater than the number of halides provided by compound a; Then
* la réaction avec au moins un composé hydrophobe monohalogéné c. * the reaction with at least one monohalogenated hydrophobic compound c.
Pour l’efficacité de la méthode selon l’invention, la présence d’une base est essentielle pour permettre la réaction du monomère polyhydroxylé b avec le composé dihalogéné a. De manière préférée selon l’invention, la base est mise en œuvre en un excès molaire par rapport à la quantité molaire de groupements OH du monomère b. De manière plus préférée, la base est mise en œuvre en une quantité molaire de 1,05 à 10, de préférence de 1,1 à 6, équivalents molaires par rapport à la quantité molaire de groupements OH du monomère b. For the effectiveness of the method according to the invention, the presence of a base is essential to allow the reaction of the polyhydroxylated monomer b with the dihalogenated compound a. Preferably according to the invention, the base is used in a molar excess relative to the molar quantity of OH groups of monomer b. More preferably, the base is used in a molar quantity of 1.05 to 10, preferably 1.1 to 6, molar equivalents relative to the molar quantity of OH groups of monomer b.
La base mise en œuvre conduit à une augmentation du pH lors de la mise en œuvre de la méthode selon l’invention. De manière préférée, la polymérisation est réalisée à un pH supérieur à 10 ou supérieur à 12. The base implemented leads to an increase in the pH during the implementation of the method according to the invention. Preferably, the polymerization is carried out at a pH greater than 10 or greater than 12.
Selon l’invention, de nombreuses bases peuvent être utilisées. De manière préférée selon l’invention, la base est une base forte minérale ou une base forte organique. Plus préférentiellement, la base est choisie parmi hydrure de sodium, hydrure de potassium, NaOH, KOH, méthanolate de sodium, méthanolate de potassium, éthanolate de sodium, éthanolate de potassium, terZ-butanolate de sodium, terZ-butanolate de potassium. La soude est la base préférée. According to the invention, numerous bases can be used. Preferably according to the invention, the base is a strong mineral base or a strong organic base. More preferably, the base is chosen from sodium hydride, potassium hydride, NaOH, KOH, sodium methanolate, potassium methanolate, sodium ethanolate, potassium ethanolate, sodium terZ-butanolate, potassium terZ-butanolate. Soda is the preferred base.
Généralement selon l’invention la base permet d’obtenir le dérivé alcoolate du composé b. Generally according to the invention the base makes it possible to obtain the alkoxide derivative of compound b.
De manière avantageuse, le traitement, total ou partiel au moyen de la base, du composé b, préalablement à la mise en œuvre de l’extrusion réactive, peut permettre d’introduire directement ce dérivé alcoolate du composé b. Le dérivé alcoolate du composé b peut éventuellement être stocké séparément puis introduit lors de la mise en œuvre de l’extrusion réactive en présence du composé a.
La méthode selon l’invention comprend la polymérisation du monomère polyhydroxylé b et du composé dihalogéné a. De manière préférée, la méthode selon l’invention met en œuvre un unique composé dihalogéné a ou bien 2 ou 3 composés dihalogénés a différents. Préférentiellement selon l’invention, le composé dihalogéné a est un composé al de formule I : L-Xx 2 (I) dans laquelle : Advantageously, the treatment, total or partial using the base, of compound b, prior to carrying out the reactive extrusion, can make it possible to directly introduce this alkoxide derivative of compound b. The alkoxide derivative of compound b can optionally be stored separately then introduced during the implementation of reactive extrusion in the presence of compound a. The method according to the invention comprises the polymerization of the polyhydroxylated monomer b and the dihalogenated compound a. Preferably, the method according to the invention uses a single dihalogenated a compound or 2 or 3 different dihalogenated a compounds. Preferably according to the invention, the dihalogenated compound a is an al compound of formula I: LX x 2 (I) in which:
- L représente indépendamment un groupement hydrocarboné divalent, de préférence un groupe Ci-Cio-alkylène, plus préférentiellement un groupe Ci-C2-alkylène, bien plus préférentiellement CH2 ; - L independently represents a divalent hydrocarbon group, preferably a Ci-Cio-alkylene group, more preferably a Ci-C2-alkylene group, much more preferably CH2;
- X1 représente indépendamment Br, Cl ou I, de préférence Br. - X 1 independently represents Br, Cl or I, preferably Br.
Également de manière préférée, la méthode selon l’invention met en œuvre un unique composé polyhydroxylé b ou bien 2 ou 3 composés polyhydroxylés b différents. De manière plus préférée selon l’invention, le composé polyhydroxylé b est un composé comprenant 2, 3 ou 4 groupements hydroxyles. Also preferably, the method according to the invention uses a single polyhydroxy compound b or 2 or 3 different polyhydroxy compounds b. More preferably according to the invention, the polyhydroxy compound b is a compound comprising 2, 3 or 4 hydroxyl groups.
Plus préférentiellement, le composé polyhydroxylé b est un composé bl de formule II : HO-Q11-OH (II) dans laquelle : More preferably, the polyhydroxy compound b is a compound b1 of formula II: HO-Q11-OH (II) in which:
- Q représente indépendamment un groupement oxyalkylène, de préférence choisi parmi oxyéthylène, oxyéthylène-oxypropylène comprenant au plus 40 % molaire d’oxypropylène, oxyéthylène-oxybutylène comprenant au plus 20 % molaire d’oxybutylène, et leurs combinaisons, - Q independently represents an oxyalkylene group, preferably chosen from oxyethylene, oxyethylene-oxypropylene comprising at most 40 mole % of oxypropylene, oxyethylene-oxybutylene comprising at most 20 mole % of oxybutylene, and their combinations,
- n représente indépendamment un nombre allant de 20 à 800. - n independently represents a number ranging from 20 to 800.
Afin que le copolymère oxyéthylène-oxypropylène conserve son caractère hydrosoluble, sa teneur en oxypropylène est inférieure à 40 % molaire, avantageusement inférieure à 35 % molaire. Afin que le copolymère oxyéthylène-oxybutylène conserve son caractère hydrosoluble, sa teneur en oxybutylène est inférieure à 20 % molaire, avantageusement inférieure à 15 % molaire. In order for the oxyethylene-oxypropylene copolymer to retain its water-soluble character, its oxypropylene content is less than 40 molar%, advantageously less than 35 molar%. In order for the oxyethylene-oxybutylene copolymer to retain its water-soluble nature, its oxybutylene content is less than 20 molar%, advantageously less than 15 molar%.
Le composé polyhydroxylé bl de formule II préféré comprend des groupements Q oxyéthylène. Préférentiellement selon l’invention, le composé polyhydroxylé b a une
masse molaire en masse (Mw) allant de 800 à 40000 g/mol, de préférence de 2 000 à 20000 g/mol, plus préférentiellement de 2 000 à 15 000 g/mol. Selon l’invention, la masse molaire du composé b est déterminée par Chromatographie d'Exclusion Stérique (CES). The preferred polyhydroxy compound b1 of formula II comprises Q oxyethylene groups. Preferably according to the invention, the polyhydroxy compound has a molar mass by mass (Mw) ranging from 800 to 40,000 g/mol, preferably from 2,000 to 20,000 g/mol, more preferably from 2,000 to 15,000 g/mol. According to the invention, the molar mass of compound b is determined by Size Exclusion Chromatography (CES).
Également de manière préférée, la méthode selon l’invention met en œuvre un unique composé hydrophobe monohalogéné c ou bien 2 ou 3 composés hydrophobes monohalogénés c différents. Also preferably, the method according to the invention uses a single monohalogenated hydrophobic compound c or 2 or 3 different monohalogenated hydrophobic compounds c.
Plus préférentiellement, le composé hydrophobe monohalogéné c est un composé cl de formule III : More preferably, the monohalogenated hydrophobic compound is a cl compound of formula III:
R-X2 (III) dans laquelle : RX 2 (III) in which:
- R représente indépendamment un groupement hydrocarboné hydrophobe, de préférence un groupement hydrocarboné linéaire, ramifié ou cyclique, saturé, insaturé ou aromatique, ou comprenant de 6 à 40 atomes de carbone ; - R independently represents a hydrophobic hydrocarbon group, preferably a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic, or comprising from 6 to 40 carbon atoms;
- X2 représente indépendamment Br, Cl ou I, de préférence Br. - X 2 independently represents Br, Cl or I, preferably Br.
Selon l’invention, le groupement hydrocarboné R représente avantageusement un groupement alkyle ou alcényle, linéaire, ramifié ou cyclique, avantageusement linéaire ou ramifié, comprenant de 6 à 40 atomes de carbone, préférentiellement de 6 à 32 atomes de carbone. According to the invention, the hydrocarbon group R advantageously represents an alkyl or alkenyl group, linear, branched or cyclic, advantageously linear or branched, comprising from 6 to 40 carbon atoms, preferably from 6 to 32 carbon atoms.
Selon l’invention, le groupement hydrocarboné R peut également représenter un groupement aromatique comprenant de 6 à 40 atomes de carbone, préférentiellement de 7 à 32 atomes de carbone. According to the invention, the hydrocarbon group R can also represent an aromatic group comprising from 6 to 40 carbon atoms, preferably from 7 to 32 carbon atoms.
Selon l’invention, le groupement hydrocarboné R peut comprendre un radical de formule IV :
dans laquelle R” représente un groupement hydrocarboné de formule C15H31-X dans
laquelle x = 0, 2, 4, 6 ; pouvant ainsi comprendre 0, 1, 2 ou 3 insaturations éthyléniques (double liaison). According to the invention, the hydrocarbon group R may comprise a radical of formula IV: in which R” represents a hydrocarbon group of formula C15H31-X in which x = 0, 2, 4, 6; thus being able to comprise 0, 1, 2 or 3 ethylenic unsaturations (double bond).
Un tel radical de formule (IV) est avantageusement dérivé du cardanol, et ainsi d’origine bio-ressourcée et non polluante. Selon l’invention, le groupement hydrocarboné R peut également comprendre un groupe tristyrylphényle (TSP) de formule :
ou un groupe distyrylphényle (DSP) de formule :
Such a radical of formula (IV) is advantageously derived from cardanol, and thus of bio-resourced and non-polluting origin. According to the invention, the hydrocarbon group R can also comprise a tristyrylphenyl group (TSP) of formula: or a distyrylphenyl group (DSP) of formula:
Selon l’invention, le copolymère P est avantageusement préparé par extrusion réactive, par rapport à la quantité molaire totale des composés a, b et c, au moyen de : According to the invention, the copolymer P is advantageously prepared by reactive extrusion, relative to the total molar quantity of compounds a, b and c, by means of:
* 5 % molaire à 60 % molaire de composé dihalogéné a ; * 5 mole % to 60 mole % of dihalogenated compound a;
* 10 % molaire à 65 % molaire de monomère polyhydroxylé b ; * 10 mole % to 65 mole % of polyhydroxylated monomer b;
* 30 % molaire à 85 % molaire de composé hydrophobe monohalogéné c. * 30 mole % to 85 mole % of monohalogenated hydrophobic compound c.
Le copolymère P peut également être préparé par extrusion réactive, par rapport à la quantité molaire totale des composés a, b et c, au moyen de : The copolymer P can also be prepared by reactive extrusion, relative to the total molar quantity of compounds a, b and c, by means of:
* 5 % molaire à 50 % molaire de composé dihalogéné a ; * 5 mole % to 50 mole % of dihalogenated compound a;
* 15 % molaire à 60 % molaire de monomère polyhydroxylé b ; * 15 mole % to 60 mole % of polyhydroxylated monomer b;
* 35 % molaire à 80 % molaire de composé hydrophobe monohalogéné c. * 35 mole % to 80 mole % of monohalogenated hydrophobic compound c.
Un exemple particulier de copolymère P peut être préparé par extrusion réactive, par rapport à la quantité molaire totale des composés a, b et c, au moyen de 20 % molaire de composé dihalogéné a, de 30 % molaire de monomère polyhydroxylé b et de 50 % molaire de composé hydrophobe monohalogéné c.
De manière particulièrement avantageuse, notamment par rapport à un procédé batch qui nécessite la dilution du milieu réactionnel, la méthode selon l’invention peut être mise en œuvre avec ou sans solvant, par exemple dans un solvant choisi parmi l’eau, un solvant organique et leurs combinaisons, de préférence de l’eau. De manière préférée selon l’invention, la méthode de préparation peut être conduite en l’absence de solvant. A particular example of copolymer P can be prepared by reactive extrusion, relative to the total molar quantity of compounds a, b and c, using 20 mole % of dihalogenated compound a, 30 mole % of polyhydroxylated monomer b and 50 Mole % of monohalogenated hydrophobic compound c. Particularly advantageously, in particular compared to a batch process which requires the dilution of the reaction medium, the method according to the invention can be implemented with or without a solvent, for example in a solvent chosen from water, an organic solvent and their combinations, preferably water. Preferably according to the invention, the preparation method can be carried out in the absence of solvent.
De manière avantageuse, la méthode de préparation selon l’invention peut comprendre également un traitement acide final du copolymère P conduisant à un pH inférieur à 8, de préférence à un pH supérieur à 6, par exemple au moyen d’un acide, notamment un acide carboxy lique tel que l’acide acétique ou l’acide lactique. Advantageously, the preparation method according to the invention may also comprise a final acid treatment of the copolymer P leading to a pH less than 8, preferably to a pH greater than 6, for example by means of an acid, in particular a carboxylic acid such as acetic acid or lactic acid.
La méthode de préparation selon l’invention comprend la réaction selon un procédé continu par extrusion réactive. L’extrusion réactive est une méthode généralement connue pour la préparation de polymères thermoplastiques qui ont des hautes températures de transition vitreuse ou de fusion. L’extrusion réactive permet généralement de réaliser toutes les étapes (mélangeage, polymérisation et purification ou dévolatilisation) dans l’extrudeuse. Bien que le composé polyhydroxylé b puisse être sensible à la chaleur, aucune dégradation n’est généralement observée. Différents types d’extrudeuse peuvent permettre le mélange des réactifs : extrudeuse monovis, à deux étages ou co-malaxeur (en anglais : co-kneader), bi-vis, à engrenage planétaire, à anneaux. Les extrudeuses bi-vis sont généralement préférées. Le rapport L/D (longueur/diamètre) de l’extrudeuse est adapté en fonction du temps de polymérisation ou de polycondensation ou encore de polyaddition, dépendant du débit et du temps de séjour. Le rapport L/D peut par exemple être supérieur ou égal à 20, plus avantageusement supérieur ou égal à 30. Les paramètres de mise en œuvre peuvent être adaptés, notamment la vitesse de rotation des vis de l’extrudeuse, son design dans les zones de mélange, par exemple en fonction du mélangeage souhaité. The preparation method according to the invention comprises the reaction in a continuous process by reactive extrusion. Reactive extrusion is a generally known method for the preparation of thermoplastic polymers that have high glass transition or melting temperatures. Reactive extrusion generally allows all steps (mixing, polymerization and purification or devolatilization) to be carried out in the extruder. Although polyhydroxy compound b may be heat sensitive, no degradation is generally observed. Different types of extruder can allow the mixing of reagents: single-screw, two-stage or co-kneader, twin-screw, planetary gear, ring extruder. Twin-screw extruders are generally preferred. The L/D ratio (length/diameter) of the extruder is adapted according to the polymerization or polycondensation or polyaddition time, depending on the flow rate and the residence time. The L/D ratio can for example be greater than or equal to 20, more advantageously greater than or equal to 30. The implementation parameters can be adapted, in particular the rotation speed of the screws of the extruder, its design in the zones mixing, for example depending on the desired mixture.
L’extrudeuse peut comprendre une ou plusieurs zones d’alimentation. Il est envisageable de pré-mélanger les composants avant introduction dans l’extrudeuse. Il peut également être envisagé de prévoir dans l’extrudeuse une zone de fusion de certains des composés avant ajout des autres composés, en particulier du composé b. L’extrudeuse peut comprendre une ou plusieurs zones de chauffage. Avantageusement, elle comprend plusieurs zones de chauffage. La réaction de polymérisation ou de polycondensation ou encore de polyaddition est avantageusement conduite à une température allant de 50°C à 350°C, plus avantageusement allant de 70°C à 300°C. La pression peut varier de 50 mbar
(5 103 Pa) jusqu’à 50 bars (5 MPa). La réaction de polymérisation ou de polycondensation ou encore de polyaddition est avantageusement conduite sous atmosphère inerte, par exemple par balayage d’azote ou d’argon. La méthode selon l’invention peut comprendre une ou plusieurs étapes d’évaporation des composants volatils n’ayant pas réagi. La méthode selon l’invention permet d’obtenir le copolymère P avec des taux de conversion élevés, en des durées compatibles avec un usage industriel. En outre, la méthode selon l’invention, comparée à un procédé discontinu en réacteur, permet une homogénéisation plus rapide des composés avec une augmentation de la vitesse de diffusion des composés et ainsi une amélioration du mélangeage. The extruder may include one or more feed zones. It is possible to pre-mix the components before introducing them into the extruder. It can also be envisaged to provide in the extruder a zone for melting some of the compounds before adding the other compounds, in particular compound b. The extruder may include one or more heating zones. Advantageously, it includes several heating zones. The polymerization or polycondensation or even polyaddition reaction is advantageously carried out at a temperature ranging from 50°C to 350°C, more advantageously ranging from 70°C to 300°C. Pressure can vary by 50 mbar (5,103 Pa) up to 50 bar (5 MPa). The polymerization or polycondensation or even polyaddition reaction is advantageously carried out under an inert atmosphere, for example by sweeping with nitrogen or argon. The method according to the invention may comprise one or more steps of evaporation of unreacted volatile components. The method according to the invention makes it possible to obtain the copolymer P with high conversion rates, in times compatible with industrial use. Furthermore, the method according to the invention, compared to a batch process in a reactor, allows more rapid homogenization of the compounds with an increase in the speed of diffusion of the compounds and thus an improvement in mixing.
Selon l’invention, les réactifs sont généralement pompés vers le réacteur à une température comprise entre 70°C et 120°C. De l'eau chaude ou de la vapeur peuvent être utilisées comme fluide caloporteur pour contrôler la température du réacteur dans la plage de 70°C à 120°C. Le réacteur peut comprendre des zones de chauffage distinctes de sorte que différentes zones peuvent être maintenues à différentes températures en fonction des exigences de préparation du copolymère P préparé. De même, le temps de séjour dans le réacteur peut être contrôlé, par exemple de moins d'une heure à plus de six heures. Une extrudeuse à double vis peut équiper l’extrémité du réacteur. According to the invention, the reagents are generally pumped to the reactor at a temperature between 70°C and 120°C. Hot water or steam can be used as the heat transfer fluid to control the reactor temperature in the range of 70°C to 120°C. The reactor may include distinct heating zones such that different zones may be maintained at different temperatures depending on the preparation requirements of the prepared P copolymer. Likewise, the residence time in the reactor can be controlled, for example from less than one hour to more than six hours. A twin screw extruder can be fitted to the end of the reactor.
La méthode de préparation selon l’invention est particulièrement avantageuse en tant que telle mais également pour permettre d’obtenir un copolymère P particulier. Ainsi, l’invention concerne également un copolymère P obtenu selon la méthode de préparation continue par extrusion réactive définie selon l’invention. De manière préférée, le copolymère P est sous forme solide à 25 °C. The preparation method according to the invention is particularly advantageous as such but also for making it possible to obtain a particular copolymer P. Thus, the invention also relates to a copolymer P obtained according to the continuous preparation method by reactive extrusion defined according to the invention. Preferably, the copolymer P is in solid form at 25°C.
De manière surprenante, la méthode de préparation selon l’invention permet également d’améliorer les propriétés viscosifiantes du copolymère P selon l’invention. Ainsi, une même quantité de copolymère P obtenu par la méthode selon l’invention sera plus épaississante qu’une quantité identique de polymère obtenu par réaction des mêmes composés, dans les mêmes proportions, mais selon un procédé discontinu dans un réacteur. Également, la méthode selon l’invention permet d’obtenir des copolymères P ayant des masses molaires (Mw) plus élevées que celles de polymères pouvant être obtenus dans un procédé discontinu dans un réacteur alors que l’augmentation de viscosité imposerait une
limite maximale de masse molaire. L’extrusion réactive est particulièrement avantageuse pour la préparation du copolymère P malgré la sensibilité du composé b à la chaleur. Surprisingly, the preparation method according to the invention also makes it possible to improve the viscosifying properties of the copolymer P according to the invention. Thus, the same quantity of copolymer P obtained by the method according to the invention will be thicker than an identical quantity of polymer obtained by reaction of the same compounds, in the same proportions, but according to a batch process in a reactor. Also, the method according to the invention makes it possible to obtain copolymers P having molar masses (Mw) higher than those of polymers which can be obtained in a batch process in a reactor while the increase in viscosity would impose a maximum molar mass limit. Reactive extrusion is particularly advantageous for the preparation of copolymer P despite the sensitivity of compound b to heat.
L’extrusion réactive permet un gain de temps, avec des temps de cycle plus courts comparativement à un procédé discontinu en réacteur. Il est alors possible de mettre en œuvre des températures plus élevées, par exemple lors de l’utilisation de polyalkyleneglycol. Le risque de dégradation thermique de ces composés est alors réduit, notamment grâce à des temps de séjour réduits. Reactive extrusion saves time, with shorter cycle times compared to a batch reactor process. It is then possible to implement higher temperatures, for example when using polyalkylene glycol. The risk of thermal degradation of these compounds is then reduced, in particular thanks to reduced residence times.
De manière préférée selon l’invention, la masse molaire (Mw) du copolymère P pourra aller jusqu’à 500 000 g/mol, avantageusement elle pourra varier de 10 000 à 500000 g/mol, de préférence de 60000 à 500 000 g/mol. Preferably according to the invention, the molar mass (Mw) of the copolymer P may go up to 500,000 g/mol, advantageously it may vary from 10,000 to 500,000 g/mol, preferably from 60,000 to 500,000 g/mol. mol.
La méthode selon l’invention permet d’atteindre des polymères (P) de masse molaire (Mw) élevée, variant avantageusement de 120 000 à 500 000 g/mol, de préférence de 150000 à 500000 g/mol, de préférence de 150000 à 300 000 g/mol. La méthode selon l’invention permet également de préparer des copolymères P de masse molaire (Mw) plus faible, variant avantageusement de 10000 à 150000 g/mol, de préférence de 60 000 à 150000 g/mol, plus préférentiellement de 60 000 à 120000 g/mol. The method according to the invention makes it possible to achieve polymers (P) of high molar mass (Mw), advantageously varying from 120,000 to 500,000 g/mol, preferably from 150,000 to 500,000 g/mol, preferably from 150,000 to 500,000 g/mol. 300,000 g/mol. The method according to the invention also makes it possible to prepare copolymers P of lower molar mass (Mw), advantageously varying from 10,000 to 150,000 g/mol, preferably from 60,000 to 150,000 g/mol, more preferably from 60,000 to 120,000. g/mol.
Selon l’invention, la masse moléculaire du copolymère P ou du composé b est déterminée par Chromatographie d'Exclusion Stérique (CES) ou en anglais « Gel Permeation Chromatography » (GPC). Cette technique met en œuvre un appareil de chromatographie liquide de marque « Waters » doté d'un détecteur. Ce détecteur est un détecteur de concentration réfractométrique de type « Waters » 2414. Cet appareillage de chromatographie liquide est doté de deux colonnes d'exclusion stérique afin de séparer les différents poids moléculaires des polymères ou composés étudiés. La phase liquide d'élution est une phase organique composée de THF (grade HPLC, non stabilisé). According to the invention, the molecular mass of the copolymer P or of the compound b is determined by Size Exclusion Chromatography (CES) or in English “Gel Permeation Chromatography” (GPC). This technique uses a “Waters” brand liquid chromatography device equipped with a detector. This detector is a “Waters” 2414 type refractometric concentration detector. This liquid chromatography equipment is equipped with two steric exclusion columns in order to separate the different molecular weights of the polymers or compounds studied. The elution liquid phase is an organic phase composed of THF (HPLC grade, unstabilized).
Lors d’une première étape, on solubilise environ 25 mg de copolymère ou de composé dans 5 mL de THF, additionné de 0,1 % molaire d’eau utilisée comme marqueur interne de débit. Puis, on filtre la solution à 0,2 pm. 50 pL sont ensuite injectés dans l'appareil de chromatographie (éluant : THF, grade HPLC, non stabilisé). In a first step, approximately 25 mg of copolymer or compound is dissolved in 5 mL of THF, to which 0.1 mole % of water is added, used as an internal flow marker. Then, the solution is filtered to 0.2 μm. 50 μL are then injected into the chromatography apparatus (eluent: THF, HPLC grade, unstabilized).
L'appareil de chromatographie liquide contient une pompe isocratique (« Waters » 515) dont le débit est réglé à 0,3 mL/min. L’appareil de chromatographie comprend également
un four qui comprend un système de colonnes en série : une colonne de type « Agilent » PLgel MiniMIX-A de 250 mm de longueur et 4,6 mm de diamètre suivie d’une colonne de type « Agilent » PLgel MiniMIX-B de 250 mm de longueur et 4,6 mm de diamètre. Le système de détection se compose d’un détecteur réfractométrique de type RI « Waters » 2414. Les colonnes sont maintenues à la température de 35 °C et le réfractomètre est porté à la température de 35 °C. The liquid chromatography apparatus contains an isocratic pump (“Waters” 515) whose flow rate is set at 0.3 mL/min. The chromatography apparatus also includes an oven which includes a system of columns in series: an “Agilent” PLgel MiniMIX-A type column of 250 mm in length and 4.6 mm in diameter followed by an “Agilent” PLgel MiniMIX-B type column of 250 mm in length and 4.6 mm in diameter. The detection system consists of an RI “Waters” 2414 type refractometric detector. The columns are maintained at a temperature of 35°C and the refractometer is brought to a temperature of 35°C.
L'appareil de chromatographie est étalonné au moyen d’étalons de polyméthacrylate de méthyle certifiés par le fournisseur « Agilent » (« EasiVial » PMMA). The chromatography device is calibrated using polymethyl methacrylate standards certified by the supplier “Agilent” (“EasiVial” PMMA).
Le copolymère P selon l’invention peut être utilisé directement ou bien il peut être associé à d’autres substances dans une composition. The copolymer P according to the invention can be used directly or it can be combined with other substances in a composition.
Utilisé directement, le copolymère P selon l’invention peut être à l’état fondu, notamment à une température supérieure à son point de fusion et compatible avec l’usage envisagé. Il peut également être utilisé directement après refroidissement, en particulier après refroidissement à une température inférieure à son point de fusion. Il peut alors être utilisé sous différentes formes solides, par exemple sous une forme choisie parmi pastille, flocon, broyât, copeau, poudre et leurs combinaisons. Used directly, the copolymer P according to the invention can be in the molten state, in particular at a temperature higher than its melting point and compatible with the intended use. It can also be used directly after cooling, especially after cooling to a temperature below its melting point. It can then be used in different solid forms, for example in a form chosen from pellet, flake, ground material, chip, powder and their combinations.
Également, l’invention fournit une composition de contrôle rhéologique comprenant au moins un copolymère P selon l’invention. La composition selon l’invention peut éventuellement être traitée de manière acide conduisant à un pH inférieur à 8, de préférence à un pH supérieur à 6, par exemple au moyen d’un acide, notamment un acide carboxy lique tel que l’acide acétique ou l’acide lactique. Also, the invention provides a rheological control composition comprising at least one copolymer P according to the invention. The composition according to the invention can optionally be treated in an acidic manner leading to a pH less than 8, preferably a pH greater than 6, for example by means of an acid, in particular a carboxylic acid such as acetic acid. or lactic acid.
De manière préférée, dans la composition de contrôle rhéologique selon l’invention, le copolymère P selon l’invention est combiné à au moins un solvant, notamment de l’eau ou un solvant de coalescence, par exemple glycol, butylglycol, butyldiglycol, monopropyleneglycol, ethyleneglycol, ethylenediglycol, produits « Dowanol » dont le numéro CAS est 34590-94-8, produits « Texanol » dont le numéro CAS est 25265-77-4 ; ou combiné à au moins un additif choisi parmi un composé amphiphile, notamment un composé tensio-actif, de préférence un composé tensio-actif hydroxy lé, par exemple alkyl- polyalkyleneglycol, notamment alkyl-polyethyleneglycol et alkyl-polypropyleneglycol ; un dérivé de polysaccharide, par exemple cyclodextrine, dérivé de cyclodextrine,
polyéthers, alkyl-glucosides ; un composé hydrotrope, un agent anti-mousse, un agent biocide et leurs combinaisons. Preferably, in the rheological control composition according to the invention, the copolymer P according to the invention is combined with at least one solvent, in particular water or a coalescence solvent, for example glycol, butyl glycol, butyl diglycol, monopropylene glycol , ethyleneglycol, ethylenediglycol, “Dowanol” products whose CAS number is 34590-94-8, “Texanol” products whose CAS number is 25265-77-4; or combined with at least one additive chosen from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxy surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl glucosides; a hydrotropic compound, an anti-foam agent, a biocidal agent and combinations thereof.
L’invention fournit également une formulation aqueuse qui peut être utilisée dans de nombreux domaines techniques. La formulation aqueuse selon l’invention comprend :The invention also provides an aqueous formulation which can be used in many technical fields. The aqueous formulation according to the invention comprises:
- au moins une composition selon l’invention ; éventuellement - at least one composition according to the invention; possibly
- au moins un pigment organique ou minéral ou des particules organiques, organo- métalliques ou minérales, par exemple carbonate de calcium, talc, kaolin, mica, silicates, silice, oxydes métalliques, notamment dioxyde de titane, oxydes de fer ; et éventuellement- at least one organic or mineral pigment or organic, organo-metallic or mineral particles, for example calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides; and eventually
- au moins un agent choisi parmi un agent espaceur de particules, un agent dispersant, un agent stabilisant stérique, un agent stabilisant électrostatique, un agent opacifiant, un agent colorant, un solvant, un agent de coalescence, un agent anti-mousse, un agent de conservation, un agent biocide, un agent d’étalement, un agent épaississant, un copolymère filmogène et leurs mélanges. - at least one agent chosen from a particle spacer, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, an opacifying agent, a coloring agent, a solvent, a coalescing agent, an anti-foaming agent, a preservative, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof.
Selon le copolymère P particulier ou les additifs qu’elle comprend la formulation selon l’invention peut être mise en œuvre dans de nombreux domaines techniques. Ainsi, la formulation selon l’invention peut être une formulation de revêtement. De préférence, la formulation selon l’invention est une formulation d’encre, une formulation d’adhésif, une formulation de vernis, une formulation de peinture, par exemple de peinture décorative ou de peinture industrielle. Depending on the particular copolymer P or the additives it comprises, the formulation according to the invention can be implemented in numerous technical fields. Thus, the formulation according to the invention can be a coating formulation. Preferably, the formulation according to the invention is an ink formulation, an adhesive formulation, a varnish formulation, a paint formulation, for example decorative paint or industrial paint.
L’invention fournit également une pâte pigmentaire aqueuse concentrée comprenant au moins un copolymère P et au moins un pigment coloré organique ou minéral. The invention also provides a concentrated aqueous pigment paste comprising at least one copolymer P and at least one organic or mineral colored pigment.
Le copolymère P et la formulation selon l’invention possèdent des propriétés permettant de les utiliser pour modifier ou contrôler la rhéologie du milieu les comprenant. Ainsi, l’invention fournit également une méthode de contrôle de la viscosité d’une composition aqueuse. Cette méthode de contrôle de la viscosité selon l’invention comprend l’addition d’au moins un copolymère P, obtenu selon l’invention, dans une composition aqueuse. The copolymer P and the formulation according to the invention have properties allowing them to be used to modify or control the rheology of the medium comprising them. Thus, the invention also provides a method for controlling the viscosity of an aqueous composition. This method of controlling viscosity according to the invention comprises the addition of at least one copolymer P, obtained according to the invention, in an aqueous composition.
De manière préférée, la méthode de contrôle de la viscosité selon l’invention est mise en œuvre pour une composition aqueuse qui est une formulation selon l’invention.
Les caractéristiques avantageuses, particulières ou préférées de la méthode de préparation selon l’invention définissent des copolymères P, des compositions aqueuses, des formulations, des pâtes pigmentaires ainsi que des méthodes de contrôle de la viscosité selon l’invention qui sont également avantageuses, particulières ou préférées. Preferably, the viscosity control method according to the invention is implemented for an aqueous composition which is a formulation according to the invention. The advantageous, particular or preferred characteristics of the preparation method according to the invention define copolymers P, aqueous compositions, formulations, pigment pastes as well as methods of controlling the viscosity according to the invention which are also advantageous, particular or preferred.
Les exemples qui suivent permettent d’illustrer les différents aspects de l’invention. The examples which follow illustrate the different aspects of the invention.
EXEMPLES : EXAMPLES:
Exemple 1 : préparation de copolymères PI à Pl i selon l’invention : Example 1: preparation of PI to Pl i copolymers according to the invention:
On utilise une extrudeuse bi-vis co-rotatives dont les paramètres géométriques sont : Diamètre = 26 mm et rapport Longueur / Diamètre = 80, équipée d’un dispositif d’introduction de gaz (par exemple de l’azote ou de l’air appauvri) et d’un système d’évacuation des gaz. Les essais sont réalisés sous atmosphère non-contrôlée et à pression atmosphérique. We use a co-rotating twin-screw extruder whose geometric parameters are: Diameter = 26 mm and Length / Diameter ratio = 80, equipped with a gas introduction device (for example nitrogen or air depleted) and a gas evacuation system. The tests are carried out in an uncontrolled atmosphere and at atmospheric pressure.
L’extrudeuse bi-vis possède 16 zones dont la température est contrôlée indépendamment. Elles peuvent être chauffées électriquement et refroidies au moyen d’une circulation d’eau. The twin-screw extruder has 16 zones whose temperature is independently controlled. They can be heated electrically and cooled by circulating water.
La zone dénommée 1 est située sous la trémie, la zone 16 correspond à la filière. Les autres zones sont numérotées 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, dans cet ordre entre la zone 1 et la zone 16. Chaque zone a une longueur égale à 5 éléments de vis. Les réactifs peuvent être stockés dans des cuves chauffées, agitées, sous azote, équipées de pompes permettant l’injection directe des réactifs dans l’extrudeuse. Les débits de chaque pompe peuvent être contrôlés indépendamment afin de contrôler les ratios entre les différents réactifs ainsi que le débit global. Il est ainsi possible d’ajuster le temps de séjour dans l’extrudeuse. Le temps de séjour peut être mesuré par ajout d’un traceur coloré. The zone called 1 is located under the hopper, zone 16 corresponds to the die. The other zones are numbered 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, in that order between zone 1 and zone 16. Each zone has a length equal to 5 screw elements. The reagents can be stored in heated, stirred tanks under nitrogen, equipped with pumps allowing direct injection of the reagents into the extruder. The flow rates of each pump can be controlled independently in order to control the ratios between the different reagents as well as the overall flow rate. It is thus possible to adjust the residence time in the extruder. The residence time can be measured by adding a colored tracer.
Pour la préparation des copolymères, on utilise les composés a, b et c suivants : For the preparation of the copolymers, the following compounds a, b and c are used:
- composé al : dibromométhane, - al compound: dibromomethane,
- composé bl : polyéthylène glycol de masse moléculaire 8 000 g/mol, - compound bl: polyethylene glycol with a molecular mass of 8,000 g/mol,
- composé b2 : polyéthylène glycol de masse moléculaire 9 000 g/mol, - compound b2: polyethylene glycol with a molecular mass of 9,000 g/mol,
- composé b3 : polyéthylène glycol de masse moléculaire 10 000 g/mol, - compound b3: polyethylene glycol with a molecular mass of 10,000 g/mol,
- composé cl : composé de formule I dans laquelle R représente un groupement Cis-alkyl linéaire et X2 représente Br,
- composé c2 : composé de formule I dans laquelle R représente un groupement Ci6-alkyl linéaire et X2 représente Br, - compound cl: compound of formula I in which R represents a linear Cis-alkyl group and X 2 represents Br, - compound c2: compound of formula I in which R represents a linear Ci6-alkyl group and X 2 represents Br,
- composé c3 : composé de formule I dans laquelle R représente un groupement Cu-alkyl linéaire et X2 représente Br, - compound c3: compound of formula I in which R represents a linear Cu-alkyl group and X 2 represents Br,
- composé c4 : composé de formule I dans laquelle R représente un groupement Ci2-alkyl linéaire et X2 représente Br. - compound c4: compound of formula I in which R represents a linear Ci2-alkyl group and X 2 represents Br.
Dans une cuve étanche chauffée à 90°C, sous vide et déshydratée jusqu’à obtenir un taux d’eau inférieur à 800 ppm, on place le composé bl. Cette cuve est ensuite purgée à l’azote. Le composé bl est injecté dans la zone 1 chauffée à 80°C de l’extrudeuse. De la soude est additionnée dans la zone 1 également. Les zones 2, 3, 4 et 5 de l’extrudeuse sont respectivement portées à 100°C, 100°C, 150°C et 150°C. Le composé al est additionné dans la zone 6 de l’extrudeuse. Les zones 6 à 9 sont chauffées à 200°C pour réaliser un copolymère des composés al et bl. Puis, le composé cl est introduit dans la zone 10 dont la température est de 160°C. Les zones 11 à 14 sont maintenues à cette température. La zone 15 est refroidie à 80°C. Le temps de séjour du milieu réactionnel dans l’extrudeuse est d’environ 9 minutes pour un débit de 3 kg/h. In a sealed tank heated to 90°C, under vacuum and dehydrated until a water content of less than 800 ppm is obtained, the compound bl is placed. This tank is then purged with nitrogen. Compound bl is injected into zone 1 heated to 80°C of the extruder. Sodium hydroxide is added to zone 1 as well. Zones 2, 3, 4 and 5 of the extruder are respectively brought to 100°C, 100°C, 150°C and 150°C. The compound al is added in zone 6 of the extruder. Zones 6 to 9 are heated to 200°C to produce a copolymer of compounds al and bl. Then, the compound cl is introduced into zone 10, the temperature of which is 160°C. Zones 11 to 14 are maintained at this temperature. Zone 15 is cooled to 80°C. The residence time of the reaction medium in the extruder is approximately 9 minutes for a flow rate of 3 kg/h.
Le copolymère PI obtenu en sortie d’extrudeuse se trouve sous forme fondue. Pour obtenir une composition de contrôle rhéologique CRI selon l’invention, le copolymère PI est introduit directement en sortie de filière de l’extrudeuse dans une composition aqueuse dont le pH final est ajusté à environ 7 au moyen d’une solution aqueuse d’acide acétique et qui comprend également un composé tensio-actif (ethoxylate alcool - « Emulan » HE 51 de « Basf »). La composition CRI comprend 30 % en poids de copolymère PI, 20 % en poids de composé tensio-actif et 50 % en poids de solution aqueuse comprenant l’acide acétique. The PI copolymer obtained at the extruder exit is in molten form. To obtain a CRI rheological control composition according to the invention, the PI copolymer is introduced directly at the outlet of the extruder die into an aqueous composition whose final pH is adjusted to approximately 7 by means of an aqueous acid solution. acetic and which also includes a surfactant compound (alcohol ethoxylate - “Emulan” HE 51 from “Basf”). The CRI composition comprises 30% by weight of PI copolymer, 20% by weight of surfactant compound and 50% by weight of aqueous solution comprising acetic acid.
De manière analogue, on prépare et on caractérise les copolymères P2 à Pl i ainsi que la composition de contrôle rhéologique CR2 selon l’invention comprenant le copolymère P2. In a similar manner, the copolymers P2 to Pl i are prepared and characterized as well as the rheological control composition CR2 according to the invention comprising the copolymer P2.
Les composés et quantités molaires des composés mis en œuvre sont présentés dans le tableau 1.
The compounds and molar quantities of the compounds used are presented in Table 1.
Tableau 1 Table 1
Exemple 2 : préparation et caractérisation de formulations aqueuses de peinture comprenant les copolymères PI et P2 selon l’invention : Example 2: preparation and characterization of aqueous paint formulations comprising the copolymers PI and P2 according to the invention:
Les compositions CRI et CR2 de copolymères PI et P2 selon l’invention sont utilisées comme agent épaississant d’une formulation de peinture mate sans solvant. Les compositions CRI et CR2 comprenant respectivement les copolymères PI et P2 épaississants ont un extrait sec de 30 % en poids de matière active. Chaque formulation de peinture est préparée en mélangeant les différents ingrédients. Les ingrédients et quantités (en g) des formulations de peinture sont détaillés dans le tableau 2.
The CRI and CR2 compositions of PI and P2 copolymers according to the invention are used as a thickening agent for a solvent-free matt paint formulation. The CRI and CR2 compositions respectively comprising the thickening copolymers PI and P2 have a dry extract of 30% by weight of active material. Each paint formulation is prepared by mixing the different ingredients. The ingredients and quantities (in g) of the paint formulations are detailed in Table 2.
Tableau 2 Table 2
Pour chaque formulation de peinture, on détermine les viscosités résultantes à différents gradients de vitesse : For each paint formulation, the resulting viscosities are determined at different speed gradients:
- à faible gradient : viscosités Brookfield à 10 et 100 tour/min, respectivement notées VB 10 et VB 100 (mPa.s), - at low gradient: Brookfield viscosities at 10 and 100 rpm, respectively noted VB 10 and VB 100 (mPa.s),
- à moyen gradient : viscosité Stormer (Krebs Unit, KU). - at medium gradient: Stormer viscosity (Krebs Unit, KU).
Ces mesures sont faites 24 heures après préparation de la formulation. Les formulations sont thermostatées à 25 ± 0,5°C. Les résultats sont présentés dans le tableau 3.
These measurements are made 24 hours after preparation of the formulation. The formulations are thermostated at 25 ± 0.5°C. The results are presented in Table 3.
Tableau 3 Table 3
Les copolymères selon l’invention permettent d’épaissir efficacement une peinture mate sans solvant à différents gradients de cisaillement. Ces copolymères peuvent être utilisés efficacement comme additifs pseudoplastiques. The copolymers according to the invention make it possible to effectively thicken a matt paint without solvent at different shear gradients. These copolymers can be used effectively as pseudoplastic additives.
Dans le domaine des peintures aqueuses, une viscosité élevée à un gradient de cisaillement faible ou moyen traduit un bon comportement statique. On assure ainsi une bonne stabilité au cours de leur stockage tout en évitant le phénomène de sédimentation et une limitation de la tendance à la coulure sur support vertical.
In the field of aqueous paints, a high viscosity at a low or medium shear rate reflects good static behavior. This ensures good stability during their storage while avoiding the phenomenon of sedimentation and limiting the tendency to flow on vertical support.
Claims
REVENDICATIONS Méthode de préparation continue d’un copolymère P par extrusion réactive comprenant : CLAIMS Method for the continuous preparation of a copolymer P by reactive extrusion comprising:
* la réaction de polymérisation en présence d’une base : a) d'au moins un composé dihalogéné a ; b) d’au moins un monomère polyhydroxylé b mis en œuvre en une quantité molaire apportant un nombre de groupements hydroxyles (OH) supérieur au nombre d’halogénures apportés par le composé a ; puis * the polymerization reaction in the presence of a base: a) of at least one dihalogenated compound a; b) at least one polyhydroxylated monomer b used in a molar quantity providing a number of hydroxyl groups (OH) greater than the number of halides provided by compound a; Then
* la réaction avec au moins un composé hydrophobe monohalogéné c. Méthode de préparation selon la revendication 1 pour laquelle :* the reaction with at least one monohalogenated hydrophobic compound c. Preparation method according to claim 1 for which:
* la base est mise en œuvre en un excès molaire par rapport à la quantité molaire de groupements OH du monomère b, de préférence mise en œuvre en une quantité molaire de 1,05 à 10, de préférence de 1,1 à 6, équivalents molaires par rapport à la quantité molaire de groupements OH du monomère b ou* the base is used in a molar excess relative to the molar quantity of OH groups of monomer b, preferably used in a molar quantity of 1.05 to 10, preferably of 1.1 to 6, equivalents molars relative to the molar quantity of OH groups of monomer b or
* la polymérisation est réalisée à un pH supérieur à 10 ou supérieur à 12 ou* the polymerization is carried out at a pH greater than 10 or greater than 12 or
* la base est une base forte minérale ou une base forte organique, de préférence une base choisie parmi hydrure de sodium, hydrure de potassium, NaOH, KOH, méthanolate de sodium, méthanolate de potassium, éthanolate de sodium, éthanolate de potassium, terZ-butanolate de sodium, terZ-butanolate de potassium. Méthode de préparation selon l’une des revendications 1 ou 2 pour laquelle :* the base is a strong mineral base or a strong organic base, preferably a base chosen from sodium hydride, potassium hydride, NaOH, KOH, sodium methanolate, potassium methanolate, sodium ethanolate, potassium ethanolate, terZ- sodium butanolate, potassium terZ-butanolate. Preparation method according to one of claims 1 or 2 for which:
* un unique composé dihalogéné a est mis en œuvre ou pour laquelle 2 ou 3 composés dihalogénés a différents sont mis en œuvre ou* a single dihalogenated compound a is used or for which 2 or 3 different dihalogenated compounds a are used or
* le composé dihalogéné a est un composé al de formule I : L-X^ (I) dans laquelle : * the dihalogenated compound a is an al compound of formula I: L-X^ (I) in which:
- L représente indépendamment un groupement hydrocarboné divalent, de préférence un groupe Ci-Cio-alkylène, plus préférentiellement un groupe C1-C2- alkylène, bien plus préférentiellement CH2 ; - L independently represents a divalent hydrocarbon group, preferably a C1-Cio-alkylene group, more preferably a C1-C2-alkylene group, much more preferably CH2;
- X1 représente indépendamment Br, Cl ou I, de préférence Br.
- X 1 independently represents Br, Cl or I, preferably Br.
4. Méthode de préparation selon l’une des revendications 1 à 3 pour laquelle :4. Preparation method according to one of claims 1 to 3 for which:
* un unique composé polyhydroxylé b est mis en œuvre ou pour laquelle 2 ou 3 composés polyhydroxylés b différents sont mis en œuvre ou* a single polyhydroxy compound b is used or for which 2 or 3 different polyhydroxy compounds b are used or
* le composé polyhydroxylé b est un composé comprenant 2, 3 ou 4 groupements hydroxyles ou * the polyhydroxy compound b is a compound comprising 2, 3 or 4 hydroxyl groups or
* le composé polyhydroxylé b est un composé bl de formule II : HO-Qn-OH (II) dans laquelle : * the polyhydroxy compound b is a compound b1 of formula II: HO-Qn-OH (II) in which:
- Q représente indépendamment un groupement oxyalkylène, de préférence choisi parmi oxyéthylène, oxyéthylène-oxypropylène comprenant au plus 40 % molaire d’oxypropylène, oxyéthylène-oxybutylène comprenant au plus 20 % molaire d’oxybutylène, et leurs combinaisons ; n représente indépendamment un nombre allant de 20 à 800 ou * le composé polyhydroxylé b a une masse molaire en masse (Mw) allant de 800 à 40 000 g/mol, de préférence de 2 000 à 20000 g/mol, plus préférentiellement de 2 000 à 15 000 g/mol. - Q independently represents an oxyalkylene group, preferably chosen from oxyethylene, oxyethylene-oxypropylene comprising at most 40 molar % of oxypropylene, oxyethylene-oxybutylene comprising at most 20 molar % of oxybutylene, and their combinations; n independently represents a number ranging from 20 to 800 or * the polyhydroxy compound b has a molar mass by mass (Mw) ranging from 800 to 40,000 g/mol, preferably from 2,000 to 20,000 g/mol, more preferably from 2,000 at 15,000 g/mol.
5. Méthode de préparation selon l’une des revendications 1 à 4 pour laquelle : 5. Preparation method according to one of claims 1 to 4 for which:
* un unique composé hydrophobe monohalogéné c est mis en œuvre ou pour laquelle 2 ou 3 composés hydrophobes monohalogénés c différents sont mis en œuvre ou* a single monohalogenated hydrophobic compound c is used or for which 2 or 3 different monohalogenated hydrophobic compounds c are used or
* le composé hydrophobe monohalogéné c est un composé cl de formule III :* the monohalogenated hydrophobic compound is a cl compound of formula III:
R-X2 (III) dans laquelle : RX 2 (III) in which:
- R représente indépendamment un groupement hydrocarboné hydrophobe, de préférence un groupement hydrocarboné linéaire, ramifié ou cyclique, saturé, insaturé ou aromatique, ou comprenant de 6 à 40 atomes de carbone ;- R independently represents a hydrophobic hydrocarbon group, preferably a linear, branched or cyclic hydrocarbon group, saturated, unsaturated or aromatic, or comprising from 6 to 40 carbon atoms;
- X2 représente indépendamment Br, Cl ou I, de préférence Br. - X 2 independently represents Br, Cl or I, preferably Br.
6. Méthode de préparation selon l’une des revendications 1 à 5 pour laquelle le copolymère P est préparé par extrusion réactive, par rapport à la quantité molaire totale des composés a, b et c, au moyen de : 6. Preparation method according to one of claims 1 to 5 for which the copolymer P is prepared by reactive extrusion, relative to the total molar quantity of compounds a, b and c, by means of:
* 5 % molaire à 60 % molaire, ou de 5 % molaire à 50 % molaire, par exemple 20 % molaire, de composé dihalogéné a ;
* 10 % molaire à 65 % molaire, ou de 15 % molaire à 60 % molaire, par exemple 30 % molaire, de monomère polyhydroxylé b ; * 5 molar% to 60 molar%, or from 5 molar% to 50 molar%, for example 20 molar%, of dihalogenated compound a; * 10 molar% to 65 molar%, or from 15 molar% to 60 molar%, for example 30 molar%, of polyhydroxylated monomer b;
* 30 % molaire à 85 % molaire, ou de 35 % molaire à 80 % molaire, par exemple 50 % molaire, de composé hydrophobe monohalogéné c. Méthode de préparation selon l’une des revendications 1 à 6 conduite en l’absence de solvant ou bien dans un solvant choisi parmi l’eau, un solvant organique et leurs combinaisons, de préférence de l’eau. Méthode de préparation selon l’une des revendications 1 à 7 comprenant également un traitement acide final du copolymère P conduisant à un pH inférieur à 8, de préférence à un pH supérieur à 6, par exemple au moyen d’un acide, notamment un acide carboxy lique tel que l’acide acétique ou l’acide lactique. Copolymère P obtenu selon la méthode de préparation continue par extrusion réactive définie selon l’une des revendications 1 à 8, de préférence sous forme fondue ou sous forme solide à 25°C ou à une température inférieure à son point de fusion, par exemple sous une forme solide choisie parmi pastille, flocon, broyât, copeau, poudre et leurs combinaisons. Composition de contrôle rhéologique comprenant au moins un copolymère P selon la revendication 9, éventuellement traitée de manière acide conduisant à un pH inférieur à 8, de préférence à un pH supérieur à 6, par exemple au moyen d’un acide, notamment un acide carboxy lique tel que l’acide acétique ou l’acide lactique. Composition de contrôle rhéologique comprenant au moins un copolymère P selon la revendication 9 combiné à au moins un solvant, notamment de l’eau ou un solvant de coalescence, par exemple glycol, butylglycol, butyldiglycol, monopropyleneglycol, ethyleneglycol, ethylenediglycol, produits « Dowanol » dont le numéro CAS est 34590-94-8, produits « Texanol » dont le numéro CAS est 25265-77-4 ; ou combiné à au moins un additif choisi parmi un composé amphiphile, notamment un composé tensio-actif, de préférence un composé tensio-actif hydroxylé, par exemple alkyl- polyalkyleneglycol, notamment alkyl-polyethyleneglycol et alkyl- polypropyleneglycol ; un dérivé de polysaccharide, par exemple cyclodextrine, dérivé
de cyclodextrine, polyéthers, alkyl-glucosides ; un composé hydrotrope, un agent antimousse, un agent biocide et leurs combinaisons. Formulation aqueuse comprenant : * 30 molar% to 85 molar%, or from 35 molar% to 80 molar%, for example 50 molar%, of monohalogenated hydrophobic compound c. Preparation method according to one of claims 1 to 6 carried out in the absence of solvent or in a solvent chosen from water, an organic solvent and combinations thereof, preferably water. Preparation method according to one of claims 1 to 7 also comprising a final acid treatment of the copolymer P leading to a pH lower than 8, preferably to a pH higher than 6, for example by means of an acid, in particular an acid carboxylic acid such as acetic acid or lactic acid. Copolymer P obtained according to the continuous preparation method by reactive extrusion defined according to one of claims 1 to 8, preferably in molten form or in solid form at 25°C or at a temperature lower than its melting point, for example under a solid form chosen from pellet, flake, ground material, chip, powder and their combinations. Rheological control composition comprising at least one copolymer P according to claim 9, optionally treated in an acid manner leading to a pH lower than 8, preferably to a pH higher than 6, for example by means of an acid, in particular a carboxy acid liqueur such as acetic acid or lactic acid. Rheological control composition comprising at least one copolymer P according to claim 9 combined with at least one solvent, in particular water or a coalescence solvent, for example glycol, butylglycol, butyldiglycol, monopropyleneglycol, ethyleneglycol, ethylenediglycol, “Dowanol” products whose CAS number is 34590-94-8, “Texanol” products whose CAS number is 25265-77-4; or combined with at least one additive chosen from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkyleneglycol, in particular alkyl-polyethyleneglycol and alkyl-polypropyleneglycol; a polysaccharide derivative, for example cyclodextrin, derivative cyclodextrin, polyethers, alkyl glucosides; a hydrotropic compound, an antifoam agent, a biocidal agent and combinations thereof. Aqueous formulation comprising:
- au moins une composition selon l’une des revendications 10 ou 11 ; éventuellement- at least one composition according to one of claims 10 or 11; possibly
- au moins un pigment organique ou minéral ou des particules organiques, organo- métalliques ou minérales, par exemple carbonate de calcium, talc, kaolin, mica, silicates, silice, oxydes métalliques, notamment dioxyde de titane, oxydes de fer ; et éventuellement - at least one organic or mineral pigment or organic, organo-metallic or mineral particles, for example calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides; and eventually
- au moins un agent choisi parmi un agent espaceur de particules, un agent dispersant, un agent stabilisant stérique, un agent stabilisant électrostatique, un agent opacifiant, un agent colorant, un solvant, un agent de coalescence, un agent antimousse, un agent de conservation, un agent biocide, un agent d’étalement, un agent épaississant, un copolymère filmogène et leurs mélanges. Formulation selon la revendication 12 de revêtement, notamment une formulation d’encre, une formulation de vernis, une formulation d’adhésif, une formulation de peinture, par exemple de peinture décorative ou de peinture industrielle. Pâte pigmentaire aqueuse concentrée comprenant au moins un copolymère P selon la revendication 9 et au moins un pigment coloré organique ou minéral. Méthode de contrôle de la viscosité d’une composition aqueuse comprenant l’addition d’au moins un copolymère P selon la revendication 9. Méthode selon la revendication 15 pour laquelle la composition aqueuse est une formulation définie selon l’une des revendications 12 ou 13.
- at least one agent chosen from a particle spacer, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, an opacifying agent, a coloring agent, a solvent, a coalescing agent, an antifoaming agent, a defoaming agent conservation, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof. Coating formulation according to claim 12, in particular an ink formulation, a varnish formulation, an adhesive formulation, a paint formulation, for example decorative paint or industrial paint. Concentrated aqueous pigment paste comprising at least one copolymer P according to claim 9 and at least one organic or mineral colored pigment. Method for controlling the viscosity of an aqueous composition comprising the addition of at least one copolymer P according to claim 9. Method according to claim 15 for which the aqueous composition is a formulation defined according to one of claims 12 or 13 .
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996031550A1 (en) | 1995-04-05 | 1996-10-10 | Aqualon Company | Associative thickeners |
WO2000034361A1 (en) | 1998-12-04 | 2000-06-15 | Hercules Incorporated | Hydrophobically modified comb copolymers |
WO2020084200A1 (en) | 2018-10-26 | 2020-04-30 | Coatex | Continuous preparation of polyurethanes or polyureas |
WO2021022153A1 (en) | 2019-08-01 | 2021-02-04 | Hercules Llc | Synthetic thickeners incorporating non-reactive diluents |
-
2022
- 2022-04-01 FR FR2202986A patent/FR3134097A1/en active Pending
-
2023
- 2023-03-28 WO PCT/FR2023/000028 patent/WO2023187261A1/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996031550A1 (en) | 1995-04-05 | 1996-10-10 | Aqualon Company | Associative thickeners |
WO2000034361A1 (en) | 1998-12-04 | 2000-06-15 | Hercules Incorporated | Hydrophobically modified comb copolymers |
US6162877A (en) * | 1998-12-04 | 2000-12-19 | Hercules Incorporated | Hydrophobically modified comb copolymers |
WO2020084200A1 (en) | 2018-10-26 | 2020-04-30 | Coatex | Continuous preparation of polyurethanes or polyureas |
US20210269580A1 (en) * | 2018-10-26 | 2021-09-02 | Coatex | Continuous preparation of polyurethanes or polyureas |
WO2021022153A1 (en) | 2019-08-01 | 2021-02-04 | Hercules Llc | Synthetic thickeners incorporating non-reactive diluents |
Also Published As
Publication number | Publication date |
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FR3134097A1 (en) | 2023-10-06 |
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