WO2001078907A1 - Method for hydrophilic modification of a substrate using a treatment in an aqueous medium with a water soluble and heat-sensitive polymer - Google Patents
Method for hydrophilic modification of a substrate using a treatment in an aqueous medium with a water soluble and heat-sensitive polymer Download PDFInfo
- Publication number
- WO2001078907A1 WO2001078907A1 PCT/FR2001/001075 FR0101075W WO0178907A1 WO 2001078907 A1 WO2001078907 A1 WO 2001078907A1 FR 0101075 W FR0101075 W FR 0101075W WO 0178907 A1 WO0178907 A1 WO 0178907A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- parts
- polymer
- soluble
- substrate
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 98
- 238000011282 treatment Methods 0.000 title claims abstract description 68
- 239000012736 aqueous medium Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 title claims description 148
- 230000004048 modification Effects 0.000 title claims description 24
- 238000012986 modification Methods 0.000 title claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 105
- 229920001577 copolymer Polymers 0.000 claims abstract description 124
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims description 109
- 239000000203 mixture Substances 0.000 claims description 86
- 229920003169 water-soluble polymer Polymers 0.000 claims description 56
- 238000001179 sorption measurement Methods 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 18
- -1 carpet Substances 0.000 claims description 17
- 239000000123 paper Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- 238000003795 desorption Methods 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000004753 textile Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 230000008030 elimination Effects 0.000 claims description 6
- 238000003379 elimination reaction Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 5
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 5
- 230000035945 sensitivity Effects 0.000 claims description 5
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000004567 concrete Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 229920003043 Cellulose fiber Polymers 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 230000000295 complement effect Effects 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 102000004190 Enzymes Human genes 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000010985 leather Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 229920006322 acrylamide copolymer Polymers 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 150000001412 amines Chemical group 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 150000003871 sulfonates Chemical class 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 73
- 238000003756 stirring Methods 0.000 description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 60
- 239000003999 initiator Substances 0.000 description 60
- 239000003795 chemical substances by application Substances 0.000 description 49
- 238000012546 transfer Methods 0.000 description 46
- 239000004744 fabric Substances 0.000 description 38
- 239000007864 aqueous solution Substances 0.000 description 35
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 34
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 34
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 32
- 230000015572 biosynthetic process Effects 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 30
- 238000009749 continuous casting Methods 0.000 description 29
- 238000003786 synthesis reaction Methods 0.000 description 29
- 239000012429 reaction media Substances 0.000 description 28
- 238000010408 sweeping Methods 0.000 description 26
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 21
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 19
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 239000002609 medium Substances 0.000 description 9
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 241000953555 Theama Species 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- KZUIKPMQAIEBOE-UHFFFAOYSA-N 2-(ethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCNCCOC(=O)C(C)=C KZUIKPMQAIEBOE-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NXBXJOWBDCQIHF-UHFFFAOYSA-N 2-[hydroxy-[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(=O)OCCOC(=O)C(C)=C NXBXJOWBDCQIHF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920008712 Copo Polymers 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 125000005011 alkyl ether group Chemical group 0.000 description 1
- BZRLYGTWEDFWCR-UHFFFAOYSA-N amino 2-methylpent-2-enoate Chemical compound CCC=C(C)C(=O)ON BZRLYGTWEDFWCR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Polymers 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- NIHIVAISWHSKJZ-UHFFFAOYSA-N n-(3-ethoxypropyl)prop-2-enamide Chemical compound CCOCCCNC(=O)C=C NIHIVAISWHSKJZ-UHFFFAOYSA-N 0.000 description 1
- MVBJSQCJPSRKSW-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]prop-2-enamide Chemical compound OCC(CO)(CO)NC(=O)C=C MVBJSQCJPSRKSW-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RZKYDQNMAUSEDZ-UHFFFAOYSA-N prop-2-enylphosphonic acid Chemical compound OP(O)(=O)CC=C RZKYDQNMAUSEDZ-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- VCISDWJIHKTDEV-UHFFFAOYSA-N triethyl(2-prop-2-enoyloxyethyl)azanium Chemical compound CC[N+](CC)(CC)CCOC(=O)C=C VCISDWJIHKTDEV-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
-
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- 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
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
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- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
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- C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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Definitions
- the present invention relates to the hydrophilic modification of the substrates, requiring treatment in an aqueous medium with polymers soluble in water, and the obtaining of hydrophilic modified dry substrates. It enhances the adsorption of these polymers on substrates, based on a treatment in water at a suitable temperature, in the presence of water-soluble polymers of heat-sensitive nature and of suitable compositions.
- the invention also covers the case where the hydrophilic modification of the substrates is only temporary.
- a first objective is to promote the adsorption of water-soluble or hydrophilic polymers on substrates imperatively requiring treatment in an aqueous medium in the presence of these polymers.
- the polymers being water-soluble or hydrophilic are, by their very high affinity with water, tend to remain in the aqueous medium instead of being adsorbed on the substrates that is desired to treat and thus modify the surface .
- a second objective is to produce temporary hydrophilic and "washable” coatings on the substrates which need to be treated in an aqueous medium. It involves providing two solutions to two different problems, the first relating to the adsorption of polymer for - '"" the formation of a hydrophilic coating on substrates intended for various applications, and the second dealing with desorption. or the elimination of the so-called “washable” hydrophilic coating on the substrates after applications. In this case, it is necessary, as previously, to promote the adsorption of water-soluble or hydrophilic polymers on substrates which imperatively require treatment.
- the second part of the problem consists in proposing, after using the modified substrates for a given application, a method allowing the desorption of these polymers on the hydrophilic modified substrate also in an aqueous medium in order to avoid the accumulation of the polymer after a series of adsorption steps.
- Polymers have been used for many decades for the modification of the properties of various substrates such as paper, textile, metal, and wood, concrete. It is often sought through these modifications, the provision or improvement of various properties, in particular the mechanical, antistatic properties, the feel, the resistance to aqueous liquids, to greases by hydrophobic and oleophobic modification of the substrates, the wettability and the aptitude. easily remove dirt during washing thanks to the hydrophilic modification of the substrates.
- the polymer can be functionalized so as to promote various interactions with the substrate, in particular:
- Precipitation of the polymer during the treatment of substrates in an aqueous medium is an approach often used to cause precipitation of the polymer on the support.
- a second additive is an approach often used to cause precipitation of the polymer on the support.
- the cellulosic fibers are treated with anionic latexes of styrene / butadiene copolymer.
- a cationic water-soluble polymer additive is incorporated to destabilize the latex which consequently precipitates on the paper fibers (for example American patents US-A-4 121 966, US -A-2 745 744).
- This precipitation approach thus makes it possible to successfully adsorb a polymer which having no functional pattern of attachment to the support.
- it has the disadvantage of incorporating a third body into the formulation.
- the present invention provides a new method based on the radical change in the solubility in water of certain water-soluble polymers as a function of temperature. More specifically, it takes advantage of the particular properties of heat-sensitive polymers, that is to say polymers soluble in water below a certain temperature commonly called LCST, but which become insoluble above this temperature LCST.
- a water-soluble polymer having an LCST for substrates to be treated in an aqueous medium by a water-soluble polymer, it proposes on the one hand, to choose a water-soluble polymer having an LCST, and on the other hand, to carry out the aqueous treatment of said substrate preferably at a temperature greater than or equal to the LCST in order to precipitate the polymer which has become insoluble in water, and thus promoting the fixation or adsorption of said water-soluble polymer on the surface of the substrate.
- the latter In the case of treatments which cannot be carried out at a temperature higher than the LCST of the thermosensitive polymer, the latter must have functional or compatibilizing patterns allowing it to be fixed on the substrate.
- the advantage of this method lies in the fact that, under the conditions of temperature higher than the LCST, the water-soluble polymer having the thermosensitive character precipitates during the treatment in an aqueous medium of the substrate, thus improving the fixing and the adsorption on the substrate then that the other non-thermosensitive water-soluble hand polymers are soluble and tend to remain mainly in water instead of clinging to the substrate.
- thermosensitive polymer In order to further enhance the adsorption of the thermosensitive polymer on the support, it may be necessary to incorporate reactive, ionic or compatibilizing units into the structure of the polymer provided, on the one hand, that the thermosensitive nature, necessary for the precipitation of the polymer be kept, and secondly, that these patterns can generate covalent bonds (chemical reaction), ionic bonds (ionic interaction), or quite simply reinforce adsorption on the substrate. In the case of treatments that cannot be carried out at a temperature higher than the LCST of the thermosensitive polymer, these reactive, ionic or compatibilizing units are also used to fix the polymer to the substrate.
- the hydrophilic modified substrate can thus be used for applications requiring a hydrophilic surface such as increasing the wettability of the substrate with hydrophilic ingredients or the provision of barrier properties between the substrate and the hydrophobic or oleophobic substances.
- the present invention provides a method based on the radical change in the solubility in water of certain water-soluble polymers as a function of temperature and pH. It takes advantage of the particular properties of these water-soluble polymers which are both thermosensitive and sensitive to pH, that is to say polymers which are soluble in water below a certain temperature (known as LCST), but which become insoluble in water at temperatures above the LCST. These same polymers are soluble in water at basic pH whatever the temperature.
- thermosensitive and pH-sensitive polymers of the invention are chosen so that the temperature required for the step of treatment of the substrate by adsorption of polymer is preferably greater than or equal to the LCST of the polymer, the separation or the precipitation of the polymer in water promoting the attachment or adsorption of the polymer to the surface of the substrate.
- this invention provides two solutions for the desorption of the coating in an aqueous medium: (1) if the temperature of the aqueous medium is higher than the LCST of the heat-sensitive polymer, it is recommended to carry out the desorption in basic medium, insofar as certain compositions of heat-sensitive polymers proposed in the invention lose their temperature sensitivity by because of the neutralization of the carboxylic acid functions present in the structure of these polymers.
- the desorption of the coating can be done by simple soaking in water whatever the pH.
- the subject of this invention is the use of the particular properties of thermosensitive polymers to reinforce the hydrophilic modification of various substrates imperatively requiring treatment in an aqueous medium with water-soluble polymers and used for various applications such as increasing the wettability of the substrate with hydrophilic ingredients or the provision of barrier properties between the substrate and hydrophobic or oleophobic substances.
- These heat-sensitive polymers must preferably have functional, reactive, ionic or compatibilizing units to improve the fixation on the substrates, but also to be able to be applied over a wider temperature range, in particular below and above the LCST of the heat-sensitive polymers. .
- the invention in a second form, relates to temporary hydrophilic coatings on substrates which require, after use of the modified hydrophilic substrate for the aforementioned applications, the removal or leaching of the hydrophilic coating on the substrate.
- the invention provides two solutions for the desorption of the coating in an aqueous medium to avoid the accumulation of polymers on the substrates after application.
- the present invention therefore relates to a process for hydrophilic modification of a substrate, characterized by the the fact that said substrate is treated in an aqueous medium with a water-soluble polymer or copolymer modifier having thermosensitive properties.
- polymer having a thermosensitive character is understood to mean a polymer having a radical change in solubility or in hydrophilic / hydrophobic transition at a critical temperature commonly called LCST. These (co) polymers are insoluble in water above the LCST and soluble in water below the LCST. Said water-soluble thermosensitive polymer or copolymer modifier has an LCST generally between 3 and 100 ° C.
- the substrate is treated in an aqueous medium with said heat-sensitive polymer or copolymer modifier at a temperature at least equal to the LCST of said heat-sensitive polymer or copolymer in order to precipitate the latter on said substrate to time of treatment due to its hydrophobic nature in this temperature range.
- the substrate to be treated does not tolerate being subjected to a temperature exceeding a value T
- the substrate is treated in an aqueous medium at a temperature below T, the water-soluble polymer or copolymer thermosensitive then being chosen from those having an LCST at most equal to the treatment temperature.
- thermosensitive water-soluble (co) polymer chooses said (co) polymer from those having functional, ionic or compatibilizing units allowing its fixation on the substrate.
- the functional units are chosen in particular from cationic, anionic, sulfonic acid, phosphatic acid, phosphate, phosphonees, hydrophobic, ethoxylated, carboxylic acid, silane, maleic, alcohol, amino, amide, sulfonate, carboxylate groups.
- Hydrophobic groups can be used to reinforce the compatibility between substrates to be treated and heat-sensitive polymers.
- the ethoxylated functions can form hydrogen bonds with the hydroxyl groups of cotton or rayon fiber textiles.
- the phosphate or phosphone functions can strengthen adhesion to metal and glass.
- the silane functions are reserved to improve adhesion on glass and concrete.
- said substrate can be treated in an aqueous medium with the water-soluble homopolymer or copolymer modifier having thermosensitive properties which has functional units (such as those indicated above) capable of bringing complementary properties other than hydrophilicity (antistatism). , adhesion, wettability, hydrophobicity, fixation of hydrophilic and hydrophobic substances, elimination of hydrophilic and hydrophobic substances), and / or which is combined with at least one other active ingredient whose retention or adsorption on the substrate results from its coating or of its encapsulation by the heat-sensitive polymer at the time of its precipitation on the substrate above the LCST.
- the water-soluble homopolymer or copolymer modifier having thermosensitive properties which has functional units (such as those indicated above) capable of bringing complementary properties other than hydrophilicity (antistatism).
- adhesion, wettability, hydrophobicity, fixation of hydrophilic and hydrophobic substances, elimination of hydrophilic and hydrophobic substances and / or which is combined with at least one other active
- the other aforementioned ingredients are chosen, for example, from hydrophobic polymers in the form of latex, aqueous polymer dispersions, fillers, enzymes, surfactants, organic materials and mineral materials; these ingredients are used to provide complementary properties to the substrates.
- the thermosensitive (co) polymer in this case acts as a transfer agent for these ingredients for more contact. intimate between them and the surface of the substrate. In addition to the coating and encapsulation following the precipitation of the thermosensitive (co) polymer, the latter can interact with these ingredients to make transport more efficient.
- the thermosensitive water-soluble homo- or copolymer can be chosen from those capable of interacting with the ingredient (s) used jointly, for example by forming hydrogen bonds with it or these.
- the substrates concerned by the treatment and modification of the properties according to the invention are chosen among others from textiles, nonwovens, metal, glass, wood, paper, leather, building substrates, carpet , fibers, polymers, concrete.
- the method according to the invention may be a hydrophilic treatment of textiles and non-woven by adsorption of the (co) polymer heat sensitive; or consist of a treatment of the paper, in particular the adsorption on the cellulose fibers for the improvement of the wet resistance of the paper and the hydrophobic and oleophobic treatment of the paper; or also consist of a treatment providing the substrates with antistatic properties, wettability, a hydrophilic or hydrophobic modification, the fixing of hydrophilic and hydrophobic substances or the elimination of hydrophilic and hydrophobic substances, barrier properties between the substrate and the hydrophobic substances or oleophobic, fixation of fatty substances.
- the present invention also relates to a method as defined above, according to which the treatment has led to a hydrophilic coating intended to be temporary having been adsorbed on said substrate.
- a hydrophilic coating intended to be temporary having been adsorbed on said substrate.
- it causes desorption of said coating: - in basic aqueous medium at a temperature above the LCST, the thermosensitive (co) polymer used carrying carboxylic acid functions and being such that it loses its sensitivity to temperature due to the neutralization of said carboxylic acid functions, or - whatever the pH at a temperature below the LCST.
- a modifier chosen from:
- thermosensitive copolymers obtained from a composition of monomers comprising, per 100 parts by moles:
- R 1 CH 2 CC-0- [R 2 -0] n -R 3 (I)
- - R represents H or -CH3; o - R represents a C alkylene residue which optionally comprises one or more OH groups, or a C3-C4 alkylene residue which comprises one or more OH groups;
- - R represents H or -CH3; and - n is an integer between 1 and
- R and R " 3 each independently represent hydrogen or C2-C4 alkyl; -1 - Y is a single bond or a C-1-C4 alkylene residue; R ° represents a C 2 alkylene residue which optionally comprises one or more OH groups, or a C 3 -C 4 alkylene residue which comprises one or more OH groups; R 'represents H or -CH3; and o is an integer between 1 and 70;
- - R ° represents H or -CH3; - R and R each independently represent a C2-C4 alkylene residue which optionally comprises one or more OH groups, R 9 and R 10 being different from each other;
- - R 11 represents H or -CH3; - p is an integer between 1 and
- R 1 z 9- and R 1 J " -? Each independently represent hydrogen or C 2 -C 4 alkyl; o
- - Y ⁇ is a single bond or a C - ⁇ - C ⁇ alkylene residue
- R 14 and R 1 - 3 each independently represent an alkylene radical in CpC ⁇ optionally comprising one or more OH groups, R 14 and R i) being different from each other;
- - r is an integer between 1 and 70;
- - s is an integer between 1 and 40;
- - R 17 represents H or -CH3
- R 1 1 R 0 represents a C 1 -C 4 alkylene residue which optionally comprises one or more OH groups (in particular the compounds in c 3 _c 4 comprise one or more OH groups in order to ensure their solubility in water) ;
- - t is an integer between 1 and 70; in which: f ) -i
- R ⁇ u and R each independently represent hydrogen or C ⁇ C ⁇ alkyl
- - Y 3 is a single bond or a C- ] _-C 4 alkylene radical
- R 22 represents a C 1 -C 4 alkylene residue which optionally comprises one or more OH groups (in particular the C 3 -C 4 compounds comprise one or more OH groups in order to ensure their solubility in water);
- R O is alkyl C 2 -C ⁇ Q, aryl or aralkyl, Cg-Cg ⁇ ;
- - u is an integer between 1 and 70;
- - A represents -O- or -NH-
- B1 represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 9 CHOHCH 9 -;
- R and R each independently represent """CH3 or a C 2 -C ] alkyl chain;
- - R represents H, -CH3 or a C 2 -C 16 alkyl chain
- A represents -O- or -NH-;
- B 2 represents -CH 2 CH 2 -, -CH 2 CH .2 CH 2 - or -CH 2 CHOH CH 2 -;
- - R 28 represents H or -CH3;
- R 3 and R or each independently represents "" CH 3 or an alkyl chain C 2 -C j _;
- R J identical or different, each independently represent H, C 1-5 alkyl ⁇ 3 u i has - optionally one or more groups
- poly (N-substituted (meth) acrylamides) such as poly (N-isopropyl acrylamide) (NIPAM) having an LCST of 35 ° C., the preparation of which is widely described in the literature (Colloids Surf 20, 247-257, 1986 and WO 97/24150), poly (N-propylacrylamide) and poly (N-ethoxypropylacylami.de); and the copolymers of N-
- (meth) acrylamide such as NIPAM /
- - R 34 represents H or CHo
- - A ° represents -0- or -NH-
- B 3 represents -CH 2 CH -, CH 2 CH 2 CH 2 - or
- poly-MADAME ethylaminoethyl methacrylate
- (VI) the polymers obtained by hydrophilic modification of the hydrophobic polymers by polyoxyethylenated units such as polyethylene glycol (PEG) units; in particular, mention may be made of - polyamide-PEG, polyester-PEG and polyethylene-PEG.
- PEG polyethylene glycol
- the preferred monomer (s) of formula (I) are chosen in particular from the compounds of formula (la):
- CH 2 [CH 2 -CH 2 -0] n -R 3 (la) in which R 1, R " and n are as defined above.
- The. preferred monomers (A) of formula (II) are especially chosen from the compounds of formula (Ha) or (Ilb): R 4 R 5
- the monomer (s) (B) are in particular chosen from methacrylic acid and acrylic acid, methacrylic acid being preferred.
- the preferred monomer (s) of formula (III) are chosen in particular from the compounds of formula (Illa) or (Illb):
- R 8 , R, p and q are as defined above.
- R o and R ⁇ represent -CH 2 -CH 2 -.
- the compound (s) (E1) of formula (VII) are chosen in particular from the halides (such as chlorides) of (meth) acryloxyethyltri ethylammonium. In particular, mention may be made of acryloxyethyltrimethylammonium chloride.
- the compound (s) (E2) of formula (VIII) are in particular chosen from acrylate and dimethylaminoethyl methacrylate.
- the compound (s) (E3) are for example 2-acrylamido-2-methyl-propane sulfonic acid and its salts.
- the compound (s) (E4) are chosen, for example, from (meth) acryloxyalkylsilanes.
- the monomer (s) (E6) are chosen in particular from allylphosphonic acid and its salts.
- the compound (s) (E7) are chosen in particular from N-vinylacetamide, N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam.
- the compound (s) (E8) are in particular chosen from acrylamide, methacrylamide, N-isopropyl acrylamide, N-ethoxypropylacrylamide, N, N-dimethylacrylamide, and N- (2-hydroxypropyl) (meth) acrylamide.
- the hydrophobic monomer (s) (F) are chosen in particular from:
- R 35 represents a C 1 -C 4 alkylene residue
- - w is 0 or is an integer between 1 and 10; and - R 36 represents a C- ] _-C3 2 alkyl or cycloalkyl residue, with the condition that, when w is 0, R 36 is a C ⁇ - ⁇ alkyl or cycloalkyl residue;
- R 37 represents a C 1 -C alkylene residue or a C 1 -C 4 alkylene residue halogen; - b is 0 or is an integer between 1 and 10;
- R represents a C1 ⁇ CQ alkyl residue, cycloalkyl, halogenated alkyl or halogenated cycloalkyl, with the condition that, when b is 0, R 38 is a halogenated C1 to C i alkyl residue or halogenated cycloalkyl;
- CH 2 CH-R 39 in which R 39 is an alkylcarboxylate or alkyl ether group containing 1 to 18 carbon atoms, an aryl or aralkyl group or a cycloalkyl group;
- R 40 and R 41 represents a hydrogen atom and the other represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms
- - Y represents a bivalent hydrocarbon chain linked to 0 by a carbon atom and which may include one or more heteroatoms chosen from oxygen, sulfur and nitrogen;
- R £ represents a perfluorinated radical with a straight or branched chain, containing 2 to 20 carbon atoms, preferably 4 to 16 carbon atoms;
- - R 42 represents H or -CH3
- R 43 represents a C3-C4 alkylene residue
- - c is an integer between 1 and 70
- - R 44 represents H or -CH3
- R ⁇ and R each independently represent hydrogen or C 2 -C 4 alkyl
- - Y is a single bond or a C 1 -C 4 alkylene residue
- - R 47 represents a C3-C4 alkylene residue
- - d is an integer between 1 and 70;
- - R 48 represents H or -CH3
- - R 49 represents H or -CH3
- R 50 and R 51 identical or different, each independently represent Cg-C 2 4 alkyl or cycloalkyl;
- the compounds of formula (XIV) are chosen, for example, from those comprising an R 43 which is a CH residue
- the compounds of formula (XV) are chosen by CH-, example from those having a which is a residue -CH 2 -C I'H- or c
- the compounds of formula (XVI) are chosen for example from N- (tert. -Butyl) (meth) acrylamide, N- decyl (meth) acrylamide, N-dodecyl (meth) acrylamide and N- (n- octadecyl) (meth) acrylamide.
- the compound (F10) is in particular N-octadecyl-triethoxysilane.
- the water-soluble thermosensitive copolymer (I) according to the invention may have been obtained from a composition of monomers as defined above in which at least one chain transfer agent has been incorporated, chosen in particular from mercapto ethanol, isopropanol, alkylmercaptans, such as methyl mercaptan, ethyl mercaptan, etc., carbon tetrachloride and triphenylmethane, the transfer agent or agents having been used in an amount in particular from 0.05 to 8 % by weight relative to the total weight of the monomers.
- a composition of monomers as defined above in which at least one chain transfer agent has been incorporated chosen in particular from mercapto ethanol, isopropanol, alkylmercaptans, such as methyl mercaptan, ethyl mercaptan, etc., carbon tetrachloride and triphenylmethane, the transfer agent or agents having been used in an amount in particular from 0.05 to 8 % by
- the LCST of the water-soluble thermosensitive copolymer (I) according to the invention can be between 6 ° C and 100 ° C, preferably between 14 ° C and 75 ° C. As illustrated by the examples, a person skilled in the art can easily adjust the
- the LCSTs of the copolymers (I) of the invention increase with the average number of ethylene oxide units of the polyethoxylated monomer used;
- the LCSTs of the copolymers (I) of the invention increase if the transfer agent is removed; - the LCSTs of the copolymers (I) according to the invention vary between 6 and 75 ° C by varying the parameters of the number of ethylene oxide units, the presence of the transfer agent, the ratio of the monomers (A) and (B), and the presence of functional patterns; - It is possible to incorporate functional units into the copolymers of the invention while preserving their heat-sensitive character;
- a copolymer (I) as defined above the radical copolymerization is carried out in an aqueous or organic medium (alcohols or ketones for example) of the water-soluble monomers as defined above.
- the polymerization is carried out in particular with a total concentration of the monomers of between 5 and 75% by weight, in particular between 15 and 50% by weight.
- This copolymerization is carried out in the presence of at least one initiator generating free radicals, chosen in particular from persulfates, such as ammonium and potassium persulfates, peroxides and diazo compounds, such as 2, 2 'hydrochloride -azobis (2- aminopropane), the initiator or initiators generating free radicals being used in a proportion in particular of 0.1 to 5% by weight, in particular of 0.5 to 3% by weight relative to the total weight of the monomers used.
- the copolymerization can also be initiated by irradiation, for example in the presence of UV radiation and photoinitiators such as benzophenone, methyl-2-anthraquinone or chloro-2-thioxanthone.
- the length of the polymer chains can, if desired, be adjusted using chain transfer agents, such as those indicated above, used in the proportions as indicated above.
- the reaction temperature can vary within wide limits, that is to say from -40 ° C. to 200 ° C., operating preferentially between 50 and 95 ° C.
- the LSCT of the targeted copolymer can be adjusted as a function of the composition of the monomers and / or of the amount of chain transfer agent used.
- the present description indicates to those skilled in the art the elements from which he can easily make any such adjustment.
- thermosensitive polymers adsorb effectively on substrates if these substrates are treated with polymers at a temperature higher than the LCST.
- the coatings formed on the substrates can be easily removed or leached by treatment in basic medium or by treatment below the LCST whatever the pH.
- the thermosensitive polymer compositions proposed indeed allow, in addition to good adsorption on the substrates in aqueous medium, an effective desorption by playing on the sensitivity of these polymers both with the pH and with the temperature.
- MAPEG6 PPG3 monomer of formula: CHo CH,
- CH 2 CC-0- [CH 2 -CH 2 -0] g- [CH 2 -CH-0] 3 -H
- MAPEG 12 monomer of formula: CHo
- MAPEG 22 monomer of formula: CHo
- ADAMQUAT MC acryloxyethyltrimethylammonium chloride
- SIPOMER BEM acryloxyethyltrimethylammonium chloride
- MAM methyl methacrylate
- MABu butyl methacrylate
- MALAU lauryl methacrylate
- n OE average number of ethylene oxide units.
- PMMA poly (methyl methacrylate)
- LCST is the temperature at which the product changes from an opaque dispersion (insoluble polymer) to a clear solution (soluble polymer).
- the product obtained is an aqueous solution of water-soluble polymer if the temperature is below T ° C and on the other hand, above T ° C, the polymer is insoluble in water and the product is in the form of dispersions of particles of polymer insoluble in water.
- the LCST is determined visually during the cooling of the product at the end of the synthesis.
- This polymer has an LCST of 35 ° C.
- This polymer has an LCST of 40 ° C. It can thus be noted that an increase in mass content of AMA from 27.9 to 30.9 has the effect of increasing the LCST of the copolymer from 35 ° C to 40 ° C.
- Example 1 is reproduced, except that no transfer agent is incorporated.
- An aqueous solution of water-soluble polymer of composition is obtained:
- This polymer has an LCST of 40 ° C. Removal of the transfer agent increases the LCST from 35 to 40 ° C.
- a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having a nOE of 8.5 (intermediate between 8 and 12.5).
- 1485 parts of water are introduced with stirring (150 revolutions / minute; stirring by anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping.
- the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
- This polymer has an LCST of 24 ° C.
- EXAMPLE 5 SYNTHESIS OF A MAPEG 8 / MAPEG 12 / AMA COPOLYMER
- Example 4 is repeated, except that no transfer agent is incorporated.
- This polymer has an LCST of 24 ° C.
- a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 9 (intermediate between 8 and 12).
- This polymer has an LCST ' of 24 ° C.
- Example 6 is repeated, except that no transfer agent is incorporated.
- An aqueous solution of water-soluble polymer of composition is obtained:
- This polymer has an LCST of 26 ° C
- a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 9 (intermediate between 8 and 12).
- 1800 parts of water are introduced with stirring (150 revolutions / minute; stirring by anchor), and the reactor is brought to temperature. 80 ° C under nitrogen sweep.
- the monomers and initiator solution are introduced by continuous casting over three hours, in the following manner:
- a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 9.5 (intermediate between 8 and 12.5).
- This polymer has an LCST of 27 ° C.
- Example 9 is repeated, except that no transfer agent is incorporated.
- An aqueous solution of water-soluble polymer of composition is obtained:
- This polymer has an LCST of 29 ° C.
- a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 10.5 (intermediate between 8 and 12.5). 1656 parts of water are introduced into a 3 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
- This polymer has an LCST of 31.5 ° C.
- This polymer has an LCST of 75 ° C, greater than 37 "C.
- This polymer is water-soluble and does not show any change in solubility in water for a temperature below 90 ° C.
- This example shows that a suitable composition of monomers, in particular nOE, is required to obtain a heat-sensitive copolymer.
- This polymer has an LSCT of 53 ° C.
- ADAMQUAT TM therefore has the effect of increasing the LCST of the MAPEG12 / AMA copolymer from 35 ° C. (cf. Example 1) to 53 ° C.
- This polymer has an LSCT of 14 ° C.
- This polymer has an LSCT over the temperature range 27-30 ° C.
- ADAMQUAT MC therefore increases the LCST of the MAPEG 8 / AMA copolymer from 14 ° C to 27-30 ° C.
- This polymer has an LCST of 18 ° C being established between 18 and 20 ° C.
- SIPOMER BEM therefore has the effect of increasing the LCST of the MAPEG 8 / AMA copolymer from 14 ° C (see Example 15) to 18-20 ° C.
- This polymer has an LCST of 18 ° C being established between 26 and 28 ° C.
- SIPOMER BEM and ADAMQUAT MC therefore have the effect of increasing the LCST of the MAPEG 8 / AMA copolymer from 14 ° C (see Example 15) to 26-28 ° C.
- This polymer has an LSCT established over the temperature range 27-29 "C.
- the AMPS therefore has the effect of increasing the LCST of the AMA / MAPEG copolymer from 14 ° C. (cf. Example 15) to 27-29 ° C.
- This polymer has an LSCT of 19 ° C.
- EMPICRYL therefore increases the LCST of the AMA / MAPEG 8 / AMA copolymer from 14 ° C (see Example 15) to 27-29 ° C.
- This polymer has an LCST of between 10 and 12 ° C.
- This polymer has an LCST of between 6 and 8 ° C.
- a liter of 10% aqueous solution of a heat-sensitive copolymer previously prepared in Examples 1 to 23 is introduced with stirring (300 rpm) using a magnetic bar. brings the assembly to a given processing temperature (Tad). After stabilization at the desired treatment temperature (Tad), the calibrated and weighed piece of tissue is introduced with stirring which is left to soak with stirring for 30 minutes. The treated tissue is then recovered using tweezers, and quickly steamed at 100 ° C for 6 hours. The difference in weight between the dry treated or modified hydrophilic fabric and the untreated starting fabric gives the weight of polymer adsorbed on the fabric during the soaking or treatment operation.
- Table 1 groups the polymer masses adsorbed as a function of the average number of ethylene oxide (nOE) and of the LCST.
- Table 1 Mass of MAPEG / AMA copolymer adsorbed on the treated fabric at 50 ° C. as a function of the average number of ethylene oxide nOE of the MAPEGs and of the LCST
- the polymer is not or only slightly adsorbed on the fabric if the LCST (75 ° C) is higher than the soaking or treatment temperature (50 ° C).
- the polymer being in a soluble form, preferentially remains in water instead of adsorbing on the fabric.
- the increase in the treatment temperature of the fabric above the LCST (78 ° C and 92 ° C) allows the adsorption of the precipitated polymer on the fabric .
- Table 6 gives the values obtained for the treatments carried out above the LCST of the polymer. We use for comparison the mass of polymer adsorbed on the hydrophilic modified dry tissue after the previous treatments in an acid medium.
- Desorption of hydrophilic coating on the fabric by treatment in basic medium Comparison between the initial mass of polymer adsorbed on the tissue after treatment in acidic aqueous medium in the presence of 10% solution of polymer and the final mass of polymer remaining on the tissue after treatment in basic aqueous medium in the presence of 10% polymer solution
- This polymer has an LCST of 0 ° C.
- This polymer has an LCST of 45 ° C.
- EXAMPLE 27 SYNTHESIS OF A MAPEG 12 / AMA / MAM COPOLYMER
- This polymer has an LCST being established in a temperature range between 40 ° C and 25 ° C.
- the mixture is stirred (150 rpm; agitation by anchor) 556.25 parts of water, and the reactor is brought to the temperature of 80 ° C under nitrogen sweep.
- the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
- This polymer has an LCST of 22 ° C.
- This polymer is not soluble in the temperature range above 4 ° C studied.
- This polymer has an LCST of 36 ° C.
- This polymer is not water-soluble and is in the form of an opaque dispersion despite the low rate of hydrophobic units. It has a change of appearance
- This polymer is not soluble and is in the form of an opaque dispersion. A change in appearance (precipitation) appears at 40 ° C, comparable to an LCST.
- the most suitable hydrophobic monomers are those having a hydrophobic character which is not too marked, such as methyl methacrylate. Its incorporation rate can go up to 40 mol%. As soon as the hydrophobic character becomes important as it is the case of butyl methacrylate and lauryl methacrylate, the rate necessary for the preservation of thermosensitivity and the solubility in water is low, namely of the order of 5 % and 0.1 mol%.
- a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having a nOE of 8.5.
- This polymer has an LCST of 18 ° C.
- a mixture of MAPEG 8 and MAPEG12 was used to prepare a copolymer having an nOE of 10.5.
- This polymer has an LCST of 35 ° C.
- a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer, having an nOE of 9.5.
- This polymer has an LCST of 27 ° C.
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Abstract
The invention concerns a method which consists in treating in an aqueous medium with a water soluble modifying (co)polymer having heat-sensitive properties, in particular a LCST between 3 and 100 °C. The method consists in treating the substrate in an aqueous medium by the heat-sensitive modifying (co)polymer at a temperature not less than the LCST of the heat-sensitive (co)polymer to precipitate the latter onto the substrate while it is being treated on account of its hydrophobic character in this temperature domain. In the case where the substrate to be treated cannot be subjected to temperature exceeding a value T, the method consists in treating the substrate in an aqueous medium at a temperature < T, the water soluble and heat-sensitive (co)polymer being then selected among those having a LCST not higher than treatment temperature. In the case where the substrate is treated in an aqueous medium at a temperature not higher than the LCST of the water soluble heat-sensitive (co)polymer, the (co)polymer is selected among those having functional, ionic or compatibility units enabling to fix it on the substrate.
Description
PROCEDE DE MODIFICATION HYDROPHILE D'UN SUBSTRAT- METTANT EN JEU UN TRAITEMENT EN MILIEU AQUEUX PAR UN POLYMÈRE SOLUBLE DANS L'EAU ET THERMOSENSIBLE.PROCESS FOR HYDROPHILIC MODIFICATION OF A SUBSTRATE USING A TREATMENT IN AN AQUEOUS MEDIUM WITH A WATER-SOLUBLE AND THERMOSENSITIVE POLYMER.
La présente invention concerne la modification hydrophile des substrats, nécessitant un traitement en milieu aqueux par les polymères solubles dans l'eau, et l'obtention de substrats secs modifiés hydrophiles. Elle apporte un renforcement de l'adsorption de ces polymères sur les substrats, basée sur un traitement dans l'eau à une température adaptée, en présence de polymères hydrosolubles à caractère thermosensible et de compositions adaptées. L'invention englobe également le cas où la modification hydrophile des substrats n'est que temporaire.The present invention relates to the hydrophilic modification of the substrates, requiring treatment in an aqueous medium with polymers soluble in water, and the obtaining of hydrophilic modified dry substrates. It enhances the adsorption of these polymers on substrates, based on a treatment in water at a suitable temperature, in the presence of water-soluble polymers of heat-sensitive nature and of suitable compositions. The invention also covers the case where the hydrophilic modification of the substrates is only temporary.
Un premier objectif est de favoriser l'adsorption des polymères solubles dans l'eau ou hydrophiles sur des substrats imposant impérativement un traitement en milieu aqueux en présence de ces polymères. Les polymères étant solubles dans l'eau ou hydrophiles ont, de par leur forte affinité avec l'eau, tendance à rester dans le milieu aqueux au lieu de s'adsorber sur les substrats que l'on souhaite traiter et ainsi modifier la' surface.A first objective is to promote the adsorption of water-soluble or hydrophilic polymers on substrates imperatively requiring treatment in an aqueous medium in the presence of these polymers. The polymers being water-soluble or hydrophilic are, by their very high affinity with water, tend to remain in the aqueous medium instead of being adsorbed on the substrates that is desired to treat and thus modify the surface .
Un second objectif est celui de réaliser des revêtements temporaires hydrophiles et "lessivables" sur les substrats nécessitant d'être traités en milieu aqueux. Il s'agit d'apporter deux solutions à deux problèmes différents, le premier relatif à l'adsorption de polymère pour-'""la formation d'un revêtement hydrophile sur des substrats destinés à diverses applications, et le second traitant de la désorption ou l'élimination du revêtement hydrophile dit "lessivable" sur les substrats après applications. Dans ce cas, il faut, comme précédemment favorisier l'adsorption des polymères solubles dans l'eau ou hydrophiles sur des substrats imposant impérativement un traitement . en milieu aqueux en présence de ces polymères ; et le second volet du problème consiste à proposer, après utilisation des substrats modifiés pour une application donnée, une méthode permettant la désorption de ces
polymères sur le substrat modifié hydrophile également en milieu aqueux afin d'éviter l'accumulation du polymère après une série d'étapes d' adsorption.A second objective is to produce temporary hydrophilic and "washable" coatings on the substrates which need to be treated in an aqueous medium. It involves providing two solutions to two different problems, the first relating to the adsorption of polymer for - '"" the formation of a hydrophilic coating on substrates intended for various applications, and the second dealing with desorption. or the elimination of the so-called "washable" hydrophilic coating on the substrates after applications. In this case, it is necessary, as previously, to promote the adsorption of water-soluble or hydrophilic polymers on substrates which imperatively require treatment. in an aqueous medium in the presence of these polymers; and the second part of the problem consists in proposing, after using the modified substrates for a given application, a method allowing the desorption of these polymers on the hydrophilic modified substrate also in an aqueous medium in order to avoid the accumulation of the polymer after a series of adsorption steps.
Les polymères sont utilisés depuis de nombreuses décennies pour la modification des propriétés de divers substrats tels que le papier, textile, métal, et bois, béton. Il est souvent recherché à travers ces modifications, l'apport ou amélioration de diverses propriétés, notamment les propriétés mécaniques, antistatiques, le toucher, la résistance aux liquides aqueux, aux graisses par modification hydrophobe et oléophobe des substrats, la mouillabilité et l'aptitude à éliminer facilement les salissures pendant les lavages grâce à la modification hydrophile des substrats. Pour réussir la modification des propriétés d'un substrat par des polymères, il est nécessaire de concevoir ces polymères de telle sorte qu'ils puissent s'adsorber ou se fixer facilement sur le substrat pendant leur application sur ce dernier. Par exemple, le polymère peut être fonctionnalisé de manière à favoriser diverses interactions avec le substrat notamment :Polymers have been used for many decades for the modification of the properties of various substrates such as paper, textile, metal, and wood, concrete. It is often sought through these modifications, the provision or improvement of various properties, in particular the mechanical, antistatic properties, the feel, the resistance to aqueous liquids, to greases by hydrophobic and oleophobic modification of the substrates, the wettability and the aptitude. easily remove dirt during washing thanks to the hydrophilic modification of the substrates. To successfully modify the properties of a substrate with polymers, it is necessary to design these polymers in such a way that they can be easily adsorbed or fixed on the substrate during their application to the latter. For example, the polymer can be functionalized so as to promote various interactions with the substrate, in particular:
(1) La fixation chimique entre le polymère et le support (réticulation, condensation) . On peut par exemple citer la fixation sur la fibre de cellulose à travers les OH de la cellulose pour les applications papier et textile. Dans le cas de certains textiles, la modification hydrophile peut être nécessaire dans le but de faciliter le lavage du textile après usage. Les polymères hydrosolubles sont utilisés pour cette application couramment appelée "soil-release", et améliorent de façon notable, l'élimination des salissures sur le tissu traité "soil-release". Le brevet américain US-A-5 962 400 propose des polymères polyamide-polysaccharides . Les brevets américains US- A-4 999 869 et US-A-5 514 288 proposent des polymères greffés poly (oxyde d' al ylène) /polyvinyl ester). Dans le domaine de fixation chimique, la demande
internationale PCT WO/99/49124 propose des polymères multifonctionnels ayant des groupes hydrophobes et des groupes hydrophiles et des polymères thermosensibles.(1) Chemical fixation between the polymer and the support (crosslinking, condensation). Mention may, for example, be made of the attachment to the cellulose fiber through the OH of the cellulose for paper and textile applications. In the case of certain textiles, the hydrophilic modification may be necessary in order to facilitate the washing of the textile after use. The water-soluble polymers are used for this application commonly called "soil-release", and significantly improve the elimination of dirt on the fabric treated "soil-release". American patent US-A-5,962,400 proposes polyamide-polysaccharide polymers. US patents US-A-4,999,869 and US-A-5,514,288 provide poly (alylene oxide) / polyvinyl ester graft polymers. In the field of chemical fixation, the demand PCT international WO / 99/49124 proposes multifunctional polymers having hydrophobic groups and hydrophilic groups and thermosensitive polymers.
(2) Les interactions ioniques et la complexation entre le support et le polymère, constitués tous les deux de motifs ioniques de charges opposées. Par exemple dans la fabrication du papier, les fibres cellulosiques négativement chargées, sont traitées en milieu aqueux par des polymères hydrosolubles cationiques pour obtenir une résistance humide améliorée (par exemple brevets américains US-A-3 556 932, US-A-3 556 933, US- A-3 700 623, US-A-3 772 076) . Des latex, des solutions aqueuses ou dispersions aqueuses de copolymères ayant des motifs cationiques sont également utilisés pour la modification du papier : (a) les latex de copoly ère styrène/butadiène cationique pour le couchage de papier(2) The ionic interactions and the complexation between the support and the polymer, both consisting of ionic units of opposite charges. For example in the manufacture of paper, negatively charged cellulosic fibers are treated in an aqueous medium with cationic water-soluble polymers to obtain improved wet strength (for example American patents US-A-3,556,932, US-A-3,556,933 , US-A-3,700,623, US-A-3,772,076). Latexes, aqueous solutions or aqueous dispersions of copolymers having cationic units are also used for the modification of paper: (a) cationic styrene / butadiene copoly latexes for coating paper
(brevets américains US-A-4 189 345, US-A- 3 926 890,(American patents US-A-4,189,345, US-A- 3,926,890,
US-A-5 200 036, demande internationale WO 96/35841), etUS-A-5 200 036, international application WO 96/35841), and
(b) les latex et solution de copolymères perfluorés cationiques pour le traitement oléophobe et hydrophobe du papier (par exemple demande internationale WO 98/23657) .(b) latexes and solution of cationic perfluorinated copolymers for the oleophobic and hydrophobic treatment of paper (for example international application WO 98/23657).
(3) La précipitation du polymère lors des traitements de substrats en milieu aqueux. L'ajout d'un second additif est une approche souvent utilisée pour provoquer la précipitation du polymère sur le support. Par exemple pour améliorer la souplesse du papier, les fibres cellulosiques sont traitées par des latex anioniques de copolymère styrène/butadiène. Afin de fixer ce dernier sur les fibres au moment de la fabrication du papier, un additif polymère hydrosoluble cationique est incorporé pour déstabiliser le latex qui précipite par conséquent sur les fibres de papier (par exemple brevets américains US-A-4 121 966, US-A-2 745 744) . Cette approche de précipitation permet ainsi de réussir l'adsorption d'un polymère ne
possédant aucun motif fonctionnel de fixation sur le support. Cependant, elle présente l'inconvénient d'incorporer un tiers corps dans la formulation.(3) Precipitation of the polymer during the treatment of substrates in an aqueous medium. The addition of a second additive is an approach often used to cause precipitation of the polymer on the support. For example, to improve the flexibility of the paper, the cellulosic fibers are treated with anionic latexes of styrene / butadiene copolymer. In order to fix the latter on the fibers at the time of papermaking, a cationic water-soluble polymer additive is incorporated to destabilize the latex which consequently precipitates on the paper fibers (for example American patents US-A-4 121 966, US -A-2 745 744). This precipitation approach thus makes it possible to successfully adsorb a polymer which having no functional pattern of attachment to the support. However, it has the disadvantage of incorporating a third body into the formulation.
(4) -L'incorporation de motifs compatibilisants dans la structure du polymère hydrosoluble pour renforcer son affinité avec le support. La demande de brevet japonais JP-10 330 727 revendique la modification hydrophile des non-tissés polypropylène avec des polymères hydrosolubles qui sont des copolymères styrène/isobutylène sulfoné qui apportent l'effet "soil-release", mais également une bonne adhésion sur le non-tissé polypropylène.(4) -The incorporation of compatibilizing units in the structure of the water-soluble polymer to reinforce its affinity with the support. Japanese patent application JP-10 330 727 claims the hydrophilic modification of polypropylene nonwovens with water-soluble polymers which are styrene / isobutylene sulfonated copolymers which bring the "soil-release" effect, but also good adhesion on the non -woven polypropylene.
En ce qui concerne la fixation ou l'adsorption de polymère hydrosoluble sur les substrats nécessitant impérativement un traitement en milieu aqueux comme par exemple le papier et le textile, il paraît évident que la méthode permettant de précipiter le polymère sur le support en le rendant insoluble dans l'eau est celle qui conduit au maximum d' adsorption. Il convient par ailleurs de coupler l'approche précipitation avec les stratégies de fixation chimique ou ionique en associant au polymère hydrosoluble à précipiter les motifs réactifs, ioniques ou compatibilisants adaptés. Enfin, il est préférable de trouver un moyen de précipitation évitant l'incorporation d'un tiers corps pouvant être incommode pour la mise en oeuvre, voire altérer les propriétés finales. Cette invention propose des solutions répondant à ces critères.With regard to the fixing or adsorption of water-soluble polymer on substrates imperatively requiring treatment in an aqueous medium such as for example paper and textile, it seems obvious that the method allowing the polymer to precipitate on the support by making it insoluble in water is that which leads to maximum adsorption. It is also necessary to couple the precipitation approach with the chemical or ionic fixing strategies by associating with the water-soluble polymer to precipitate the reactive, ionic or compatibilizing units suitable. Finally, it is preferable to find a means of precipitation avoiding the incorporation of a third body which may be inconvenient for the implementation, or even alter the final properties. This invention provides solutions that meet these criteria.
La présente invention propose une nouvelle méthode s 'appuyant sur le changement radical de la solubilité dans l'eau de certains polymères hydrosolubles en fonction de la température. Plus précisément, elle tire profit des propriétés particulières des polymères thermosensibles, c'est-à-dire des polymères solubles dans l'eau en dessous d'une certaine température couramment appelée LCST, mais qui deviennent insolubles au-dessus de cette température LCST. Pour les substrats devant être traités en milieu aqueux par
un polymère hydrosoluble, elle propose d'une part, de choisir un polymère hydrosoluble ayant une LCST, et d'autre part, de réaliser le traitement aqueux dudit substrat de préférence à une température supérieure ou égale à la LCST afin de précipiter le polymère devenu insoluble dans l'eau, et ainsi favoriser la fixation ou l'adsorption dudit polymère hydrosoluble à la surface du substrat. Dans le cas des traitements ne pouvant être réalisés à une température supérieure à la LCST du polymère thermosensible, ce dernier doit avoir des motifs fonctionnels ou compatibilisants permettant sa fixation sur le substrat.The present invention provides a new method based on the radical change in the solubility in water of certain water-soluble polymers as a function of temperature. More specifically, it takes advantage of the particular properties of heat-sensitive polymers, that is to say polymers soluble in water below a certain temperature commonly called LCST, but which become insoluble above this temperature LCST. For substrates to be treated in an aqueous medium by a water-soluble polymer, it proposes on the one hand, to choose a water-soluble polymer having an LCST, and on the other hand, to carry out the aqueous treatment of said substrate preferably at a temperature greater than or equal to the LCST in order to precipitate the polymer which has become insoluble in water, and thus promoting the fixation or adsorption of said water-soluble polymer on the surface of the substrate. In the case of treatments which cannot be carried out at a temperature higher than the LCST of the thermosensitive polymer, the latter must have functional or compatibilizing patterns allowing it to be fixed on the substrate.
L'avantage de cette méthode tient au fait que, dans les conditions de température supérieure à la LCST, le polymère hydrosoluble ayant le caractère thermosensible précipite pendant le traitement en milieu aqueux du substrat, améliorant ainsi la fixation et l'adsorption sur le substrat alors que les autres polymères hydrosolubles main non thermosensibles sont solubles et ont tendance à rester majoritairement dans l'eau au lieu de s'accrocher sur le substrat. Le choix judicieux de la nature ainsi que de la bonne composition de polymères thermosensibles de telle sorte que la LCST soit inférieure à la température requise pour le traitement du substrat (en fonction de l'application finale) , permet de s'affranchir de l'incorporation incommode de nouveaux ingrédients ou tiers corps, que sont les agents précipitants, ou agents séquestrants, pour précipiter et adsorber le polymère hydrosoluble sur le substrat. Par ailleurs, l'agent précipitant peut être incompatible avec l'application finale. Dans le cas d'une modification par un polymère thermosensible, l'étape de séchage du substrat qui suit celle d' adsorption, conduit directement à un substrat sec modifié hydrophile.The advantage of this method lies in the fact that, under the conditions of temperature higher than the LCST, the water-soluble polymer having the thermosensitive character precipitates during the treatment in an aqueous medium of the substrate, thus improving the fixing and the adsorption on the substrate then that the other non-thermosensitive water-soluble hand polymers are soluble and tend to remain mainly in water instead of clinging to the substrate. The judicious choice of the nature as well as of the right composition of heat-sensitive polymers so that the LCST is lower than the temperature required for the treatment of the substrate (depending on the final application), makes it possible to dispense with the inconvenient incorporation of new ingredients or third bodies, which are the precipitating agents, or sequestering agents, to precipitate and adsorb the water-soluble polymer on the substrate. Furthermore, the precipitating agent may be incompatible with the final application. In the case of a modification with a heat-sensitive polymer, the step of drying the substrate which follows that of adsorption, leads directly to a dry hydrophilic modified substrate.
Afin de renforcer davantage l'adsorption du polymère thermosensible sur le support, il peut être nécessaire d'incorporer des motifs réactifs, ioniques ou compatibilisants dans la structure du polymère à condition d'une part que le caractère thermosensible, nécessaire pour la précipitation du polymère soit conservé, et d'autre part,
que ces motifs puissent générer des liaisons covalentes (réaction chimique) , ioniques (interaction ionique) , ou tout simplement renforcer l'adsorption sur le substrat. Dans le cas des traitements ne pouvant être réalisés à une température supérieure à la LCST du polymère thermosensible, ces motifs réactifs, ioniques ou compatibilisants sont également mis à profit pour fixer le polymère au substrat. Le substrat modifié hydrophile peut ainsi être utilisé pour des applications nécessitant une surface hydrophile telles que l'augmentation de la mouillabilite du substrat avec des ingrédients hydrophiles ou l'apport de propriétés barrière entre le substrat et les substances hydrophobes ou oléophobes.In order to further enhance the adsorption of the thermosensitive polymer on the support, it may be necessary to incorporate reactive, ionic or compatibilizing units into the structure of the polymer provided, on the one hand, that the thermosensitive nature, necessary for the precipitation of the polymer be kept, and secondly, that these patterns can generate covalent bonds (chemical reaction), ionic bonds (ionic interaction), or quite simply reinforce adsorption on the substrate. In the case of treatments that cannot be carried out at a temperature higher than the LCST of the thermosensitive polymer, these reactive, ionic or compatibilizing units are also used to fix the polymer to the substrate. The hydrophilic modified substrate can thus be used for applications requiring a hydrophilic surface such as increasing the wettability of the substrate with hydrophilic ingredients or the provision of barrier properties between the substrate and the hydrophobic or oleophobic substances.
Dans le cas des revêtements temporaires, la présente invention propose une méthode basée sur le changement radical de la solubilité dans l'eau de certains polymères hydrosolubles en fonction de la température et du pH. Elle tire profit des propriétés particulières de ces polymères hydrosolubles à la fois thermosensible et sensible au pH, c'est-à-dire des polymères solubles dans l'eau en dessous d'une certaine température (dite LCST), mais qui deviennent insolubles dans l'eau aux températures supérieures à la LCST. Ces mêmes polymères sont solubles dans l'eau à pH basique quelle que soit la température. Les polymères thermosensibles et pH-sensibles de l'invention sont choisis de telle sorte que la température requise pour l'étape de traitement du substrat par adsorption de polymère soit de préférence supérieure ou égale à la LCST du polymère, la séparation ou la précipitation du polymère dans l'eau favorisant la fixation ou l'adsorption du polymère à la surface du substrat.In the case of temporary coatings, the present invention provides a method based on the radical change in the solubility in water of certain water-soluble polymers as a function of temperature and pH. It takes advantage of the particular properties of these water-soluble polymers which are both thermosensitive and sensitive to pH, that is to say polymers which are soluble in water below a certain temperature (known as LCST), but which become insoluble in water at temperatures above the LCST. These same polymers are soluble in water at basic pH whatever the temperature. The thermosensitive and pH-sensitive polymers of the invention are chosen so that the temperature required for the step of treatment of the substrate by adsorption of polymer is preferably greater than or equal to the LCST of the polymer, the separation or the precipitation of the polymer in water promoting the attachment or adsorption of the polymer to the surface of the substrate.
Pour les applications de revêtement temporaire qui nécessite après usage du substrat modifié hydrophile dans les applications précitées, l'élimination ou le lessivage du revêtement hydrophile sur le substrat, cette invention propose deux solutions pour la désorption du revêtement en milieu aqueux :
(1) si la température du milieu aqueux est supérieure à la LCST du polymère thermosensible, il est préconisé de réaliser la désorption en milieu basique, dans la mesure où certaines compositions de polymères thermosensibles proposées dans l'invention perdent leur sensibilité à la température en raison de la neutralisation des fonctions acides carboxyliques présentes dans la structure de ces polymères.For temporary coating applications which, after use of the hydrophilic modified substrate in the aforementioned applications, the elimination or leaching of the hydrophilic coating on the substrate, this invention provides two solutions for the desorption of the coating in an aqueous medium: (1) if the temperature of the aqueous medium is higher than the LCST of the heat-sensitive polymer, it is recommended to carry out the desorption in basic medium, insofar as certain compositions of heat-sensitive polymers proposed in the invention lose their temperature sensitivity by because of the neutralization of the carboxylic acid functions present in the structure of these polymers.
(2) si la température est inférieure à la LCST, la désorption du revêtement peut se faire par simple trempage dans l'eau quel que soit le pH.(2) if the temperature is lower than the LCST, the desorption of the coating can be done by simple soaking in water whatever the pH.
Sous une première forme, cette invention a pour objet l'utilisation des propriétés particulières des polymères thermosensibles pour renforcer la modification hydrophile de divers substrats nécessitant impérativement un traitement en milieu aqueux par des polymères hydrosolubles et utilisées pour diverses applications telles que l'augmentation de la mouillabilite du substrat avec des ingrédients hydrophiles ou l'apport de propriétés barrière entre le substrat et les substances hydrophobes ou oléophobes. Ces polymères thermosensibles doivent avoir de préférence des motifs fonctionnels, réactifs, ioniques ou compatibilisants pour améliorer la fixation sur les substrats, mais également pour pouvoir être appliqués sur une plage de température plus large, notamment en dessous et au dessus de la LCST des polymères thermosensibles.In a first form, the subject of this invention is the use of the particular properties of thermosensitive polymers to reinforce the hydrophilic modification of various substrates imperatively requiring treatment in an aqueous medium with water-soluble polymers and used for various applications such as increasing the wettability of the substrate with hydrophilic ingredients or the provision of barrier properties between the substrate and hydrophobic or oleophobic substances. These heat-sensitive polymers must preferably have functional, reactive, ionic or compatibilizing units to improve the fixation on the substrates, but also to be able to be applied over a wider temperature range, in particular below and above the LCST of the heat-sensitive polymers. .
Sous une seconde forme, l'invention concerne les revêtements hydrophiles temporaires sur les substrats qui nécessitent après utilisation du substrat modifié hydrophile pour les applications précitées, l'élimination ou le lessivage du revêtement hydrophile sur le substrat. L' invention propose deux solutions pour la désorption du revêtement en milieu aqueux pour éviter l'accumulation des polymères sur les substrats après application. La présente invention a donc pour objet un procédé de modification hydrophile d'un substrat, caractérisé par le
fait que l'on traite ledit substrat en milieu aqueux par un modifiant polymère ou copolymère hydrosoluble ayant des propriétés thermosensibles. On entend par polymère ayant un caractère thermosensible, un polymère présentant un changement radical de solubilité ou de transition hydrophile/hydrophobe à une température critique couramment appelée la LCST. Ces (co) polymères sont insolubles dans l'eau au-dessus de la LCST et solubles dans l'eau au-dessous de la LCST. Ledit modifiant polymère ou copolymère hydrosoluble thermosensible a une LCST généralement comprise entre 3 et 100°C.In a second form, the invention relates to temporary hydrophilic coatings on substrates which require, after use of the modified hydrophilic substrate for the aforementioned applications, the removal or leaching of the hydrophilic coating on the substrate. The invention provides two solutions for the desorption of the coating in an aqueous medium to avoid the accumulation of polymers on the substrates after application. The present invention therefore relates to a process for hydrophilic modification of a substrate, characterized by the the fact that said substrate is treated in an aqueous medium with a water-soluble polymer or copolymer modifier having thermosensitive properties. The term “polymer having a thermosensitive character” is understood to mean a polymer having a radical change in solubility or in hydrophilic / hydrophobic transition at a critical temperature commonly called LCST. These (co) polymers are insoluble in water above the LCST and soluble in water below the LCST. Said water-soluble thermosensitive polymer or copolymer modifier has an LCST generally between 3 and 100 ° C.
Conformément à un premier mode de réalisation de ce procédé, on traite le substrat en milieu aqueux par ledit modifiant polymère ou copolymère thermosensible à une température au moins égale à la LCST dudit polymère ' ou copolymère thermosensible afin de faire précipiter ce dernier sur ledit substrat au moment du traitement en raison de son caractère hydrophobe dans ce domaine de température. Conformément à un second mode de réalisation de ce procédé suivant lequel le substrat à traiter ne supporte pas d'être soumis à une température dépassant une valeur T, on traite le substrat en milieu aqueux à une température inférieure à T, le polymère ou copolymère hydrosoluble thermosensible étant alors choisi parmi ceux ayant une LCST au plus égale à la température de traitement. Autrement dit pour certaines applications (la modification hydrophile de certains textiles par exemple) , dont la température de traitement est imposée et ne peut être modifiée, il convient, contrairement à ce qui est indiqué au paragraphe précédent, d'adapter la nature ou la composition du polymère thermosensible de manière à obtenir une LCST de préférence inférieure ou égale à la température de traitement.In accordance with a first embodiment of this process, the substrate is treated in an aqueous medium with said heat-sensitive polymer or copolymer modifier at a temperature at least equal to the LCST of said heat-sensitive polymer or copolymer in order to precipitate the latter on said substrate to time of treatment due to its hydrophobic nature in this temperature range. In accordance with a second embodiment of this process according to which the substrate to be treated does not tolerate being subjected to a temperature exceeding a value T, the substrate is treated in an aqueous medium at a temperature below T, the water-soluble polymer or copolymer thermosensitive then being chosen from those having an LCST at most equal to the treatment temperature. In other words for certain applications (the hydrophilic modification of certain textiles for example), the treatment temperature of which is imposed and cannot be modified, it is advisable, contrary to what is indicated in the preceding paragraph, to adapt the nature or the composition thermosensitive polymer so as to obtain an LCST preferably less than or equal to the treatment temperature.
Conformément à un troisième mode de réalisation du procédé, suivant lequel on traite le substrat en milieu aqueux à une température au plus égale à la LCST du (co) polymère hydrosoluble thermosensible (cas des traitements ne pouvant être réalisés à une température supérieure à la LCST du (co) polymère thermosensible), on
choisit ledit (co) polymère parmi ceux ayant des motifs fonctionnels, ioniques ou compatibilisants permettant sa fixation sur le substrat. Les motifs fonctionnels sont choisis notamment parmi les fonctions cationiques, anioniques, acide sulfonique, acide phosphaté, phosphate, phosphonees, groupes hydrophobes, éthoxylées, acide carboxylique, silanées, maléique, alcool, aminé, amide, sulfonates, carboxylates .In accordance with a third embodiment of the method, according to which the substrate is treated in an aqueous medium at a temperature at most equal to the LCST of the thermosensitive water-soluble (co) polymer (case of treatments which cannot be carried out at a temperature higher than the LCST thermosensitive (co) polymer), chooses said (co) polymer from those having functional, ionic or compatibilizing units allowing its fixation on the substrate. The functional units are chosen in particular from cationic, anionic, sulfonic acid, phosphatic acid, phosphate, phosphonees, hydrophobic, ethoxylated, carboxylic acid, silane, maleic, alcohol, amino, amide, sulfonate, carboxylate groups.
Les groupes hydrophobes peuvent être mis à profit pour renforcer la compatibilité entre substrats à traiter et polymères thermosensibles.Hydrophobic groups can be used to reinforce the compatibility between substrates to be treated and heat-sensitive polymers.
Les fonctions éthoxylées, par exemple, peuvent former des liaisons hydrogènes avec les groupes hydroxyle des textiles en coton ou en fibre de rayonne. Les-fonctions phosphate ou phosphonees peuvent renforcer l'adhésion sur le métal et le verre. Les fonctions silanées sont réservées pour améliorer l'adhésion sur le verre et le béton.The ethoxylated functions, for example, can form hydrogen bonds with the hydroxyl groups of cotton or rayon fiber textiles. The phosphate or phosphone functions can strengthen adhesion to metal and glass. The silane functions are reserved to improve adhesion on glass and concrete.
Par ailleurs, on peut traiter ledit substrat en milieu aqueux par le modifiant homopolymère ou copolymère hydrosoluble ayant des propriétés thermosensibles qui a des motifs fonctionnels (tels que ceux indiqués ci-dessus) susceptibles d' apporter des propriétés complémentaires autres que l' hydrophilie (antistatisme, adhésion, mouillabilite, hydrophobie, fixation des substances hydrophiles et hydrophobes, élimination des substances hydrophiles et hydrophobes) , et/ou qui est combinée avec au moins un autre ingrédient actif dont la rétention ou l'adsorption sur le substrat résulte de son enrobage ou de son encapsulation par le polymère thermosensible au moment de sa précipitation sur le substrat au-dessus de la LCST.Furthermore, said substrate can be treated in an aqueous medium with the water-soluble homopolymer or copolymer modifier having thermosensitive properties which has functional units (such as those indicated above) capable of bringing complementary properties other than hydrophilicity (antistatism). , adhesion, wettability, hydrophobicity, fixation of hydrophilic and hydrophobic substances, elimination of hydrophilic and hydrophobic substances), and / or which is combined with at least one other active ingredient whose retention or adsorption on the substrate results from its coating or of its encapsulation by the heat-sensitive polymer at the time of its precipitation on the substrate above the LCST.
Les autres ingrédients précités sont choisis par exemple parmi les polymères hydrophobes sous forme de latex, les dispersions aqueuses de polymères, les charges, les enzymes, les tensio-actifs, les matières organiques et les matières minérales ; ces ingrédients sont utilisés pour apporter des propriétés complémentaires aux substrats. Le (co) polymère thermosensible joue dans ce cas le rôle d'un agent de transfert de ces ingrédients pour un contact plus
intime entre ces derniers et la surface du substrat. En plus de l'enrobage et l' encapsulation suite à la précipitation du (co) polymère thermosensible, ce dernier peut interagir avec ces ingrédients pour rendre le transport plus efficace. Ainsi, on peut choisir l'homo- ou copolymère hydrosoluble thermosensible parmi ceux aptes à interagir avec le ou les ingrédients utilisés conjointement, par exemple en formant des liaisons hydrogène avec celui-ci ou ceux-ci . Les substrats concernés par le traitement et la modification des propriétés selon l'invention sont choisis entre autres parmi le textile, les non-tissés, le métal, le verre, le bois, le papier, le cuir, les substrats du bâtiment, la moquette, les fibres, les polymères, le béton. Le procédé selon l'invention peut consister en un traitement hydrophile des textiles et non-tissés par adsorption du (co) polymère' thermosensible ; ou consister en un traitement du papier, en particulier l'adsorption sur les fibres de cellulose pour l'amélioration de la résistance humide du papier et le traitement hydrophobe et oleophobe du papier ; ou encore consister en un traitement apportant aux substrats des propriétés antistatiques, la mouillabilite, une modification hydrophile ou hydrophobe, la fixation des substances hydrophiles et hydrophobes ou l'élimination des substances hydrophiles et hydrophobes, des propriétés barrière entre le substrat et les substances hydrophobes ou oléophobes, la fixation de substances grasses.The other aforementioned ingredients are chosen, for example, from hydrophobic polymers in the form of latex, aqueous polymer dispersions, fillers, enzymes, surfactants, organic materials and mineral materials; these ingredients are used to provide complementary properties to the substrates. The thermosensitive (co) polymer in this case acts as a transfer agent for these ingredients for more contact. intimate between them and the surface of the substrate. In addition to the coating and encapsulation following the precipitation of the thermosensitive (co) polymer, the latter can interact with these ingredients to make transport more efficient. Thus, the thermosensitive water-soluble homo- or copolymer can be chosen from those capable of interacting with the ingredient (s) used jointly, for example by forming hydrogen bonds with it or these. The substrates concerned by the treatment and modification of the properties according to the invention are chosen among others from textiles, nonwovens, metal, glass, wood, paper, leather, building substrates, carpet , fibers, polymers, concrete. The method according to the invention may be a hydrophilic treatment of textiles and non-woven by adsorption of the (co) polymer heat sensitive; or consist of a treatment of the paper, in particular the adsorption on the cellulose fibers for the improvement of the wet resistance of the paper and the hydrophobic and oleophobic treatment of the paper; or also consist of a treatment providing the substrates with antistatic properties, wettability, a hydrophilic or hydrophobic modification, the fixing of hydrophilic and hydrophobic substances or the elimination of hydrophilic and hydrophobic substances, barrier properties between the substrate and the hydrophobic substances or oleophobic, fixation of fatty substances.
La présente invention porte également sur un procédé tel que défini ci-dessus, suivant lequel le traitement a conduit à un revêtement hydrophile prévu pour être temporaire s' étant adsorbé sur ledit substrat. Pour éliminer ou lessiver ledit revêtement hydrophile après utilisation du substrat ainsi modifié hydrophile, on provoque une désorption dudit revêtement : — en milieu aqueux basique à une température supérieure à la LCST, le (co) polymère thermosensible utilisé portant des fonctions acide carboxylique et étant tel qu' il perd sa sensibilité à la température en raison de
la neutralisation desdites fonctions acide carboxylique, ou — quel que soit le pH à une température inférieure à la LCST. On utilise avantageusement un modifiant choisi parmi :The present invention also relates to a method as defined above, according to which the treatment has led to a hydrophilic coating intended to be temporary having been adsorbed on said substrate. To remove or leach said hydrophilic coating after using the hydrophilic modified substrate, it causes desorption of said coating: - in basic aqueous medium at a temperature above the LCST, the thermosensitive (co) polymer used carrying carboxylic acid functions and being such that it loses its sensitivity to temperature due to the neutralization of said carboxylic acid functions, or - whatever the pH at a temperature below the LCST. Advantageously, a modifier chosen from:
(I) les copolymères hydrosolubles thermosensibles obtenus à partir d'une composition de monomères comprenant, pour 100 parties en moles :(I) the water-soluble thermosensitive copolymers obtained from a composition of monomers comprising, per 100 parts by moles:
(A) de 1 à 98 parties en moles d'au moins un composé hydrosoluble choisi parmi ceux des formules (I) et (II) suivantes :(A) from 1 to 98 parts by moles of at least one water-soluble compound chosen from those of formulas (I) and (II) below:
R1 CH2 = C-C-0-[R2-0]n-R3 (I)R 1 CH 2 = CC-0- [R 2 -0] n -R 3 (I)
OO
dans laquelle :in which :
- R représente H ou -CH3 ; o - R représente un reste alkylène en Co qui comporte éventuellement un ou plusieurs groupes OH, ou un reste alkylène en C3-C4 qui comporte un ou plusieurs groupes OH ;- R represents H or -CH3; o - R represents a C alkylene residue which optionally comprises one or more OH groups, or a C3-C4 alkylene residue which comprises one or more OH groups;
- R représente H ou -CH3 ; et - n est un nombre entier compris entre 1 et- R represents H or -CH3; and - n is an integer between 1 and
70 ;70;
R4 R5 R 4 R 5
\\
C = C-Y1-0-[R6-0]^-R7 (II) / °C = CY 1 -0- [R 6 -0] ^ -R 7 (II) / °
HH
dans laquelle :in which :
- R et R"3 représentent chacun indépendamment hydrogène ou alkyle en C2-C4 ; -1 - Y est une liaison simple ou un reste alkylène en C-1-C4 ;
R° représente un reste alkylène en C2 qui comporte éventuellement un ou plusieurs groupes OH, ou un reste alkylène en C3-C4 qui comporte un ou plusieurs groupes OH ; R' représente H ou -CH3 ; et o est un nombre entier compris entre 1 et 70 ;- R and R " 3 each independently represent hydrogen or C2-C4 alkyl; -1 - Y is a single bond or a C-1-C4 alkylene residue; R ° represents a C 2 alkylene residue which optionally comprises one or more OH groups, or a C 3 -C 4 alkylene residue which comprises one or more OH groups; R 'represents H or -CH3; and o is an integer between 1 and 70;
(B) de 2 à 95 parties en moles d'au moins un monomère hydrosoluble choisi parmi les acides carboxyliques à insaturation éthylénique et les anhydrides d'acides carboxyliques à insaturation éthylénique ;(B) from 2 to 95 parts by mole of at least one water-soluble monomer chosen from ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic acid anhydrides;
(C) de 0 à 70 parties en moles d'au moins un composé hydrosoluble choisi parmi ceux des formules (III) et (IV) :(C) from 0 to 70 parts by mole of at least one water-soluble compound chosen from those of formulas (III) and (IV):
R8 CH2 = C-C-O-[R9-O]p-[R10-O]q-R1:L (III)R 8 CH 2 = CCO- [R 9 -O] p - [R 10 -O] q -R 1: L (III)
OO
dans laquelle :in which :
- R° représente H ou -CH3 ; - R et R représentent chacun indépendamment un reste alkylène en C2-C4 qui comporte éventuellement un ou plusieurs groupes OH, R9 et R10 étant différents l'un de l'autre ;- R ° represents H or -CH3; - R and R each independently represent a C2-C4 alkylene residue which optionally comprises one or more OH groups, R 9 and R 10 being different from each other;
- R11 représente H ou -CH3 ; - p est un nombre entier compris entre 1 et- R 11 represents H or -CH3; - p is an integer between 1 and
70 ; et70; and
- q est un nombre entier compris entre 1 et 40 ;- q is an integer between 1 and 40;
R12 R13 R 12 R 13
C = C-Y2-0-[R14-0]r,-[R15-0]„-R16 (IV)C = CY 2 -0- [R 14 -0] r , - [R 15 -0] „- R 16 (IV)
/ r / r
H
dans laquelleH in which
- R 1 z9- et R 1 J "-? représentent chacun indépendamment hydrogène ou alkyle en C2-C^; o- R 1 z 9- and R 1 J " -? Each independently represent hydrogen or C 2 -C 4 alkyl; o
- Y^ est une liaison simple ou un reste alkylène en C-^-C^ ;- Y ^ is a single bond or a C - ^ - C ^ alkylene residue;
- R14 et R1-3 représentent chacun indépendamment un radical alkylène en C-p-C^ comportant éventuellement un ou plusieurs groupes OH, R14 et R i) étant différents l'un de l'autre ;- R 14 and R 1 - 3 each independently represent an alkylene radical in CpC ^ optionally comprising one or more OH groups, R 14 and R i) being different from each other;
- R1& représente H ou -CH3 ;- R 1 & represents H or -CH3;
- r est un nombre entier compris entre 1 et 70 ; et- r is an integer between 1 and 70; and
- s est un nombre entier compris entre 1 et 40 ;- s is an integer between 1 and 40;
(D) de 0 à 30 parties en moles d'au moins un composé hydrosoluble choisi parmi ceux des formules (V) et (VI) :(D) from 0 to 30 parts by moles of at least one water-soluble compound chosen from those of formulas (V) and (VI):
R17 R 17
CH2 = C-C-0-[R18-0]t-R19 (V) OCH 2 = CC-0- [R 18 -0] t -R 19 (V) O
dans laquelle :in which :
- R17 représente H ou -CH3 ;- R 17 represents H or -CH3;
- R1 1 R0 représente un reste alkylène en C -C^ qui comporte éventuellement un ou plusieurs groupes OH (en particulier les composés en c3_c4 comportent un ou plusieurs groupes OH afin d'assurer leur solubilité dans l'eau) ;- R 1 1 R 0 represents a C 1 -C 4 alkylene residue which optionally comprises one or more OH groups (in particular the compounds in c 3 _c 4 comprise one or more OH groups in order to ensure their solubility in water) ;
- R 1:? représente une chaîne alkyle en C2-C4Q, aryle ou aralkyle en Cg-CgQ ; et- R 1 :? represents a C2-C4 Q alkyl, aryl or Cg-Cg Q aralkyl chain; and
- t est un nombre entier compris entre 1 et 70 ;
dans laquelle : f) -i- t is an integer between 1 and 70; in which: f ) -i
- R^ u et R représentent chacun indépendamment hydrogène ou alkyle en C^C^;- R ^ u and R each independently represent hydrogen or C ^ C ^ alkyl;
- Y3 est une liaison simple ou un radical alkylène en C-]_-C4 ;- Y 3 is a single bond or a C- ] _-C 4 alkylene radical;
- R22 représente un reste alkylène en C -C^ qui comporte éventuellement un ou plusieurs groupes OH (en particulier les composés en C3-C4 comportent un ou plusieurs groupes OH afin d'assurer leur solubilité dans l'eau) ;- R 22 represents a C 1 -C 4 alkylene residue which optionally comprises one or more OH groups (in particular the C 3 -C 4 compounds comprise one or more OH groups in order to ensure their solubility in water);
9 "D9 "D
- R O est un reste alkyle en C2-C^Q, aryle ou aralkyle en Cg-Cgβ ; et- R O is alkyl C 2 -C ^ Q, aryl or aralkyl, Cg-Cg β; and
- u est un nombre entier compris entre 1 et 70 ;- u is an integer between 1 and 70;
(E) de 0 à 30 parties en moles d'au moins un monomère hydrosoluble choisi parmi :(E) from 0 to 30 parts by mole of at least one water-soluble monomer chosen from:
(El) les composés hydrosolubles de formule (VII) :(E1) the water-soluble compounds of formula (VII):
9494
- R^ représente H ou -CH3 ;- R ^ represents H or -CH3;
- A représente -O- ou -NH- ;- A represents -O- or -NH-;
Bl représente -CH2CH2-, -CH2CH2CH2- ou -CH9CHOHCH9- ;B1 represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 9 CHOHCH 9 -;
- R et R représentent chacun indépendamment """CH3 ou une chaîne alkyle en C2-C]_ ;- R and R each independently represent """CH3 or a C 2 -C ] alkyl chain;
- R représente H, -CH3 ou une chaîne alkyle en C2-C16 ;- R represents H, -CH3 or a C 2 -C 16 alkyl chain;
- XΘ représente un anion monovalent, tel que C1Θ, SCNθ,CH3S03 θ et Brθ ;
(E2) les composés hydrosolubles de formule (VIII) :- X Θ represents a monovalent anion, such as C1 Θ , SCN θ , CH 3 S0 3 θ and Br θ ; (E2) the water-soluble compounds of formula (VIII):
dans laquelle :in which :
A représente -O- ou -NH- ; B2 représente -CH2CH2-, -CH2CH.2CH2- ou -CH2CHOH CH2- ; - R28 représente H ou -CH3 ; etA represents -O- or -NH-; B 2 represents -CH 2 CH 2 -, -CH 2 CH .2 CH 2 - or -CH 2 CHOH CH 2 -; - R 28 represents H or -CH3; and
9 n on9 n on
R^3 et Rou représentent chacun indépendamment ""CH3 ou une chaîne alkyle en C2-C-j_ ;R 3 and R or each independently represents "" CH 3 or an alkyl chain C 2 -C j _;
(E3) les monomères hydrosolubles sulfones à insaturation éthylénique et leurs sels ;(E3) the water-soluble ethylenically unsaturated monomers and their salts;
(E4) les monomères hydrosolubles silanés à insaturation éthylénique ;(E4) water-soluble ethylenically unsaturated monomers;
(E5) les monomères hydrosolubles à fonction phosphate à insaturation éthylénique ;(E5) the water-soluble monomers containing ethylenically unsaturated phosphate;
(E6) les monomères hydrosolubles phosphonés à insaturation éthylénique et leurs sels ;(E6) the water-soluble phosphonated ethylenically unsaturated monomers and their salts;
(E7) les monomères hydrosolubles ayant des groupes N-vinyle ;(E7) water-soluble monomers having N-vinyl groups;
(E8) les composés hydrosolubles de formule (IX) :(E8) the water-soluble compounds of formula (IX):
-
et RJ , identiques ou différents, représentent chacun indépendamment H, alkyle en cl-5 <3ui comporte - éventuellement un ou plusieurs groupes- and R J , identical or different, each independently represent H, C 1-5 alkyl <3 u i has - optionally one or more groups
OH ou (alcoxy en
;OH or (alkoxy in ;
(E9) l' acrylonitrile ;(E9) acrylonitrile;
(E10) l'allyl alcool ;(E10) allyl alcohol;
(Eli) la vinylpyridine ; (E12) la N- (méth) acryloyltris (hydroxyméthyl)méthyl- amine ;(Eli) vinylpyridine; (E12) N- (meth) acryloyltris (hydroxymethyl) methylamine;
(E13) le 2-sulfoéthyl (méth) acrylate ; et(E13) 2-sulfoethyl (meth) acrylate; and
(E14) le 2- (acétoacétoxy) éthyl (méth) acrylate ;(E14) 2- (acetoacetoxy) ethyl (meth) acrylate;
(F) de 0 à 50 parties en moles d'au moins un monomère hydrophobe ;(F) from 0 to 50 parts by moles of at least one hydrophobic monomer;
(II) l'hydroxypropylcellulose (LSCT = 44°C) et l' hydroxypropylcellulose méthylée, dont la modification hydrophobe par méthylation de l'hydroxypropylcellulose permet de réduire la LCST dans la plage de 19-35 °C (sa préparation est décrite dans le brevet américain US-A-5 770 528) ;(II) hydroxypropylcellulose (LSCT = 44 ° C) and methylated hydroxypropylcellulose, the hydrophobic modification of which by methylation of hydroxypropylcellulose makes it possible to reduce the LCST in the range of 19-35 ° C (its preparation is described in US Patent US-A-5,770,528);
(III) le polyvinyl méthyl éther ayant une LCST de 35 °C(III) polyvinyl methyl ether having an LCST of 35 ° C
(WO 98/29157) ;(WO 98/29157);
(IV) les poly (N-substitué (méth) acrylamides) , tels que le poly (N-isopropyl acrylamide) (NIPAM) ayant une LCST de 35 °C, dont la préparation est largement décrite dans la littérature (Colloids Surf 20, 247-257, 1986 et WO 97/24150) , le poly (N-propylacrylamide) et le poly (N- ethoxypropylacylami.de) ; et les copolymères de N-(IV) poly (N-substituted (meth) acrylamides), such as poly (N-isopropyl acrylamide) (NIPAM) having an LCST of 35 ° C., the preparation of which is widely described in the literature (Colloids Surf 20, 247-257, 1986 and WO 97/24150), poly (N-propylacrylamide) and poly (N-ethoxypropylacylami.de); and the copolymers of N-
(méth) acrylamide, tels que les copolymères NIPAM /(meth) acrylamide, such as NIPAM /
ADAMQUATS et les particules coeur/écorce polystyrène/polyNIPAM, polystyrène/copo (NIPAM/ méthacrylate d' aminoéthyle) dont la préparation est
décrite dans la littérature (Colloids and Polymer Science 276, 3, 219-231, 1998) ;ADAMQUATS and the core / shell polystyrene / polyNIPAM, polystyrene / copo (NIPAM / aminoethyl methacrylate) particles, the preparation of which is described in the literature (Colloids and Polymer Science 276, 3, 219-231, 1998);
(V) les homopolymères des composés de formule (IX) :(V) homopolymers of the compounds of formula (IX):
- R34 représente H ou CHo ;- R 34 represents H or CHo;
- A° représente -0- ou -NH- ;- A ° represents -0- or -NH-;
B3 représente -CH2CH -, CH2CH2CH2- ouB 3 represents -CH 2 CH -, CH 2 CH 2 CH 2 - or
-CH CHOHCHo-; et - R°° et R représentent chacun indépendamment-CH CHOHCHo-; and - R °° and R each independently represent
-CH3 ou -CH2-CH3 ; on peut en particulier citer le poly (méthacrylate de di éthylaminoéthyle (poly-MADAME) de LCST = 0°C ;-CH 3 or -CH 2 -CH 3 ; mention may in particular be made of poly (ethylaminoethyl methacrylate (poly-MADAME) of LCST = 0 ° C .;
(VI) les polymères obtenus par modification hydrophile des polymères hydrophobes par des motifs polyoxyéthylénés tels que des motifs de polyéthylèneglycol (PEG) ; en particulier, on peut citer les - polyamide-PEG, polyester-PEG et polyéthylène-PEG.(VI) the polymers obtained by hydrophilic modification of the hydrophobic polymers by polyoxyethylenated units such as polyethylene glycol (PEG) units; in particular, mention may be made of - polyamide-PEG, polyester-PEG and polyethylene-PEG.
Le ou les monomères (A) de formule (I) préférés sont notamment choisis parmi les composés de formule (la) :The preferred monomer (s) of formula (I) are chosen in particular from the compounds of formula (la):
CH2 = [CH2-CH2-0]n-R3 (la)
dans laquelle R 1 , R " et n sont tels que définis ci-dessus.CH 2 = [CH 2 -CH 2 -0] n -R 3 (la) in which R 1, R " and n are as defined above.
Le ou les. monomères (A) de formule (II) préférés sont notamment choisis parmi les composés de formule (Ha) ou (Ilb) : R4 R5 The. preferred monomers (A) of formula (II) are especially chosen from the compounds of formula (Ha) or (Ilb): R 4 R 5
C = CI-0-[R Çbs-0] -R i' (Ha)C = CI-0- [R Ç b s-0] -R i '(Ha)
//
H
R4 R5 H R 4 R 5
C = CI-CH2-0-[R (b,-0]o-R i (Hb) HC = CI-CH 2 -0- [R ( b , -0] o -R i (Hb) H
dans lesquelles R4 à R' et o sont tels que définis ci- dessus .in which R 4 to R 'and o are as defined above.
Le ou les monomères (B) sont notamment choisis parmi l'acide methacrylique et l'acide acrylique, l'acide methacrylique étant préféré.The monomer (s) (B) are in particular chosen from methacrylic acid and acrylic acid, methacrylic acid being preferred.
Le ou les monomères (C) de formule (III) préférés sont notamment choisis parmi les composés de formule (Illa) ou (Illb) :The preferred monomer (s) of formula (III) are chosen in particular from the compounds of formula (Illa) or (Illb):
CH2 g-R11 (Illa)
CH 2 gR 11 (Illa)
CH 2 = ]p-[CH2-CH2-0]q-R 1J-1JL (Illb)
CH 2 =] p - [CH 2 -CH 2 -0] q -R 1 J -1 JL (Illb)
dans lesquelles R8, R , p et q sont tels que définis ci- dessus .in which R 8 , R, p and q are as defined above.
Le ou les monomères (D) de formule (V) et (VI)The monomer (s) of formula (V) and (VI)
1 o 99 sont par exemple ceux dans lesquels R o et R^ représentent -CH2-CH2-.1 o 99 are for example those in which R o and R ^ represent -CH 2 -CH 2 -.
Le ou les composés (El) de formule (VII) sont choisis notamment parmi les halogenures (tels que les chlorures) de (méth) acryloxyéthyltri éthylammonium. En particulier, on peut citer le chlorure d' acryloxyéthyltriméthylammonium.The compound (s) (E1) of formula (VII) are chosen in particular from the halides (such as chlorides) of (meth) acryloxyethyltri ethylammonium. In particular, mention may be made of acryloxyethyltrimethylammonium chloride.
Le ou les composés (E2) de formule (VIII) sont notamment choisis parmi l' acrylate et le methacrylate de diméthylaminoéthyle .The compound (s) (E2) of formula (VIII) are in particular chosen from acrylate and dimethylaminoethyl methacrylate.
Le ou les composés (E3) sont par exemple l'acide 2-acrylamido-2-méthyl-propane sulfonique et ses sels.The compound (s) (E3) are for example 2-acrylamido-2-methyl-propane sulfonic acid and its salts.
Le ou les composés (E4) sont choisis par exemple parmi les (méth) acryloxyalkylsilanes .
Le ou les monomères (E6) sont choisis notamment parmi l'acide allylphosphonique et ses sels.The compound (s) (E4) are chosen, for example, from (meth) acryloxyalkylsilanes. The monomer (s) (E6) are chosen in particular from allylphosphonic acid and its salts.
Le ou les composés (E7) sont choisis notamment parmi le N-vinylacétamide, la N-vinylpyrrolidone, le N- vinylimidazole et le N-vinylcaprolactame.The compound (s) (E7) are chosen in particular from N-vinylacetamide, N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam.
Le ou les composés (E8) sont notamment choisis parmi l' acrylamide, la méthacrylamide, le N-isopropyl acrylamide, le N-éthoxypropylacrylamide, le N,N-diméthyl- acrylamide, et le N- (2-hydroxypropyl) (méth) acrylamide. Le ou les monomères hydrophobes (F) sont notamment choisis parmi :The compound (s) (E8) are in particular chosen from acrylamide, methacrylamide, N-isopropyl acrylamide, N-ethoxypropylacrylamide, N, N-dimethylacrylamide, and N- (2-hydroxypropyl) (meth) acrylamide. The hydrophobic monomer (s) (F) are chosen in particular from:
(FI) les monomères de formule (X) :(FI) the monomers of formula (X):
CH2
CH 2
dans laquelle : - R34 représente H ou -CH3 ;in which: - R 34 represents H or -CH3;
- v vaut 0 ou 1 ;- v is 0 or 1;
- R35 représente un reste alkylène en C-j_-Cg ;- R 35 represents a C 1 -C 4 alkylene residue;
- w vaut 0 ou est un entier compris entre 1 et 10 ; et - R36 représente un reste alkyle en C-]_-C32 ou cycloalkyle, avec la condition que, lorsque w vaut 0, R36 est un reste alkyle en C^- ^ ou cycloalkyle ;- w is 0 or is an integer between 1 and 10; and - R 36 represents a C- ] _-C3 2 alkyl or cycloalkyl residue, with the condition that, when w is 0, R 36 is a C ^ - ^ alkyl or cycloalkyl residue;
(F2) les monomères de formule (X) :(F2) the monomers of formula (X):
CH2 = CH-C-[0-CH2-C]a-[0-R37]b-0-R38 (XI)CH 2 = CH-C- [0-CH 2 -C] a - [0-R 37 ] b -0-R 38 (XI)
O OO O
dans laquelle :in which :
- a vaut 0 ou 1 ;- a is 0 or 1;
- R37 représente un reste alkylène en C-j_-Cg ou un reste alkylène en C-^-Cg halogène ;
- b vaut 0 ou est un entier compris entre 1 et 10 ;- R 37 represents a C 1 -C alkylene residue or a C 1 -C 4 alkylene residue halogen; - b is 0 or is an integer between 1 and 10;
- R représente un reste alkyle en C-L~C Q, cycloalkyle, alkyle halogène ou cycloalkyle halogène, avec la condition que, lorsque b vaut 0, R38 est un reste alkyle halogène en ci~Cχ ou cycloalkyle halogène ;- R represents a C1 ~ CQ alkyl residue, cycloalkyl, halogenated alkyl or halogenated cycloalkyl, with the condition that, when b is 0, R 38 is a halogenated C1 to C i alkyl residue or halogenated cycloalkyl;
(F3) les monomères hydrophobes vinyliques de formule (XII) :(F3) vinyl hydrophobic monomers of formula (XII):
CH2 = CH-R39 dans laquelle R39 est un groupement alkylcarboxylate ou alkyl éther contenant 1 à 18 atomes de carbone, un groupement aryle ou aralkyle ou un groupement cycloalkyle ;CH 2 = CH-R 39 in which R 39 is an alkylcarboxylate or alkyl ether group containing 1 to 18 carbon atoms, an aryl or aralkyl group or a cycloalkyl group;
(F4) les monomères de formule (XIII) :(F4) the monomers of formula (XIII):
(XIII)
(XIII)
dans laquelle :in which :
— l'un parmi R40 et R41 représente un atome d'hydrogène et l'autre représente un atome d'hydrogène ou un radical alkyle contenant 1 à 4 atomes de carbone ; — Y représente un enchaînement hydrocarboné bivalent lié à 0 par un atome de carbone et pouvant comporter un ou plusieurs hétéroatomes choisis parmi oxygène, soufre et azote ; et- one of R 40 and R 41 represents a hydrogen atom and the other represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms; - Y represents a bivalent hydrocarbon chain linked to 0 by a carbon atom and which may include one or more heteroatoms chosen from oxygen, sulfur and nitrogen; and
— R£ représente un radical perfluoré à chaîne droite ou ramifiée, contenant 2 à 20 atomes de carbone, de préférence 4 à 16 atomes de carbone ;- R £ represents a perfluorinated radical with a straight or branched chain, containing 2 to 20 carbon atoms, preferably 4 to 16 carbon atoms;
(F5) les monomères choisis parmi les chlorure et fluorure de vinyle et les chlorure et fluorure de vinylidène ;
(F6) les monomères hydrophobes de formule (XIV) :(F5) the monomers chosen from vinyl chloride and fluoride and vinylidene chloride and fluoride; (F6) the hydrophobic monomers of formula (XIV):
R42 R 42
CH ≈ C-C-0-[R43-OJV-R44 (XIV) IICH ≈ CC-0- [R 43 -O J VR 44 (XIV) II
00
dans laquelle :in which :
- R42 représente H ou -CH3 ;- R 42 represents H or -CH3;
- R43 représente un reste alkylène en C3-C4 ; - c est un nombre entier compris entre 1 et 70 ; et- R 43 represents a C3-C4 alkylene residue; - c is an integer between 1 and 70; and
- R44 représente H ou -CH3 ;- R 44 represents H or -CH3;
(F7) les monomères hydrophobes de formule (XV) :(F7) the hydrophobic monomers of formula (XV):
[R47-0] -R48 (XV)
[R 47 -0] -R 48 (XV)
dans laquelle : - R ^ et R représentent chacun indépendamment hydrogène ou alkyle en C2-C4 ;in which: - R ^ and R each independently represent hydrogen or C 2 -C 4 alkyl;
- Y est une liaison simple ou un reste alkylène en C^-C^ ;- Y is a single bond or a C 1 -C 4 alkylene residue;
- R47 représente un reste alkylène en C3-C4 ; - d est un nombre entier compris entre 1 et 70 ; et- R 47 represents a C3-C4 alkylene residue; - d is an integer between 1 and 70; and
- R48 représente H ou -CH3 ;- R 48 represents H or -CH3;
(F8) les fluorostyrènes ;(F8) fluorostyrenes;
(F9) les composés de formule (XVI) :(F9) the compounds of formula (XVI):
- R49 représente H ou -CH3 ;- R 49 represents H or -CH3;
- R50 et R51, identiques ou différents, représentent chacun indépendamment alkyle en Cg- C24 ou cycloalkyle ; et- R 50 and R 51 , identical or different, each independently represent Cg-C 2 4 alkyl or cycloalkyl; and
(F10) les composés n-alkyltriéthoxysilanes et les n-alkyl- triméthoxysilanes ayant des groupes alkyle en Cg-C-]_g.(F10) The compounds n-alkyltriethoxysilanes and n-alkyl trimethoxysilanes having alkyl Cg-C] _g.
Les composés de formule (XIV) sont choisis par exemple parmi ceux comportant un R43 qui est un reste CHThe compounds of formula (XIV) are chosen, for example, from those comprising an R 43 which is a CH residue
II
-CH2-CH- ou -CH2-CH2-CH2-CH2 .-CH 2 -CH- or -CH 2 -CH 2 -CH 2 -CH 2 .
Les composés de formule (XV) sont choisis par CH-, exemple parmi ceux ayant un
qui est un reste -CH2-C I'H- ou cThe compounds of formula (XV) are chosen by CH-, example from those having a which is a residue -CH 2 -C I'H- or c
-CH2-CH2-CH2-CH2 et un YJ qui est une simple liaison ou -CH2- . Les composés de formule (XVI) sont choisis par exemple parmi le N- (tert. -butyl) (méth) acrylamide, le N- décyl (méth) acrylamide, le N-dodécyl (méth) acrylamide et le N- (n-octadécyl) (méth) acrylamide.-CH 2 -CH 2 -CH 2 -CH 2 and a Y J which is a single bond or -CH 2 -. The compounds of formula (XVI) are chosen for example from N- (tert. -Butyl) (meth) acrylamide, N- decyl (meth) acrylamide, N-dodecyl (meth) acrylamide and N- (n- octadecyl) (meth) acrylamide.
Le composé (F10) est notamment le N-octadécyl- triéthoxysilane.The compound (F10) is in particular N-octadecyl-triethoxysilane.
Par ailleurs, le copolymère hydrosoluble thermosensible (I) selon l'invention peut avoir été obtenu à partir d'une composition de monomères telle que définie ci-dessus à laquelle a été incorporé au moins un agent de transfert de chaîne, choisi notamment parmi le mercapto éthanol, l' isopropanol, les alkylmercaptans, tels que le méthyl mercaptan, l'éthyl mercaptan, etc., le tétrachlorure de carbone et le triphénylméthane, le ou les agents de transfert ayant été utilisés à raison notamment de 0,05 à 8% en poids par rapport au poids total des monomères.Furthermore, the water-soluble thermosensitive copolymer (I) according to the invention may have been obtained from a composition of monomers as defined above in which at least one chain transfer agent has been incorporated, chosen in particular from mercapto ethanol, isopropanol, alkylmercaptans, such as methyl mercaptan, ethyl mercaptan, etc., carbon tetrachloride and triphenylmethane, the transfer agent or agents having been used in an amount in particular from 0.05 to 8 % by weight relative to the total weight of the monomers.
La LCST du copolymère hydrosoluble thermosensible (I) selon l'invention peut être comprise entre 6°C et 100°C,
de préférence entre 14 °C et 75 °C. Comme illustré par les exemples, l'homme du métier pourra sans difficulté régler laThe LCST of the water-soluble thermosensitive copolymer (I) according to the invention can be between 6 ° C and 100 ° C, preferably between 14 ° C and 75 ° C. As illustrated by the examples, a person skilled in the art can easily adjust the
LCST des copolymères de l'invention. En particulier, il ressort des exemples ci-après que : - les LCST des copolymères (I) de l'invention augmentent avec le nombre moyen de motifs oxyde d' éthylène du monomère polyéthoxylé utilisé ;LCST of the copolymers of the invention. In particular, it emerges from the examples below that: the LCSTs of the copolymers (I) of the invention increase with the average number of ethylene oxide units of the polyethoxylated monomer used;
- les LCST des copolymères (I) de l'invention augmentent si l'on supprime l'agent de transfert ; - les LCST des copolymères (I) selon l'invention varient entre 6 et 75 °C en jouant sur les paramètres du nombre de motifs oxyde d' éthylène, de la présence de l'agent de transfert, du rapport des monomères (A) et (B) , et de la présence de motifs fonctionnels ; - il est possible d'incorporer des motifs fonctionnels dans les copolymères de l'invention tout en préservant leur caractère thermosensible ;the LCSTs of the copolymers (I) of the invention increase if the transfer agent is removed; - the LCSTs of the copolymers (I) according to the invention vary between 6 and 75 ° C by varying the parameters of the number of ethylene oxide units, the presence of the transfer agent, the ratio of the monomers (A) and (B), and the presence of functional patterns; - It is possible to incorporate functional units into the copolymers of the invention while preserving their heat-sensitive character;
- la fonctionnalisation des copolymères (I) selon l'invention par des motifs cationiques, des motifs hydrophobes à base de chaîne alkyle grasse, des motifs acide sulfonique, des motifs acide phosphaté, conduit à l'augmentation de la LCST ; et- The functionalization of the copolymers (I) according to the invention by cationic units, hydrophobic units based on fatty alkyl chain, sulphonic acid units, phosphate acid units, leads to the increase in LCST; and
- en plus de l'apport de propriétés spécifiques pour l'application finale, la fonctionnalisation peut ainsi également contribuer à l'ajustement de la LCST des copolymères .- in addition to providing specific properties for the final application, functionalization can also contribute to the adjustment of the LCST of the copolymers.
Pour préparer un copolymère (I) tel que défini ci- dessus, on conduit la copolymerisation radicalaire en milieu aqueux ou organique (alcools ou cétones par exemple) des monomères hydrosolubles tels que définis ci-dessus. On effectue notamment la polymérisation avec une concentration totale des monomères comprise en 5 et 75% en poids, en particulier entre 15 et 50% en poids.To prepare a copolymer (I) as defined above, the radical copolymerization is carried out in an aqueous or organic medium (alcohols or ketones for example) of the water-soluble monomers as defined above. The polymerization is carried out in particular with a total concentration of the monomers of between 5 and 75% by weight, in particular between 15 and 50% by weight.
On effectue cette copolymerisation en présence d'au moins un amorceur générateur de radicaux libres, choisi notamment parmi les persulfates, tels que les persulfates d'ammonium et de potassium, les peroxydes et les composés diazoïques, tels que le chlorhydrate de 2, 2 ' -azobis (2-
aminopropane) , le ou les amorceurs générateurs de radicaux libres étant utilisés à raison notamment de 0,1 à 5% en poids, en particulier de 0,5 à 3% en poids par rapport au poids total des monomères engagés. On peut également amorcer la copolymerisation par irradiation, par exemple en présence de rayonnements UV et de photoinitiateurs tels que la benzophénone, la méthyl-2-anthraquinone ou la chloro-2- thioxanthone .This copolymerization is carried out in the presence of at least one initiator generating free radicals, chosen in particular from persulfates, such as ammonium and potassium persulfates, peroxides and diazo compounds, such as 2, 2 'hydrochloride -azobis (2- aminopropane), the initiator or initiators generating free radicals being used in a proportion in particular of 0.1 to 5% by weight, in particular of 0.5 to 3% by weight relative to the total weight of the monomers used. The copolymerization can also be initiated by irradiation, for example in the presence of UV radiation and photoinitiators such as benzophenone, methyl-2-anthraquinone or chloro-2-thioxanthone.
La longueur des chaînes polymériques peut, si on le désire, être réglée à l'aide d'agents de transfert de chaînes, tels que ceux indiqués ci-dessus, utilisés dans les proportions telle qu'indiquées ci-dessus.The length of the polymer chains can, if desired, be adjusted using chain transfer agents, such as those indicated above, used in the proportions as indicated above.
La température de réaction peut varier dans de larges limites c'est-à-dire de -40 °C à 200 °C, en opérant de façon préférentielle entre 50 et 95 °C.The reaction temperature can vary within wide limits, that is to say from -40 ° C. to 200 ° C., operating preferentially between 50 and 95 ° C.
Comme indiqué ci-dessus, on peut ajuster la LSCT du copolymère visé en fonction de la composition des monomères et/ou de la quantité de l'agent de transfert de chaîne mis en oeuvre. La présente description indique à l'homme du métier les éléments à partir desquels il pourra sans difficulté aucune réaliser un tel ajustement.As indicated above, the LSCT of the targeted copolymer can be adjusted as a function of the composition of the monomers and / or of the amount of chain transfer agent used. The present description indicates to those skilled in the art the elements from which he can easily make any such adjustment.
La Société déposante a montré que les copolymères (I) décrits précédemment présentent des propriétés thermosensibles avec des LCST ajustables en fonction de la nature et de la composition des monomères. Elle a également montré que les polymères thermosensibles s'adsorbent efficacement sur des substrats si ces substrats sont traités avec des polymères à une température supérieure à la LCST. Enfin, les revêtements formés sur les substrats peuvent être facilement éliminés ou lessivés par traitement en milieu basique ou par traitement en dessous de la LCST quel que soit le pH. En ce qui concerne les applications liées aux revêtements temporaires, les compositions de polymères thermosensibles proposés permettent en effet outre une bonne adsorption sur les substrats en milieu aqueux, une désorption efficace en jouant sur la sensibilité de ces polymères tant avec le pH qu'avec la température.
Les Exemples suivants illustrent la présente invention sans toutefois en limiter la portée. Dans ces Exemples, les parties et les pourcentages sont exprimés en poids sauf indication contraire, et les abréviations suivantes ont été utilisées :The Applicant Company has shown that the copolymers (I) described above have heat-sensitive properties with LCSTs adjustable according to the nature and the composition of the monomers. It has also shown that thermosensitive polymers adsorb effectively on substrates if these substrates are treated with polymers at a temperature higher than the LCST. Finally, the coatings formed on the substrates can be easily removed or leached by treatment in basic medium or by treatment below the LCST whatever the pH. With regard to the applications linked to temporary coatings, the thermosensitive polymer compositions proposed indeed allow, in addition to good adsorption on the substrates in aqueous medium, an effective desorption by playing on the sensitivity of these polymers both with the pH and with the temperature. The following Examples illustrate the present invention without, however, limiting its scope. In these Examples, the parts and percentages are expressed by weight unless otherwise indicated, and the following abbreviations have been used:
AMA acide methacryliqueAMA methacrylic acid
MAPEG 6 monomère de formuleMAPEG 6 monomer of formula
CHoCHo
II
CH2 = C-C-0-[CH2-CH2-0]g-HCH 2 = CC-0- [CH 2 -CH 2 -0] gH
OO
MAPEG6 PPG3 : monomère de formule : CHo CH,MAPEG6 PPG3: monomer of formula: CHo CH,
CH2 = C-C-0-[CH2-CH2-0] g-[CH2-CH-0]3-HCH 2 = CC-0- [CH 2 -CH 2 -0] g- [CH 2 -CH-0] 3 -H
O MAPEG 8 : monomère de formule : CHoO MAPEG 8: monomer of formula: CHo
II
CH2 = C-C-0 -[CH2-CH2-0]8-CH3 CH 2 = CC-0 - [CH 2 -CH 2 -0] 8 -CH 3
OO
MAPEG 12 : monomère de formule : CHoMAPEG 12: monomer of formula: CHo
II
CH2 = C-C-0 -[CH2-CH2-0]12 5-CH3CH 2 = CC-0 - [CH 2 -CH 2 -0] 12 5-CH3
00
MAPEG 22 : monomère de formule : CHoMAPEG 22: monomer of formula: CHo
II
CH2 = C-C-0 -[CH2-CH2-0]22 7-CH3 O
MAPEG 45 : monomère de formuleCH 2 = CC-0 - [CH 2 -CH 2 -0] 22 7-CH3 O MAPEG 45: monomer of formula
CH:CH:
CH2 = C-C-0 -[CH2-CH2-0]45-CH3 OCH 2 = CC-0 - [CH 2 -CH 2 -0] 45 -CH 3 O
ADAMQUAT MC : chlorure d' acryloxyéthyltriméthylammonium SIPOMER BEM :ADAMQUAT MC: acryloxyethyltrimethylammonium chloride SIPOMER BEM:
CHoCHo
II
CH2 - C_ » ~0 _ [ CH2~CH2"0 ] 25~C24H25 O CH 2 - C_ " ~ 0 _ [CH 2 ~ CH 2 " 0] 25 ~ C 24 H 25 O
AMPS :AMPS:
EMPICRYL monomère acide phosphaté de la f ormule suivante :EMPICRYL phosphate acid monomer of the following formula:
CH: OCH: O
////
CH- OCH- O
\\
O- CH2-CH2-0 P - [OH] v u constitué de :O- CH 2 -CH 2 -0 P - [OH] seen consisting of:
— 60% de 2-propénoique acide, 2-méthyl-, 2-hydroxy- éthyl ester phosphate (u = 1 ; v = 2) ; et- 60% of 2-propenoic acid, 2-methyl-, 2-hydroxy-ethyl phosphate ester (u = 1; v = 2); and
— 40% de bis (2-méthacryloyloxyéthyl) phosphate (u = 2, v = 1)- 40% bis (2-methacryloyloxyethyl) phosphate (u = 2, v = 1)
MAM : methacrylate de méthyle MABu : methacrylate de butyle MALAU : methacrylate de lauryle n OE : nombre moyen d'unités d'oxyde d' éthylène.
PMMA : poly (methacrylate de méthyle)MAM: methyl methacrylate MABu: butyl methacrylate MALAU: lauryl methacrylate n OE: average number of ethylene oxide units. PMMA: poly (methyl methacrylate)
Détermination de la LCST :LCST determination:
La LCST est la température à laquelle le produit passe d'une dispersion opaque (polymère insoluble) à une solution limpide (polymère soluble) .LCST is the temperature at which the product changes from an opaque dispersion (insoluble polymer) to a clear solution (soluble polymer).
Si l'on indique que le polymère a une LCST de T°C, ceci signifie que le produit obtenu est une solution aqueuse de polymère hydrosoluble si la température est inférieure à T°C et qu'en revanche, au-dessus de T°C, le polymère est insoluble dans l'eau et le produit se présente sous la forme de dispersions de particules de polymère insoluble dans 1' eau.If it is indicated that the polymer has an LCST of T ° C, this means that the product obtained is an aqueous solution of water-soluble polymer if the temperature is below T ° C and on the other hand, above T ° C, the polymer is insoluble in water and the product is in the form of dispersions of particles of polymer insoluble in water.
Dans tous les Exemples, la LCST est déterminée visuellement au cours du refroidissement du produit en fin de synthèse.In all the Examples, the LCST is determined visually during the cooling of the product at the end of the synthesis.
EXEMPLE 1 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12 / AMAEXAMPLE 1 SYNTHESIS OF A MAPEG 12 / AMA COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 528 parties d'eau, et on porte le réacteur à la température de 80 "C sous balayage d'azote. Quand la température du milieu réactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :528 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the medium the reaction is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(2) coulée en trois heures d'un mélange monomères/agent de transfert comprenant :(2) pouring in three hours of a monomer / transfer agent mixture comprising:
66,9 parties d'AMA ; 174,9 parties de MAPEG 12 ; et66.9 parts of AMA; 174.9 parts of MAPEG 12; and
- 3,264 parties de mercapto éthanol (agent de transfert) ;- 3,264 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 48 parties d'eau ; et
— 5,9 parties de persulfate d'ammonium.- 48 parts of water; and - 5.9 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 35 °C.This polymer has an LCST of 35 ° C.
EXEMPLE 2 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12 / AMAEXAMPLE 2 SYNTHESIS OF A MAPEG 12 / AMA COPOLYMER
(modification du rapport AMA/MAPEG 12 par rapport à l' Exemple 1) .(modification of the AMA / MAPEG 12 ratio compared to Example 1).
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 374 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80°C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :374 parts of water are introduced under stirring (150 revolutions / minute; stirring with an anchor) into a 1 liter reactor, and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant :(1) pouring in three hours of a monomer / transfer agent mixture comprising:
67,9 parties d'AMA ; 153,6 parties de MAPEG 12 ; et67.9 parts of AMA; 153.6 parts of MAPEG 12; and
2,992 parties de mercapto éthanol (agent de transfert) ;2.992 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 44 parties d'eau ; et- 44 parts of water; and
— 5,41 parties de persulfate d'ammonium.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :- 5.41 parts of ammonium persulfate. After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 40 °C. On peut ainsi noter qu'une augmentation de taux massique d'AMA de 27,9 à 30,9 a pour effet d'augmenter la LCST du copolymère de 35 °C à 40°C.This polymer has an LCST of 40 ° C. It can thus be noted that an increase in mass content of AMA from 27.9 to 30.9 has the effect of increasing the LCST of the copolymer from 35 ° C to 40 ° C.
EXEMPLE 3 SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12 / AMAEXAMPLE 3 SYNTHESIS OF A MAPEG 12 / AMA COPOLYMER
On reproduit l'Exemple 1, excepté que l'on n'incorpore pas d'agent de transfert. On obtient une solution aqueuse de polymère hydrosoluble de composition :Example 1 is reproduced, except that no transfer agent is incorporated. An aqueous solution of water-soluble polymer of composition is obtained:
EXEMPLE 4: SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8/ MAPEG 12/ AMAEXAMPLE 4 SYNTHESIS OF A MAPEG 8 / MAPEG 12 / AMA COPOLYMER
Un mélange de MAPEG 8 et MAPEG 12 a été utilisé afin de préparer un copolymère ayant un nOE de 8,5 (intermédiaire entre 8 et 12,5).
Dans un réacteur de 3 litres, on introduit sous agitation (150 tours/minute ; agitation par ancre) 1485 parties d'eau, et on porte le réacteur à la température de 80°C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :A mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having a nOE of 8.5 (intermediate between 8 and 12.5). Into a 3-liter reactor, 1485 parts of water are introduced with stirring (150 revolutions / minute; stirring by anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant : - 380,4 parties d'AMA ;(1) pouring in three hours of a monomer / transfer agent mixture comprising: - 380.4 parts of AMA;
610 parties de MAPEG 8 ;610 parts of MAPEG 8;
116 parties de MAPEG 12 ; et116 parts of MAPEG 12; and
- 14,96 parties de mercapto éthanol (agent de transfert) ;- 14.96 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 187 parties d'eau ; et- 187 parts of water; and
- 27 parties de persulfate d'ammonium.- 27 parts of ammonium persulfate.
Au bout des trois heures de coulée, on ajoute 6,77 parties de persulfate d'ammonium dissous dans 44 parties d'eau et on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, 6.77 parts of ammonium persulfate dissolved in 44 parts of water are added and the reaction is allowed to continue for a further two hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 24 °C.
EXEMPLE 5: SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8/ MAPEG 12/ AMAThis polymer has an LCST of 24 ° C. EXAMPLE 5 SYNTHESIS OF A MAPEG 8 / MAPEG 12 / AMA COPOLYMER
On reproduit l'Exemple 4, excepté que l'on n'incorpore pas d'agent de transfert.Example 4 is repeated, except that no transfer agent is incorporated.
On obtient une solution aqueuse de polymère hydrosoluble de composition :An aqueous solution of water-soluble polymer of composition is obtained:
Ce polymère a une LCST de 24 °C.This polymer has an LCST of 24 ° C.
EXEMPLE 6: SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8/ MAPEG 12/ AMAEXAMPLE 6 SYNTHESIS OF A MAPEG 8 / MAPEG 12 / AMA COPOLYMER
Un mélange de MAPEG 8 et MAPEG 12 a été utilisé afin de préparer un copolymère ayant un nOE de 9 (intermédiaire entre 8 et 12) .A mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 9 (intermediate between 8 and 12).
Dans un réacteur de 3 litres, on introduit sous agitation (150 tours/minute ; agitation par ancre) 1700 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :1700 parts of water are introduced into a 3 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant :(1) pouring in three hours of a monomer / transfer agent mixture comprising:
336,8 parties d'AMA ; 480 parties de MAPEG 8 ; 188 parties de MAPEG 12 ; et - 13,6 parties de mercapto éthanol (agent de transfert) ;336.8 parts of AMA; 480 parts of MAPEG 8; 188 parts of MAPEG 12; and - 13.6 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d'amorcePur contenant : - 170 parties d'eau ; et
— 24,6 parties de persulfate d'ammonium.(2) pouring in three hours of a primer solution Pur containing: - 170 parts of water; and - 24.6 parts of ammonium persulfate.
Au bout des trois heures de coulée, on ajoute 6,15 parties de persulfate d'ammonium dissous dans 40 parties d' eau et on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, 6.15 parts of ammonium persulfate dissolved in 40 parts of water are added and the reaction is allowed to continue for another two hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST' de 24 °C.This polymer has an LCST ' of 24 ° C.
EXEMPLE 7: SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8/ MAPEG 12/ AMAEXAMPLE 7 SYNTHESIS OF A MAPEG 8 / MAPEG 12 / AMA COPOLYMER
On reproduit l'Exemple 6, excepté que l'on n'incorpore pas d'agent de transfert. On obtient une solution aqueuse de polymère hydrosoluble de composition :Example 6 is repeated, except that no transfer agent is incorporated. An aqueous solution of water-soluble polymer of composition is obtained:
Ce polymère a une LCST de 26°C,This polymer has an LCST of 26 ° C,
EXEMPLE 8 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8/ MAPEG 12/ AMAEXAMPLE 8 SYNTHESIS OF A MAPEG 8 / MAPEG 12 / AMA COPOLYMER
Un mélange de MAPEG 8 et MAPEG 12 a été utilisé afin de préparer un copolymère ayant un nOE de 9 (intermédiaire entre 8 et 12) . Dans un réacteur de 3 litres, on introduit sous agitation (150 tours/minute ; agitation par ancre) 1800 parties d'eau, et on porte le réacteur à la température
de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80°C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :A mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 9 (intermediate between 8 and 12). In a 3 liter reactor, 1800 parts of water are introduced with stirring (150 revolutions / minute; stirring by anchor), and the reactor is brought to temperature. 80 ° C under nitrogen sweep. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, in the following manner:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant :(1) pouring in three hours of a monomer / transfer agent mixture comprising:
386,8 parties d'AMA ;386.8 parts of AMA;
- 480 parties de MAPEG 8 ; 188 parties de MAPEG 12 ; et- 480 parts of MAPEG 8; 188 parts of MAPEG 12; and
- 13, 6 parties de mercapto éthanol (agent de transfert) ;- 13.6 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 170 parties d'eau ; et- 170 parts of water; and
- 24,6 parties de persulfate d'ammonium.- 24.6 parts of ammonium persulfate.
Au bout des trois heures de coulée, on ajoute 6,15 parties de persulfate d'ammonium dissous dans 40 parties d' eau et on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20°C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, 6.15 parts of ammonium persulfate dissolved in 40 parts of water are added and the reaction is allowed to continue for another two hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Un mélange de MAPEG 8 et MAPEG 12 a été utilisé afin de préparer un copolymère ayant un nOE de 9,5 (intermédiaire entre 8 et 12,5).A mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 9.5 (intermediate between 8 and 12.5).
Dans un réacteur de 3 litres, on introduit sous agitation (150 tours/minute ; agitation par ancre) 1656 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :1656 parts of water are introduced into a 3 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant :(1) pouring in three hours of a monomer / transfer agent mixture comprising:
309,4 parties d'AMA ; - 372,1 parties de MAPEG 8 ;309.4 parts of AMA; - 372.1 parts of MAPEG 8;
269 parties de MAPEG 12 ; et269 parts of MAPEG 12; and
- 12,24 parties de mercapto éthanol (agent de transfert) ;- 12.24 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 126 parties d'eau ; et- 126 parts of water; and
- 22,14 parties de persulfate d'ammonium.- 22.14 parts of ammonium persulfate.
Au bout des trois heures de coulée, on ajoute 5,54 parties de persulfate d'ammonium dissous dans 36 parties d'eau et on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, 5.54 parts of ammonium persulfate dissolved in 36 parts of water are added and the reaction is allowed to continue for two additional hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
EXEMPLE 10 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8/ MAPEG 12/ AMAEXAMPLE 10 SYNTHESIS OF A MAPEG 8 / MAPEG 12 / AMA COPOLYMER
On reproduit l'Exemple 9, excepté que l'on n'incorpore pas d'agent de transfert. On obtient une solution aqueuse de polymère hydrosoluble de composition :Example 9 is repeated, except that no transfer agent is incorporated. An aqueous solution of water-soluble polymer of composition is obtained:
Ce polymère a une LCST de 29°C.This polymer has an LCST of 29 ° C.
EXEMPLE 11 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8/ MAPEG 12/ AMAEXAMPLE 11 SYNTHESIS OF A MAPEG 8 / MAPEG 12 / AMA COPOLYMER
Un mélange de MAPEG 8 et MAPEG 12 a été utilisé afin de préparer un copolymère ayant un nOE de 10,5 (intermédiaire entre 8 et 12,5). Dans un réacteur de 3 litres, on introduit sous agitation (150 tours/minute ; agitation par ancre) 1656 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :A mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 10.5 (intermediate between 8 and 12.5). 1656 parts of water are introduced into a 3 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant :(1) pouring in three hours of a monomer / transfer agent mixture comprising:
292,2 parties d'AMA ; - 233,6 parties de MAPEG 8 ;292.2 parts of AMA; - 233.6 parts of MAPEG 8;
423,4 parties de MAPEG 12 ; et — 12,24 parties de mercapto éthanol (agent de transfert) ;
(2) coulée en trois heures d'une solution d' amorceur contenant :423.4 parts of MAPEG 12; and - 12.24 parts of mercapto ethanol (transfer agent); (2) pouring in three hours of an initiator solution containing:
- 126 parties d'eau ; et- 126 parts of water; and
- 22,14 parties de persulfate d'ammonium.- 22.14 parts of ammonium persulfate.
Au bout des trois heures de coulée, on ajouteAfter three hours of pouring, add
5,54 parties de persulfate d'ammonium dissous dans 36 parties d'eau et on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :5.54 parts of ammonium persulfate dissolved in 36 parts of water and the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 31,5°C.This polymer has an LCST of 31.5 ° C.
EXEMPLE 12 : Synthèse d'un copolymère MAPEG 22/ AMAEXAMPLE 12 Synthesis of a MAPEG 22 / AMA copolymer
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 387 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :387 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant :(1) pouring in three hours of a monomer / transfer agent mixture comprising:
49,5 parties d'AMA ; 441 parties de MAPEG 22 ; et — 2,45 parties de mercapto éthanol (agent de transfert) ;49.5 parts of AMA; 441 parts of MAPEG 22; and - 2.45 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur comprenant :
- 36 parties d'eau ; et(2) pouring in three hours of an initiator solution comprising: - 36 parts of water; and
- 4,43 parties de persulfate d'ammonium.- 4.43 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 75°C, supérieure à 37 "C.This polymer has an LCST of 75 ° C, greater than 37 "C.
EXEMPLE 13 : Synthèse d'un copolymère MAPEG 45/ AMAEXAMPLE 13 Synthesis of a MAPEG 45 / AMA copolymer
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 387 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :387 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant :(1) pouring in three hours of a monomer / transfer agent mixture comprising:
28,4 parties d'AMA ; 483 parties de MAPEG 45 ; et - 2,45 parties de mercapto éthanol (agent de transfert) ;28.4 parts of AMA; 483 parts of MAPEG 45; and - 2.45 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 36 parties d'eau ; et- 36 parts of water; and
- 4,43 parties de persulfate d'ammonium.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :- 4.43 parts of ammonium persulfate. After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère est hydrosoluble et ne présente pas de changement de solubilité dans l'eau pour une température inférieure à 90 °C.This polymer is water-soluble and does not show any change in solubility in water for a temperature below 90 ° C.
Cet exemple montre qu' il faut une composition adaptée en monomères, notamment le nOE, pour obtenir un copolymère thermosensible.This example shows that a suitable composition of monomers, in particular nOE, is required to obtain a heat-sensitive copolymer.
EXEMPLE 14 SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12 / AMA / ADAMOUAT MCEXAMPLE 14 SUMMARY OF A MAPEG 12 / AMA / ADAMOUAT ™ COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 484 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :484 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant :(1) pouring in three hours of a monomer / transfer agent mixture comprising:
60,99 parties d'AMA ; 156,1 parties de MAPEG 12 ;60.99 parts of AMA; 156.1 parts of MAPEG 12;
5,64 parties de solution à 80% d'ADAMQUAT MC ; - 2,992 parties de mercapto éthanol (agent de transfert) ;5.64 parts of 80% ADAMQUAT ™ solution; - 2,992 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :
- 44 parties d'eau ; et(2) pouring in three hours of an initiator solution containing: - 44 parts of water; and
- 5,41 parties de persulfate d'ammonium.- 5.41 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20°C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LSCT de 53 °C.This polymer has an LSCT of 53 ° C.
L'ADAMQUAT MC a donc pour effet l'augmentation de la LCST du copolymère MAPEG12 / AMA de 35°C (cf. Exemple 1) à 53°C.ADAMQUAT ™ therefore has the effect of increasing the LCST of the MAPEG12 / AMA copolymer from 35 ° C. (cf. Example 1) to 53 ° C.
EXEMPLE 15 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8/ AMAEXAMPLE 15 SUMMARY OF A MAPEG 8 / AMA COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 528 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80°C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :528 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant : - 85,75 parties d'AMA ;(1) pouring in three hours of a monomer / transfer agent mixture comprising: - 85.75 parts of AMA;
155,8 parties de MAPEG 8 ; et - 3,264 parties de mercapto éthanol (agent de transfert) ;155.8 parts of MAPEG 8; and - 3,264 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 48 parties d'eau ; et
- 5,9 parties de persulfate d'ammonium.- 48 parts of water; and - 5.9 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LSCT de 14 °C.This polymer has an LSCT of 14 ° C.
EXEMPLE 16 SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8 / AMA / ADAMOUAT MCEXAMPLE 16 SUMMARY OF A MAPEG 8 / AMA / ADAMOUAT ™ COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 384 parties d'eau, et on porte le réacteur à la température de 80°C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :384 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange eau/monomères/agent de transfert comprenant :(1) pouring in three hours of a water / monomer / transfer agent mixture comprising:
- 100 parties d'eau ;- 100 parts of water;
77,60 parties d'AMA ; 138,07 parties de MAPEG 8 ;77.60 parts of AMA; 138.07 parts of MAPEG 8;
7,15 parties de solution à 80% d'ADAMQUAT MC ;7.15 parts of 80% ADAMQUAT ™ solution;
- 2,992 parties de mercapto éthanol (agent de transfert) ;- 2,992 parts of mercapto ethanol (transfer agent);
coulée en trois heures d'une solution d' amorceur contenant :pouring in three hours of an initiator solution containing:
- 44 parties d'eau ; et- 44 parts of water; and
- 5,41 parties de persulfate d'ammonium.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :- 5.41 parts of ammonium persulfate. After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LSCT s' établissant sur la plage de température 27-30°C.This polymer has an LSCT over the temperature range 27-30 ° C.
L' ADAMQUAT MC a donc pour effet l'augmentation de la LCST du copolymère MAPEG 8 / AMA de 14 °C à 27-30 °C.ADAMQUAT MC therefore increases the LCST of the MAPEG 8 / AMA copolymer from 14 ° C to 27-30 ° C.
EXEMPLE 17 SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8 / AMA / SIPOMER BEMEXAMPLE 17 SUMMARY OF A MAPEG 8 / AMA / SIPOMER BEM COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 484 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80°C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :484 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange monomères/agent de transfert comprenant :(1) pouring in three hours of a monomer / transfer agent mixture comprising:
77,93 parties d'AMA ; -' 140,50 parties de MAPEG 8 ;77.93 parts of AMA; - ' 140.50 parts of MAPEG 8;
5,735 parties de solution à 52% de SIPOMER BEM ; et - 2,992 parties de mercapto éthanol (agent de transfert) ;5.735 parts of 52% SIPOMER BEM solution; and - 2,992 parts of mercapto ethanol (transfer agent);
(3) coulée en trois heures d'une solution d' amorceur contenant :
- 44 parties d'eau ; et(3) pouring in three hours of an initiator solution containing: - 44 parts of water; and
— 5,41 parties de persulfate d'ammonium.- 5.41 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 18 °C s' établissant entre 18 et 20°C.This polymer has an LCST of 18 ° C being established between 18 and 20 ° C.
Le SIPOMER BEM a donc pour effet l'augmentation de la LCST du copolymère MAPEG 8/ AMA de 14 °C (cf Exemple 15) à 18-20°C.SIPOMER BEM therefore has the effect of increasing the LCST of the MAPEG 8 / AMA copolymer from 14 ° C (see Example 15) to 18-20 ° C.
EXEMPLE 18 SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8 / AMA / SIPOMER BEM / ADAMQUAT MCEXAMPLE 18 SUMMARY OF A MAPEG 8 / AMA / SIPOMER BEM / ADAMQUAT ™ COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 384 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :384 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange eau / monomères / agent de transfert comprenant : - 99,99 parties d'eau ; 76,93 parties d'AMA ; 135,8 parties de MAPEG 8 ;(1) pouring in three hours of a water / monomer / transfer agent mixture comprising: - 99.99 parts of water; 76.93 parts of AMA; 135.8 parts of MAPEG 8;
5,77 parties de solution à 52% de SIPOMER BEM ;
7 , 09 parties de solution à 80% D' ADAMQUAT5.77 parts of 52% SIPOMER BEM solution; 7, 09 parts of 80% ADAMQUAT solution
MC ; etMC; and
- 2 , 992 parties de mercapto éthanol ( agent de transfert ) ;- 2.992 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 44 parties d'eau ; et- 44 parts of water; and
- 5,41 parties de persulfate d'ammonium.- 5.41 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20°C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 18 °C s' établissant entre 26 et 28°C.This polymer has an LCST of 18 ° C being established between 26 and 28 ° C.
Le SIPOMER BEM et l' ADAMQUAT MC ont donc pour effet l'augmentation de la LCST du copolymère MAPEG 8 / AMA de 14°C (cf Exemple 15) à 26-28°C.SIPOMER BEM and ADAMQUAT MC therefore have the effect of increasing the LCST of the MAPEG 8 / AMA copolymer from 14 ° C (see Example 15) to 26-28 ° C.
EXEMPLE 19 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8 / AMA / AMPSEXAMPLE 19 SYNTHESIS OF A MAPEG 8 / AMA / AMPS COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 384 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :384 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(1) coulée en trois heures d'un mélange eau / monomères / agent de transfert comprenant :
100 parties d'eau ; 77,45 parties d'AMA ; 137,81 parties de MAPEG 8 ; • 6,12 parties d'AMPS ; et(1) pouring in three hours of a water / monomer / transfer agent mixture comprising: 100 parts of water; 77.45 parts of AMA; 137.81 parts of MAPEG 8; • 6.12 parts of AMPS; and
2,992 parties de mercapto éthanol (agent de transfert) ;2.992 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 44 parties d'eau ; et- 44 parts of water; and
- 5,41 parties de persulfate d'ammonium.- 5.41 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LSCT s' établissant sur la plage de température 27-29 "C. L'AMPS a donc pour effet l'augmentation de la LCST du copolymère AMA /MAPEG de 14 °C (cf Exemple 15) à 27-29°C.This polymer has an LSCT established over the temperature range 27-29 "C. The AMPS therefore has the effect of increasing the LCST of the AMA / MAPEG copolymer from 14 ° C. (cf. Example 15) to 27-29 ° C.
EXEMPLE 20 SYNTHÈSE D'UN COPOLYMÈRE MAPEG 8 / AMA / EMPICRYLEXAMPLE 20 SUMMARY OF A MAPEG 8 / AMA / EMPICRYL COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 384 parties d'eau, et on porte le réacteur à la température de 80°C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :
(1) coulée en trois heures d'un mélange eau / monomères / agent de transfert comprenant :384 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel: (1) pouring in three hours of a water / monomer / transfer agent mixture comprising:
- 100 parties d'eau ;- 100 parts of water;
77,00 parties d'AMA ; - 137,0 parties de MAPEG 8 ;77.00 parts of AMA; - 137.0 parts of MAPEG 8;
7,37 parties d'EMPICRYL ; et7.37 parts of EMPICRYL; and
- 2,992 parties de mercapto éthanol (agent de transfert) ;- 2,992 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 44 parties d'eau ; et- 44 parts of water; and
- 5,41 parties de persulfate d'ammonium.- 5.41 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
L'EMPICRYL a donc pour effet l'augmentation de la LCST du copolymère AMA / MAPEG 8 / AMA de 14 °C (cf Exemple 15) à 27-29°C.EMPICRYL therefore increases the LCST of the AMA / MAPEG 8 / AMA copolymer from 14 ° C (see Example 15) to 27-29 ° C.
EXEMPLE 21 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 6 / AMAEXAMPLE 21 SYNTHESIS OF A MAPEG 6 / AMA COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 532,8 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et
parallèlement les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor, 532.8 parts of water are introduced with stirring (150 rpm; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., it is introduced by continuous casting over three hours, separately and in parallel, the monomers and initiator solution as follows:
(1) coulée en trois heures d'un mélange monomères / agent de transfert comprenant : - 100,29 parties d'AMA ;(1) pouring in three hours of a monomer / transfer agent mixture comprising: - 100.29 parts of AMA;
141,12 parties de MAPEG 6 ; et141.12 parts of MAPEG 6; and
- 3,264 parties de mercapto éthanol (agent de transfert) ;- 3,264 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 43,2 parties d'eau ; et- 43.2 parts of water; and
- 5,9 parties de persulfate d'ammonium.- 5.9 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 8°C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 8 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST comprise entre 10 et 12 °C.This polymer has an LCST of between 10 and 12 ° C.
EXEMPLE 22 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 6 PPG3 / AMAEXAMPLE 22 SYNTHESIS OF A MAPEG 6 PPG3 / AMA COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 436,8 parties d'eau, et on porte le réacteur à la température de 80°C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80°C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :
(1) coulée en trois heures d'un mélange eau / monomères / agent de transfert comprenant :436.8 parts of water are introduced under stirring (150 revolutions / minute; stirring with an anchor) into a 1 liter reactor, and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, in the following manner: (1) pouring in three hours of a water / monomer / transfer agent mixture comprising:
- 96 parties d'eau ; 78,09 parties d'AMA ;- 96 parts of water; 78.09 parts of AMA;
163,55 parties de MAPEG 6 PPG3 ; et163.55 parts of MAPEG 6 PPG3; and
- 3,264 parties de mercapto éthanol (agent de transfert) ;- 3,264 parts of mercapto ethanol (transfer agent);
(2) coulée en trois heures d'une solution d' amorceur contenant :(2) pouring in three hours of an initiator solution containing:
- 43,2 parties d'eau ; et- 43.2 parts of water; and
— 5,9 parties de persulfate d'ammonium.- 5.9 parts of ammonium persulfate.
• Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 8°C et on ' récupère une solution aqueuse de polymère hydrosoluble de composition : • After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor was cooled to 8 ° C and 'recovered an aqueous solution of water-soluble polymer composition:
Ce polymère a une LCST comprise entre 6 et 8°C.This polymer has an LCST of between 6 and 8 ° C.
EXEMPLE 23 : TRAITEMENT DE TISSU DE COTON PAR LES SOLUTIONS DE COPOLYMÈRES THERMOSENSIBLES DESEXAMPLE 23 TREATMENT OF COTTON FABRIC WITH THE SOLUTIONS OF THERMOSENSITIVE COPOLYMERS OF
EXEMPLES 1 à DETERMINATION DE LAEXAMPLES 1 TO DETERMINATION OF THE
QUANTITE DE POLYMERE ADSORBE LORS DE LA MODIFICATION HYDROPHILEQUANTITY OF POLYMER ADSORBED DURING HYDROPHILIC MODIFICATION
Les copolymères thermosensibles des Exemples 1 àThe heat-sensitive copolymers of Examples 1 to
23 sont utilisés séparément pour des essais d' adsorption sur des tissus de coton calibrés de tailles identiques (6 x 8 cm) et préalablement pesés (poids = 0,428 g).23 are used separately for adsorption tests on calibrated cotton fabrics of identical sizes (6 x 8 cm) and previously weighed (weight = 0.428 g).
Le mode opératoire dont les variables sont la température de traitement du tissu et la composition du
copolymère est décrit dans le paragraphe suivant. Il s'applique à tous les copolymères des Exemples 1 à 22.The procedure, the variables of which are the temperature of treatment of the tissue and the composition of the copolymer is described in the following paragraph. It applies to all the copolymers of Examples 1 to 22.
Dans un bêcher de 2 1, on introduit sous agitation (300 tours/minute) à l'aide d'un barreau magnétique, un litre de solution aqueuse à 10% d'un copolymère thermosensible préparé précédemment dans les Exemples 1 à 23. On porte l'ensemble à une température de traitement donnée (Tad) . Après stabilisation à la température de traitement désirée (Tad) , on introduit sous agitation le morceau de tissu calibré et pesé que l'on laisse tremper sous agitation pendant 30 minutes. Le tissu traité est ensuite récupéré à l'aide d'une pince à épiler, et rapidement étuvé à 100 °C pendant 6 heures. La différence de poids entre le tissu sec traité ou modifié hydrophile et le tissu de départ non traité donne le poids de polymère adsorbé sur le tissu au cours de l'opération de trempage ou de traitement.In a 2 1 beaker, a liter of 10% aqueous solution of a heat-sensitive copolymer previously prepared in Examples 1 to 23 is introduced with stirring (300 rpm) using a magnetic bar. brings the assembly to a given processing temperature (Tad). After stabilization at the desired treatment temperature (Tad), the calibrated and weighed piece of tissue is introduced with stirring which is left to soak with stirring for 30 minutes. The treated tissue is then recovered using tweezers, and quickly steamed at 100 ° C for 6 hours. The difference in weight between the dry treated or modified hydrophilic fabric and the untreated starting fabric gives the weight of polymer adsorbed on the fabric during the soaking or treatment operation.
Les tableaux ci-dessous donnent les poids de polymère adsorbé sur le tissu traité pour les différents copolymères thermosensibles aux différentes températures de traitement (au-dessus en au-dessous des LCST correspondants) .The tables below give the weights of polymer adsorbed on the treated fabric for the different heat-sensitive copolymers at the different treatment temperatures (above and below the corresponding LCSTs).
(A) Traitement du tissu à la température de 50 °C des copolymères des Exemples 1, 2, 4 et 5 ayant différentes LCST (respectivement 24, 28, 35, 75) et préparés à partir de monomères MAPEG ayant différents nombres moyens d'oxyde d' éthylène nOE (respectivement 9, 9,5, 12,5 et 22,7)(A) Treatment of the fabric at the temperature of 50 ° C. of the copolymers of Examples 1, 2, 4 and 5 having different LCSTs (respectively 24, 28, 35, 75) and prepared from MAPEG monomers having different average numbers of ethylene oxide nOE (9, 9.5, 12.5 and 22.7, respectively)
Le Tableau 1 regroupe les masses de polymère adsorbées en fonction du nombre moyen d'oxyde d' éthylène (nOE) et de la LCST.
Tableau 1 : Masse de copolymère MAPEG/AMA adsorbée sur le tissu traité à 50 °C en fonction du nombre moyen d'oxyde d' éthylène nOE des MAPEG et de la LCSTTable 1 groups the polymer masses adsorbed as a function of the average number of ethylene oxide (nOE) and of the LCST. Table 1: Mass of MAPEG / AMA copolymer adsorbed on the treated fabric at 50 ° C. as a function of the average number of ethylene oxide nOE of the MAPEGs and of the LCST
Il ressort du Tableau 1 les commentaires suivants :Table 1 shows the following comments:
(1) On constate qu'il y a adsorption du polymère sur le tissu si la LCST du polymère est inférieure à la température de traitement du tissu (LCST = 24, 28 et 35°C) . Le polymère devenu insoluble dans l'eau au- dessus de la LCST, précipite, ce qui favorise son adsorption sur le tissu.(1) It is noted that there is adsorption of the polymer on the fabric if the LCST of the polymer is lower than the treatment temperature of the fabric (LCST = 24, 28 and 35 ° C). The polymer, which becomes insoluble in water above the LCST, precipitates, which promotes its adsorption on the fabric.
(2) Le polymère n'est pas ou faiblement adsorbé sur le tissu si la LCST (75°C) est supérieure à la température de trempage ou de traitement (50 °C) . Le polymère étant sous une forme soluble, reste préférentiellement dans l'eau au lieu de s'adsorber sur le tissu.(2) The polymer is not or only slightly adsorbed on the fabric if the LCST (75 ° C) is higher than the soaking or treatment temperature (50 ° C). The polymer being in a soluble form, preferentially remains in water instead of adsorbing on the fabric.
(3) Dans les conditions de traitement favorables à l'adsorption (Tadd > LCST), les copolymères ayant les LCST les plus faibles qui sont obtenus avec un nombre moyen d'oxyde d' éthylène (nOE) plus faible permettent une meilleure adsorption. L'adsorption diminue quand la LCST ou nOE augmente.(3) Under the treatment conditions favorable to adsorption (Tadd> LCST), the copolymers having the lowest LCSTs which are obtained with a lower average number of ethylene oxide (nOE) allow better adsorption. Adsorption decreases when LCST or nOE increases.
(B) Traitement de tissus par le copolymère MAPEG/AMA avant une LCST = 75 °C à différentes températures de traitement (nOE = 27, copolymère de l'Exemple 12)(B) Treatment of fabrics with the MAPEG / AMA copolymer before an LCST = 75 ° C. at different treatment temperatures (nOE = 27, copolymer of Example 12)
Le Tableau 2 présente les résultats obtenus.
Tableau 2 Masse de copolymère MAPEG/AMA (Copolymère de l'Exemple 12, LCST = 75°C et nOE = 22,7) adsorbé sur le tissu traité à différentes températuresTable 2 presents the results obtained. Table 2 Mass of MAPEG / AMA copolymer (Copolymer of Example 12, LCST = 75 ° C and nOE = 22.7) adsorbed on the treated fabric at different temperatures
Contrairement au traitement à 50 °C, présenté dans le Tableau 1 précédent, l'augmentation de la température de traitement du tissu au-dessus de la LCST (78°C et 92°C) permet l'adsorption du polymère précipité sur le tissu.Unlike the treatment at 50 ° C, presented in Table 1 above, the increase in the treatment temperature of the fabric above the LCST (78 ° C and 92 ° C) allows the adsorption of the precipitated polymer on the fabric .
Dans les conditions de traitement favorables à l'adsorptionIn treatment conditions favorable to adsorption
(Tad > LCST), l'adsorption est d'autant plus importante que la différence de température entre la LCST et la température de traitement est importante. Ce point est confirmé par les Tableaux 3, 4 et 5 correspondant aux copolymères des Exemples 6 et 8 ayant respectivement des LCST de 24 et 20 °C et obtenus avec des MAPEG ayant un nOE identique mais des rapports MAM/MAPEG différents (nOE = 9) .(Tad> LCST), the adsorption is all the more important as the temperature difference between the LCST and the treatment temperature is important. This point is confirmed by Tables 3, 4 and 5 corresponding to the copolymers of Examples 6 and 8 having respectively LCSTs of 24 and 20 ° C and obtained with MAPEGs having an identical nOE but different MAM / MAPEG ratios (nOE = 9 ).
Tableau 3 LCST 24°C (nOE 9, copolymère de l'Exemple 6) : Influence de la température de traitement du tissu sur la masse de polymère adsorbé par le tissuTable 3 LCST 24 ° C (nOE 9, copolymer of Example 6): Influence of the fabric treatment temperature on the mass of polymer adsorbed by the fabric
Tableau 5 LCST = 18-20 °C (nOE ≈ 8, copolymère MAPEG / MAM / SIPOMER BEM de l'Exemple 17) : Influence de la température de traitement du tissu sur la masse de polymère adsorbé par le tissuTable 5 LCST = 18-20 ° C (nOE ≈ 8, MAPEG / MAM / SIPOMER BEM copolymer of Example 17): Influence of the fabric treatment temperature on the mass of polymer adsorbed by the fabric
Les résultats obtenus avec les deux copolymères à base d' un MAPEG ayant un nombre moyen d' oxyde d' éthylène identique (nOE = 9) mais caractérisé par des LCST différentes (ici 20 et 24°C), utilisés pour un traitement comparatif à différentes températures (Tad = 12°C, 22,5°C et 35 °C) permettent de faire les commentaire suivants :The results obtained with the two copolymers based on a MAPEG having an identical average number of ethylene oxide (nOE = 9) but characterized by different LCSTs (here 20 and 24 ° C.), used for a comparative treatment with. different temperatures (Tad = 12 ° C, 22.5 ° C and 35 ° C) allow the following comments to be made:
(a) Pour une température de traitement de 22,5°C, on adsorbé le polymère à LCST égale à 20 °C, ce qui n'est pas le cas du polymère à LCST de 24 °C. Quand la température de traitement est de 12 °C, c'est-à-dire inférieure aux LCST des deux polymères, il n'y a pas ou peu d' adsorption. Ceci rejoint les conclusions précédentes selon lesquelles il est important de se situer au-dessus de la LCST du polymère pour pouvoir fixer de manière efficace le polymère sur le tissu.(a) For a treatment temperature of 22.5 ° C., the polymer with LCST equal to 20 ° C. is adsorbed, which is not the case for the polymer with LCST of 24 ° C. When the treatment temperature is 12 ° C, that is to say lower than the LCST of the two polymers, there is little or no adsorption. This ties in with the previous conclusions that it is important to be above the LCST of the polymer in order to be able to fix the polymer effectively on the fabric.
(b) Pour une température de traitement de 35°C, c'est-à- dire supérieure aux LCST des deux polymères, les deux polymères s'adsorbent sur le tissu mais la masse
adsorbée est plus importante pour le polymère ayant la(b) For a treatment temperature of 35 ° C., that is to say higher than the LCST of the two polymers, the two polymers adsorb on the fabric but the mass adsorbed is more important for the polymer having the
LCST la plus faible (2,22 g pour la LCST = 20°C comparé à 1,34 g pour la LCST = 24°C). Cette observation corrobore également celle faite précédemment, montrant une meilleure adsorption pour les copolymères à plus faibles LCST.Lowest LCST (2.22 g for LCST = 20 ° C compared to 1.34 g for LCST = 24 ° C). This observation also corroborates that previously made, showing better adsorption for the copolymers with lower LCSTs.
(c) Les observations faites en (a) et (b) montrent que le paramètre principal qui gouverne l'adsorption sur le tissu est plus la LCST du polymère que le nombre moyen d'oxyde d' éthylène utilisé pour la préparation du copolymère.(c) The observations made in (a) and (b) show that the main parameter which governs the adsorption on the fabric is more the LCST of the polymer than the average number of ethylene oxide used for the preparation of the copolymer.
EXEMPLE 24 : TESTS DE DÉSORPTION DE REVÊTEMENT DEEXAMPLE 24 TESTS OF DESORPTION OF COATING OF
POLYMÈRES THERMOSENSIBLES SUR LES TISSUSTHERMOSENSITIVE POLYMERS ON FABRICS
Les tissus secs adsorbés de copolymères thermosensibles obtenus dans les exemples précédents sont utilisés séparément pour des essais de désorption dans les solutions à 10% de ces polymères et dont le pH a été augmenté à 10. On constate que tous les copolymères thermosensibles obtenus précédemment perdent leur caractère thermosensible en pH basique c'est-à-dire qu'ils ne présentent plus de transition soluble / insoluble avec la température et sont complètement solubles dans l'eau quelle que soit la température. Ces conditions sont favorables pour la désorption du revêtement hydrophile sur le substrat comme le montrent les essais décrits ci-dessous.The dry fabrics adsorbed from heat-sensitive copolymers obtained in the previous examples are used separately for desorption tests in solutions at 10% of these polymers and whose pH has been increased to 10. It can be seen that all the heat-sensitive copolymers obtained previously lose their thermosensitive in basic pH, that is to say that they no longer have a soluble / insoluble transition with temperature and are completely soluble in water whatever the temperature. These conditions are favorable for the desorption of the hydrophilic coating on the substrate as shown by the tests described below.
Le mode opératoire dont les variables sont la température de traitement du tissu et la composition du copolymère est décrit dans le paragraphe suivant. Il s'applique à tous les tissus traités précédemment. Dans un bêcher de 2 1, on introduit sous agitationThe procedure, the variables of which are the fabric treatment temperature and the composition of the copolymer, is described in the following paragraph. It applies to all previously treated fabrics. In a 2 1 beaker, the mixture is introduced with stirring
(300 tours/minute) à l'aide d'un barreau magnétique, un litre de solution aqueuse à 10% d'un copolymère thermosensible préparé précédemment. On y ajoute quelques gouttes d'ammoniaque (NH4OH) de manière à obtenir un pH de 10. On porte l'ensemble à une température de traitement donnée (Tad) supérieure ou inférieure à la LCST du polymère.
Après stabilisation à la température de traitement désirée (Tad) , on introduit sous agitation le morceau de tissu traité précédemment (sec et ayant le revêtement de polymère) que l'on laisse tremper sous agitation pendant 30 minutes, le tissu traité est ensuite récupéré à l'aide d'une pince à épiler, et rapidement étuvé à 100 °C pendant 6 heures. La différence de poids entre le tissu sec traité ou modifié hydrophile et le tissu de départ non traité donne le poids de polymère adsorbé sur le tissu au cours de l'opération de trempage ou de traitement.(300 rpm) using a magnetic bar, one liter of 10% aqueous solution of a heat-sensitive copolymer prepared previously. A few drops of ammonia (NH4OH) are added thereto so as to obtain a pH of 10. The whole is brought to a given treatment temperature (Tad) higher or lower than the LCST of the polymer. After stabilization at the desired treatment temperature (Tad), the previously treated piece of fabric (dry and having the polymer coating) is introduced with stirring, which is left to soak with stirring for 30 minutes, the treated fabric is then recovered at using tweezers, and quickly steamed at 100 ° C for 6 hours. The difference in weight between the dry treated or modified hydrophilic fabric and the untreated starting fabric gives the weight of polymer adsorbed on the fabric during the soaking or treatment operation.
Le Tableau 6 suivant donne les valeurs obtenues pour les traitements réalisés au-dessus de la LCST du polymère. Nous reprenons pour comparaison la masse de polymère adsorbé sur le tissu sec modifié hydrophile après les traitements précédents en milieu acide.Table 6 below gives the values obtained for the treatments carried out above the LCST of the polymer. We use for comparison the mass of polymer adsorbed on the hydrophilic modified dry tissue after the previous treatments in an acid medium.
Tableau 6Table 6
Désorption de revêtement hydrophile sur le tissu par traitement en milieu basique : Comparaison entre la masse initiale de polymère adsorbé sur le tissu après traitement en milieu aqueux acide en présence de solution à 10% de polymère et la masse finale de polymère restant sur le tissu après traitement en milieu aqueux basique en présence de solution à 10% de polymèreDesorption of hydrophilic coating on the fabric by treatment in basic medium: Comparison between the initial mass of polymer adsorbed on the tissue after treatment in acidic aqueous medium in the presence of 10% solution of polymer and the final mass of polymer remaining on the tissue after treatment in basic aqueous medium in the presence of 10% polymer solution
EXEMPLE 25 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12 / AMAEXAMPLE 25 SYNTHESIS OF A MAPEG 12 / AMA COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 528 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement les monomères et solution d' amorceur de la façon suivante :528 parts of water are introduced into a 1 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
(3) coulée en trois heures d'un mélange de monomères comprenant :(3) pouring in three hours of a mixture of monomers comprising:
- 66,9 parties d'AMA ; et - 174,9 parties de MAPEG 12 ;- 66.9 parts of AMA; and - 174.9 parts of MAPEG 12;
(4) coulée en trois heures d'une solution d' amorceur contenant :(4) pouring in three hours of an initiator solution containing:
- 48 parties d'eau ; et- 48 parts of water; and
- 5,9 parties de persulfate d'ammonium.- 5.9 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
EXEMPLE 26 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12/AMA/MAMEXAMPLE 26 SYNTHESIS OF A MAPEG 12 / AMA / MAM COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 556,25 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement, les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor, 556.25 parts of water are added with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
- coulée en trois heures d'un mélange de monomères :- pouring in three hours of a mixture of monomers:
- 62,64 parties d'AMA ;- 62.64 parts of AMA;
- 164,4 parties de MAPEG 12 ; et- 164.4 parts of MAPEG 12; and
- 9,84 parties de MAM ;- 9.84 parts of MAM;
- coulée en trois heures d'une solution d' amorceur contenant :- pouring in three hours of an initiator solution containing:
- 43,75 parties d'eau ; et- 43.75 parts of water; and
- 6,15 parties de persulfate d'ammonium.- 6.15 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 45 °C.
EXEMPLE 27 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12/AMA/MAMThis polymer has an LCST of 45 ° C. EXAMPLE 27 SYNTHESIS OF A MAPEG 12 / AMA / MAM COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 556,25 parties d'eau, et on porte le réacteur à la température de 80°C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement, les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor, 556.25 parts of water are added with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
- coulée en trois heures d'un mélange de monomères :- pouring in three hours of a mixture of monomers:
- 58,52 parties d'AMA ;- 58.52 parts of AMA;
- 153,6 parties de MAPEG 12 ; et- 153.6 parts of MAPEG 12; and
- 39,41 parties de MAM ;- 39.41 parts of MAM;
coulée en trois heures d'une solution d' amorceur contenant :pouring in three hours of an initiator solution containing:
- 43,75 parties d'eau ; et- 43.75 parts of water; and
- 6,15 parties de persulfate d'ammonium.- 6.15 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
EXEMPLE 28 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12/AMA/MAMEXAMPLE 28 SYNTHESIS OF A MAPEG 12 / AMA / MAM COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre)
556,25 parties d'eau, et on porte le réacteur à la température de 80°C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement, les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor, the mixture is stirred (150 rpm; agitation by anchor) 556.25 parts of water, and the reactor is brought to the temperature of 80 ° C under nitrogen sweep. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
coulée en trois heures d'un mélange de monomèrespouring in three hours of a mixture of monomers
- 53,81 parties d'AMA ;- 53.81 parts of AMA;
- 141,23 parties de MAPEG 12 ; et- 141.23 parts of MAPEG 12; and
- 56,37 parties de MAM ;- 56.37 parts of MAM;
- coulée en trois heures d'une solution d' amorceur contenant :- pouring in three hours of an initiator solution containing:
- 43,75 parties d'eau ; et- 43.75 parts of water; and
- 6,15 parties de persulfate d'ammonium.- 6.15 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires . On refroidit le réacteur à 20°C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 22 °C.This polymer has an LCST of 22 ° C.
EXEMPLE 29 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12/AMA/MAMEXAMPLE 29 SYNTHESIS OF A MAPEG 12 / AMA / MAM COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 556,25 parties d'eau, et on porte le réacteur à la température de 80°C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et
parallèlement, les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor, 556.25 parts of water are added with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., it is introduced by continuous casting over three hours, separately and in parallel, the monomers and initiator solution as follows:
- coulée en trois heures d'un mélange de monomères :- pouring in three hours of a mixture of monomers:
- 51,19 parties d'AMA ;- 51.19 parts of AMA;
- 134,35 parties de MAPEG 12 ; et- 134.35 parts of MAPEG 12; and
- 65,81 parties de MAM ;- 65.81 parts of MAM;
coulée en trois heures d'une solution d' amorceur contenant :pouring in three hours of an initiator solution containing:
- 43,75 parties d'eau ; et- 43.75 parts of water; and
- 6,15 parties de persulfate d'ammonium.- 6.15 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère n' est pas soluble dans la plage de température supérieure à 4°C étudiée.This polymer is not soluble in the temperature range above 4 ° C studied.
EXEMPLE 30 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12/AMA/MABuEXAMPLE 30 SYNTHESIS OF A MAPEG 12 / AMA / MABu COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 556,25 parties d'eau, et on porte le réacteur à la température de 80°C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement, les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor, 556.25 parts of water are added with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
coulée en trois heures d'un mélange de monomères
- 77,88 parties d'AMA ;pouring in three hours of a mixture of monomers - 77.88 parts of AMA;
- 165,09 parties de MAPEG 12 et- 165.09 parts of MAPEG 12 and
- 8,69 parties de MABu ;- 8.69 parts of MABu;
- coulée en trois heures d'une solution d' amorceur contenant :- pouring in three hours of an initiator solution containing:
- 43,75 parties d'eau ; et- 43.75 parts of water; and
- 6,15 parties de persulfate d'ammonium.- 6.15 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires . On refroidit le réacteur à 20°C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 36°C.This polymer has an LCST of 36 ° C.
EXEMPLE 31 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12/AMA/MABuEXAMPLE 31 SYNTHESIS OF A MAPEG 12 / AMA / MABu COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 556,25 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement, les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor, 556.25 parts of water are added with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
— coulée en trois heures d'un mélange de monomères :- pouring in three hours of a mixture of monomers:
- 74,48 parties d'AMA ;- 74.48 parts of AMA;
- 149,48 parties de MAPEG 12 ; et- 149.48 parts of MAPEG 12; and
- 27,53 parties de MABu ;- 27.53 parts of MABu;
— coulée en trois heures d'une solution d' amorceur contenant :
- 43,75 parties d'eau ; et- pouring in three hours of an initiator solution containing: - 43.75 parts of water; and
-- 6,15 parties de persulfate d'ammonium.- 6.15 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère un polymère non soluble dans l'eau de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and a polymer insoluble in water of composition is recovered:
Ce polymère n' est pas hydrosoluble et se présente sous forme de dispersion opaque malgré le faible taux de motifs hydrophobes. Il présente un changement d'aspectThis polymer is not water-soluble and is in the form of an opaque dispersion despite the low rate of hydrophobic units. It has a change of appearance
(précipitation) comparable à une LCST à une température de 40°C.(precipitation) comparable to an LCST at a temperature of 40 ° C.
EXEMPLE 32 : SYNTHÈSE D'UN COPOLYMÈRE MAPEG 12/AMA/MALAUEXAMPLE 32 SYNTHESIS OF A MAPEG 12 / AMA / MALAU COPOLYMER
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 556,25 parties d'eau, et on porte le réacteur à la température de 80 °C sous ' balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement, les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor are introduced with stirring (150 revolutions / min; after anchor stirring) 556.25 parts of water are added and the reactor at the temperature of 80 ° C under the nitrogen sweep. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
- coulée en trois heures d' un mélange de monomères :- casting in three hours of a mixture of monomers:
- 74,38 parties d'AMA ;- 74.38 parts of AMA;
- 161,16 parties de MAPEG 12 ; et- 161.16 parts of MAPEG 12; and
- 16,07 parties de MALAU ;- 16.07 parts of MALAU;
— coulée en trois heures d'une solution d' amorceur contenant :- pouring in three hours of an initiator solution containing:
- 43,75 parties d'eau ; et- 43.75 parts of water; and
- 6,15 parties de persulfate d'ammonium.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires . On refroidit le réacteur à 20 °C et on récupère un polymère non soluble dans l'eau de composition :- 6.15 parts of ammonium persulfate. After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and a polymer insoluble in water of composition is recovered:
Ce polymère n' est pas soluble et se présente sous forme de dispersion opaque. Un changement d'aspect (précipitation) apparaît à 40 °C, comparable à une LCST.This polymer is not soluble and is in the form of an opaque dispersion. A change in appearance (precipitation) appears at 40 ° C, comparable to an LCST.
EXEMPLES 33 36 SYNTHESE DE COPOLYMERES MAPEGEXAMPLES 33 36 SYNTHESIS OF MAPEG COPOLYMERS
12 /AMA/MALAU12 / AMA / MALAU
Les modes opératoires utilisés sont identiques à celui de l'Exemple 32 précédent. Le Tableau 7 ci-après donne les résultats obtenus.
The procedures used are identical to that of Example 32 above. Table 7 below gives the results obtained.
Tableau 7Table 7
Il ressort des Exemples 25 à 36 que :It appears from Examples 25 to 36 that:
- il est possible d'incorporer des motifs hydrophobes dans la structure des copolymères à base d' acide methacrylate et methacrylate polyéthoxylé en préservant la solubilité dans l'eau ainsi que la sensibilité à la température ;- It is possible to incorporate hydrophobic units in the structure of copolymers based on methacrylate acid and polyethoxylated methacrylate while preserving the solubility in water as well as the temperature sensitivity;
- les monomères hydrophobes les plus adaptés sont ceux ayant un caractère hydrophobe pas trop marqué comme le methacrylate de méthyle. Son taux d'incorporation peut aller jusqu'à 40% molaire. Dès que le caractère hydrophobe devient important comme c' est le cas du methacrylate de butyle et du methacrylate de lauryle, le taux nécessaire à la préservation de thermosensibilité et la solubilité dans l'eau est faible, à savoir respectivement de l'ordre de 5% et 0,1% molaire.- the most suitable hydrophobic monomers are those having a hydrophobic character which is not too marked, such as methyl methacrylate. Its incorporation rate can go up to 40 mol%. As soon as the hydrophobic character becomes important as it is the case of butyl methacrylate and lauryl methacrylate, the rate necessary for the preservation of thermosensitivity and the solubility in water is low, namely of the order of 5 % and 0.1 mol%.
EXEMPLE 37 : SYNTHÈSE D'UN COPOLYMÈREEXAMPLE 37 SYNTHESIS OF A COPOLYMER
MAPEG 12 /MAPEG 8/AMA/MAMMAPEG 12 / MAPEG 8 / AMA / MAM
Un mélange de MAPEG 8 et de MAPEG 12 a été utilisé afin de préparer un copolymère ayant un nOE de 8,5.A mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having a nOE of 8.5.
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 555 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80°C, on introduit par coulée continue en trois heures, séparément et parallèlement, les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor, 555 parts of water are introduced under stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
- coulée en trois heures d' un mélange de monomères : - 74,66 parties d'AMA ;- casting in three hours of a mixture of monomers: - 74.66 parts of AMA;
- 26,96 parties de MAPEG 12 ;- 26.96 parts of MAPEG 12;
- 120,52 parties de MAPEG 8 ; et- 120.52 parts of MAPEG 8; and
- 29,33 parties de MAM ;
- coulée en trois heures d'une solution d' amorceur contenant :- 29.33 parts of MAM; - pouring in three hours of an initiator solution containing:
- 43,75 parties d'eau ; et- 43.75 parts of water; and
- 6,15 parties de persulfate d'ammonium.- 6.15 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 18 °C.This polymer has an LCST of 18 ° C.
EXEMPLE 38 : SYNTHESE D'UN COPOLYMERE MAPEG 12/MAPEG 8/AMA/MAMEXAMPLE 38 SYNTHESIS OF A MAPEG 12 / MAPEG 8 / AMA / MAM COPOLYMER
Un mélange de MAPEG 8 et MAPEG12 a été utilisé afin de préparer un copolymère ayant un nOE de 10,5.A mixture of MAPEG 8 and MAPEG12 was used to prepare a copolymer having an nOE of 10.5.
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; agitation par ancre) 444 parties d'eau, et on porte le réacteur à la température de 80°C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement, les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor, 444 parts of water are introduced under stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
coulée en trois heures d'un mélange de monomèrespouring in three hours of a mixture of monomers
- 54,19 parties d'AMA ;- 54.19 parts of AMA;
- 81,07 parties de MAPEG 12 ;- 81.07 parts of MAPEG 12;
- 44,71 parties de MAPAG 8 ; et- 44.71 parts of MAPAG 8; and
- 21,29 parties de MAM;
- coulée en trois heures d'une solution d' amorceur contenant :- 21.29 parts of MAM; - pouring in three hours of an initiator solution containing:
- 43,75 parties d'eau ;' et- 43.75 parts of water; ' and
- 6,15 parties de persulfate d'ammonium.- 6.15 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20°C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 35 °C.This polymer has an LCST of 35 ° C.
EXEMPLE 39 SYNTHESE D'UN COPOLYMERE MAPEG 12/MAPEG 8/AMA/MAMEXAMPLE 39 SYNTHESIS OF A MAPEG 12 / MAPEG 8 / AMA / MAM COPOLYMER
Un mélange de MAPEG 8 et MAPEG 12 a été utilisé afin de préparer un copolymère, ayant un nOE de 9,5.A mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer, having an nOE of 9.5.
Dans un réacteur de 1 litre, on introduit sous agitation (150 tours/minute ; . agitation par ancre) 555 parties d'eau, et on porte le réacteur à la température de 80 °C sous balayage d'azote. Quand la température du milieu reactionnel est stabilisée à 80 °C, on introduit par coulée continue en trois heures, séparément et parallèlement, les monomères et solution d' amorceur de la façon suivante :In a 1 liter reactor, 555 parts of water are introduced under stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
— coulée en trois heures d'un mélange de monomères- pouring in three hours of a mixture of monomers
- 71,22 parties d'AMA ;- 71.22 parts of AMA;
- 63,93 parties de MAPEG 12 ;- 63.93 parts of MAPEG 12;
- 88,40 parties de MAPAG 8 ; et- 88.40 parts of MAPAG 8; and
- 27,98 parties de MAM ;
- coulée en trois heures d'une solution d' amorceur contenant :- 27.98 parts of MAM; - pouring in three hours of an initiator solution containing:
- 43,75 parties d'eau ; et- 43.75 parts of water; and
- 6,15 parties de persulfate d'ammonium.- 6.15 parts of ammonium persulfate.
Au bout des trois heures de coulée, on laisse la réaction se poursuivre pendant deux heures supplémentaires. On refroidit le réacteur à 20 °C et on récupère une solution aqueuse de polymère hydrosoluble de composition :After three hours of pouring, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered:
Ce polymère a une LCST de 27 °C.This polymer has an LCST of 27 ° C.
Le Tableau 8 ci-dessous donne l'évolution de la LCST en fonction du n"θE.
Table 8 below gives the evolution of the LCST as a function of n " θE.
Tableau 8Table 8
-5
-5
Claims
REVENDICATIONS
1 - Procédé de modification hydrophile d' un substrat, caractérisé par le fait que l'on traite ledit substrat en milieu aqueux par un modifiant polymère ou copolymère hydrosoluble ayant des propriétés thermosensibles.1 - Process for hydrophilic modification of a substrate, characterized in that said substrate is treated in an aqueous medium with a water-soluble polymer or copolymer modifier having thermosensitive properties.
2 - Procédé selon la revendication 1, caractérisé par le fait que le modifiant polymère ou copolymère hydrosoluble thermosensible a une LCST comprise entre 3 et 100°C.2 - Method according to claim 1, characterized in that the thermosensitive water-soluble polymer or copolymer modifier has an LCST of between 3 and 100°C.
3 - Procédé selon l'une des revendications 1 et 2, caractérisé par le fait que l'on traite le substrat en milieu aqueux par ledit modifiant polymère ou copolymère thermosensible à une température au moins égale à la LCST dudit polymère ou copolymère thermosensible afin de faire précipiter ce dernier sur ledit substrat au moment du traitement en raison de son caractère hydrophobe dans ce domaine de température .3 - Method according to one of claims 1 and 2, characterized in that the substrate is treated in an aqueous medium with said thermosensitive polymer or copolymer modifier at a temperature at least equal to the LCST of said thermosensitive polymer or copolymer in order to cause the latter to precipitate on said substrate at the time of treatment due to its hydrophobic nature in this temperature range.
4 - Procédé selon l'une des revendications 1 et 2, suivant lequel le substrat à traiter ne supporte pas d'être soumis à une température dépassant une valeur T, caractérisé par le fait que l'on traite le substrat en milieu aqueux à une température inférieure à T, le polymère ou copolymère hydrosoluble thermosensible étant • alors choisi parmi ceux ayant une LCST au plus égale à la température de traitement.4 - Method according to one of claims 1 and 2, according to which the substrate to be treated does not withstand being subjected to a temperature exceeding a value T, characterized in that the substrate is treated in an aqueous medium at a temperature lower than T, the thermosensitive water-soluble polymer or copolymer then being • then chosen from those having an LCST at most equal to the treatment temperature.
5 - Procédé selon l'une des revendications 1 et 2, suivant lequel on traite le substrat en milieu aqueux à une température au plus égale à la LCST du (co) polymère hydrosoluble thermosensible, caractérisé par le fait que l'on choisit ledit (co) polymère parmi ceux ayant des motifs fonctionnels, ioniques ou compatibilisants permettant sa fixation sur le substrat.5 - Method according to one of claims 1 and 2, according to which the substrate is treated in an aqueous medium at a temperature at most equal to the LCST of the thermosensitive water-soluble (co) polymer, characterized in that said ( co) polymer among those having functional, ionic or compatibilizing units allowing its attachment to the substrate.
6 - Procédé selon la revendication 5, caractérisé par le fait que les motifs fonctionnels sont choisis parmi les fonctions cationiques, anioniques, acide sulfonique, acide phosphaté, posphate, phosphonees, groupes hydrophobes, éthoxylées, acide carboxylique, silanées, maléique, alcool, aminé, amide, sulfonates, carboxylates .
7 - Procédé selon l'une des revendications 1 à 6, caractérisé par le fait que l'on traite ledit substrat en milieu aqueux par le modifiant homopolymère ou copolymère hydrosoluble ayant des propriétés thermosensibles qui a des motifs fonctionnels susceptibles d'apporter des propriétés complémentaires autres que l' hydrophilie, et/ou qui est combiné avec au moins un autre ingrédient actif dont la rétention ou l'adsorption sur le substrat résulte de son enrobage ou de son encapsulation par le polymère thermosensible au moment de sa précipitation sur le substrat au-dessus de la LCST.6 - Method according to claim 5, characterized in that the functional units are chosen from cationic, anionic, sulfonic acid, phosphate acid, phosphate, phosphonees, hydrophobic, ethoxylated, carboxylic acid, silanated, maleic, alcohol, amine functions , amide, sulfonates, carboxylates. 7 - Method according to one of claims 1 to 6, characterized in that said substrate is treated in an aqueous medium with the water-soluble homopolymer or copolymer modifier having thermosensitive properties which has functional units capable of providing complementary properties other than hydrophilicity, and/or which is combined with at least one other active ingredient whose retention or adsorption on the substrate results from its coating or its encapsulation by the thermosensitive polymer at the time of its precipitation on the substrate at above the LCST.
8 - Procédé selon la revendication 7, caractérisé par le fait que les autres ingrédients sont choisis parmi les polymères hydrophobes sous forme de latex, les dispersions aqueuses de polymères, les charges, les enzymes, les tensio-actifs, les matières organiques et les matières minérales .8 - Process according to claim 7, characterized in that the other ingredients are chosen from hydrophobic polymers in the form of latex, aqueous dispersions of polymers, fillers, enzymes, surfactants, organic materials and materials minerals.
9 - Procédé selon l'une des revendications 7 et 8, caractérisé par le fait que l'on choisit l'homo- ou copolymère hydrosoluble thermosensible parmi ceux aptes à interagir avec le ou les ingrédients utilisés conjointement, par exemple en formant des liaisons hydrogène avec celui-ci ou ceux-ci.9 - Method according to one of claims 7 and 8, characterized in that the thermosensitive water-soluble homo- or copolymer is chosen from among those capable of interacting with the ingredient(s) used jointly, for example by forming hydrogen bonds with this one or these.
10 - Procédé selon l'une des revendications 1 à 9, caractérisé par le fait que le substrat est choisi parmi le textile, les non-tissés, le métal, le verre, le bois, le papier, le cuir, les substrats du bâtiment, la moquette, les fibres, les polymères, le béton.10 - Method according to one of claims 1 to 9, characterized in that the substrate is chosen from textile, non-wovens, metal, glass, wood, paper, leather, building substrates , carpet, fibers, polymers, concrete.
11 - Procédé selon l'une des revendications 1 à 9, caractérisé par le fait qu'il consiste en un traitement hydrophile des textiles et non-tissés par adsorption du polymère thermosensible.11 - Method according to one of claims 1 to 9, characterized in that it consists of a hydrophilic treatment of textiles and non-wovens by adsorption of the thermosensitive polymer.
12 - Procédé selon l'une des revendications 1 à 9, caractérisé par le fait qu'il consiste en un traitement du papier, en particulier l'adsorption sur les fibres de cellulose pour l'amélioration de la résistance humide du papier et le traitement hydrophobe et oleophobe du papier.
13 - Procédé selon l'une des revendications 1 à12 - Method according to one of claims 1 to 9, characterized in that it consists of a treatment of the paper, in particular adsorption on cellulose fibers for improving the wet resistance of the paper and the treatment hydrophobic and oleophobic of paper. 13 - Method according to one of claims 1 to
9, caractérisé par le fait qu'il consiste en un traitement apportant aux "substrats des propriétés antistatiques, la mouillabilite, une modification hydrophile ou hydrophobe, la fixation des substances hydrophobes et hydrophiles ou l'élimination des substances hydrophobes et hydrophiles, des propriétés barrière entre le substrat et les substances hydrophobes ou oléophobes, la fixation de substances grasses . 14 - Procédé • selon l'une des revendications 1 à9, characterized by the fact that it consists of a treatment providing " substrates with antistatic properties, wettability, a hydrophilic or hydrophobic modification, the fixation of hydrophobic and hydrophilic substances or the elimination of hydrophobic and hydrophilic substances, barrier properties between the substrate and hydrophobic or oleophobic substances, the fixation of fatty substances. 14 - Method • according to one of claims 1 to
10, caractérisé par le fait que le traitement a conduit à un revêtement hydrophile prévu pour être temporaire s' étant adsorbé sur ledit substrat, et que, pour éliminer ou lessiver ledit revêtement hydrophile après utilisation du substrat ainsi modifié hydrophile, on provoque une désorption dudit revêtement :10, characterized in that the treatment has led to a hydrophilic coating intended to be temporary having adsorbed on said substrate, and that, to eliminate or leach said hydrophilic coating after use of the substrate thus modified hydrophilic, a desorption of said covering:
— en milieu aqueux basique à une température supérieure à la LCST, le (co) polymère thermosensible utilisé portant des fonctions acide carboxylique et étant tel qu'il perd sa sensibilité à la température en raison de la neutralisation desdites fonctions acide carboxylique, ou— in a basic aqueous medium at a temperature above the LCST, the thermosensitive (co)polymer used carrying carboxylic acid functions and being such that it loses its sensitivity to temperature due to the neutralization of said carboxylic acid functions, or
- quel que soit le pH à une température inférieure à la LCST. 15 - Procédé selon l'une des revendications 1 à- whatever the pH at a temperature below the LCST. 15 - Method according to one of claims 1 to
14, caractérisé par le fait que l'on utilise un modifiant choisi parmi :14, characterized by the fact that a modifier chosen from:
(I) les copolymères hydrosolubles thermosensibles obtenus à partir d'une composition de monomères comprenant, pour 100 parties en moles :(I) water-soluble thermosensitive copolymers obtained from a composition of monomers comprising, per 100 mole parts:
(A) de 1 à 98 parties en moles d' au moins un composé hydrosoluble choisi parmi ceux des formules (I) et (II) suivantes :(A) from 1 to 98 parts by moles of at least one water-soluble compound chosen from those of the following formulas (I) and (II):
11
- R représente H ou -CH3 ;- R represents H or -CH3;
9 -- R représente un reste alkylène en C2 qui comporte éventuellement un ou plusieurs groupes OH, ou un reste alkylène en C3-C4 qui comporte plusieurs groupes OH ; 9 -- R represents a C 2 alkylene residue which optionally contains one or more OH groups, or a C3-C4 alkylene residue which contains several OH groups;
- R^ représente H ou -CH3 ; et- R^ represents H or -CH3; And
- n est un nombre entier compris entre 1 et 70 ;- n is an integer between 1 and 70;
[R6-0] -R7 (II)
[R 6 -0] -R 7 (II)
dans laquelle : πin which: π
- R et R représentent chacun indépendamment hydrogène ou alkyle en C2-C4 ;- R and R each independently represent hydrogen or C 2 -C4 alkyl;
- Y1 est une liaison simple ou un reste alkylène en C -C ; - ' R6 représente un reste alkylène en C2 qui comporte éventuellement un ou plusieurs groupes OH, ou reste alkylène en C3-C4 qui comporte un ou plusieurs groupes OH ;- Y 1 is a single bond or a C -C alkylene residue; - ' R 6 represents a C 2 alkylene residue which optionally contains one or more OH groups, or a C3-C4 alkylene residue which contains one or more OH groups;
- R' représente H ou -CH3 ; et - o est un nombre entier compris entre 1 et- R' represents H or -CH3; and - o is an integer between 1 and
70 ;70;
(B) de 2 à 95 parties en moles d'au moins un monomère hydrosoluble choisi parmi les acides carboxyliques à insaturation éthylénique et les anhydrides d'acides carboxyliques à insaturation éthylénique;(B) from 2 to 95 mole parts of at least one water-soluble monomer chosen from ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic acid anhydrides;
(C) de 0 à 70 parties en moles d'au moins un composé hydrosoluble choisi parmi ceux- des formulés (III) et (IV) :(C) from 0 to 70 parts by moles of at least one water-soluble compound chosen from those formulated (III) and (IV):
Rc R c
CH2 = C-C-O- [R9-0] -[R10-O] -R11 ( 111 ; 0
dans laquelle :CH 2 = CCO- [R 9 -0] -[R 10 -O] -R 11 (111; 0 in which :
- R° représente H ou -CH3 ;- R° represents H or -CH3;
- R9 et R ° représentent chacun indépendamment un reste alkylène en C2-C qui comporte éventuellement un ou plusieurs groupes OH, Ry et R1 étant différents l'un de l'autre ;- R 9 and R ° each independently represent a C 2 -C alkylene residue which optionally comprises one or more OH groups, R y and R 1 being different from each other;
- R-*--*- représente H ou -CH3 ;- R-*--*- represents H or -CH3;
- p est un nombre entier compris entre 1 et 70 ; et - q est un nombre entier compris entre 1 et- p is an integer between 1 and 70; and - q is an integer between 1 and
40 ;40;
R12 R13 C = C-Y2-0-[R14-0]r~[R15-0]s-R16 (IV) R 12 R 13 C = CY 2 -0-[R 14 -0] r ~[R 15 -0] s -R 16 (IV)
HH
dans laquelle :in which :
- R-^ et R1"-^ représentent chacun indépendamment hydrogène ou alkyle en C2-C4,-- R-^ and R 1 "-^ each independently represent hydrogen or C 2 -C4 alkyl,-
- Y2 est une liaison simple ou un reste alkylène en C-L-C ;- Y 2 is a single bond or an alkylene residue in CLC;
- R14 et R1"3 représentent chacun indépendamment un radical alkylène en C2-C4 comportant éventuellement un ou plusieurs groupes OH,- R 14 and R 1 " 3 each independently represent a C 2 -C4 alkylene radical optionally comprising one or more OH groups,
R14 et
étant différents l'un de l'autreR 14 and being different from each other
- R représente H ou -CH3 ;- R represents H or -CH3;
- r est un nombre entier compris entre 1 et 70 ; et s est un nombre entier compris entre 1 et 40 ;- r is an integer between 1 and 70; and s is an integer between 1 and 40;
(D) de 0 à 30 parties en moles d'au moins un composé hydrosoluble choisi parmi ceux des formules (V) et (VI) :
R 17(D) from 0 to 30 parts by moles of at least one water-soluble compound chosen from those of formulas (V) and (VI): R17
CH9 = C- -O- [R18-O -R1 9 (V)
CH 9 = C- -O- [R 18 -O -R 1 9 (V)
dans laquelle :in which :
- R1' représente H ou -CH3 ;- R 1 'represents H or -CH3;
- R18 représente un reste alkylène en C2~C qui comporte éventuellement un ou plusieurs groupes OH ;- R 18 represents a C 2 ~C alkylene residue which optionally comprises one or more OH groups;
- R^" représente une chaîne alkyle en C2-C Q, aryle ou aralkyle'en C -C Q ; et- R^" represents a C 2 -CQ alkyl, aryl or C -C Q aralkyl chain; and
- t est un nombre entier compris entre 1 et 70 ;- t is an integer between 1 and 70;
[R22-0],,-R23 (VI)
dans laquelle :[R 22 -0],,-R 23 (VI) in which :
-
représentent chacun indépendamment hydrogène ou alkyle en C2-C ;- each independently represent hydrogen or C 2 -C alkyl;
- Y3 est une liaison simple ou un radical alkylène en C-j_-C ; - R22 représente un reste alkylène en C2-C4 qui comporte éventuellement un ou plusieurs groupes OH ;- Y 3 is a single bond or a C- j _-C alkylene radical; - R 22 represents a C 2 -C4 alkylene residue which optionally contains one or more OH groups;
- R23 est un reste alkyle en C2~C4Q, aryle ou aralkyle en Cg-Cg0 ; et - u est un nombre entier compris entre 1 et- R 23 is a C 2 ~C4 Q alkyl, aryl or Cg-Cg 0 aralkyl residue; and - u is an integer between 1 and
70 ;70;
(E) de 0 à 30 parties en moles d' au moins un monomère hydrosoluble choisi parmi :(E) from 0 to 30 parts by moles of at least one water-soluble monomer chosen from:
(El) les composés hydrosolubles de formule (VII) :
R2 4 R27 R2 5 (El) the water-soluble compounds of formula (VII): R 2 4 R 27 R 2 5
//
CH^ C I -C-A 1±-B 11- N Xfc (VII ) \CH^ CI -CA 1 ± -B 1 1 - NX fc (VII) \
0 R 26 dans laquelle :0 R 26 in which:
- R24 représente H ou -CH3 ;- R 24 represents H or -CH3;
-1-1
- A représente -O- ou -NH- ; - Bl représente -CH2CH2-, -CH2CH2CH2- ou -CH2CHOHCH2- ;- A represents -O- or -NH-; - Bl represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CHOHCH 2 -;
- R25 et R26 représentent chacun indépendamment -CH ou une chaîne alkyle en C2~C^g ; - R2 ' représente H, -CH3 ou une chaîne alkyle en C2-C]_ ;- R 25 and R 26 each independently represent -CH or a C 2 ~C^g alkyl chain; - R 2 'represents H, -CH3 or a C 2 -C ] _ alkyl chain;
- X° représente un anion monovalent, tel que Cle, SCNθ,CH3S03 Θ et Brθ ;- X° represents a monovalent anion, such as Cl e , SCN θ , CH 3 S0 3 Θ and Br θ ;
(E2) les composés hydrosolubles de formule(E2) the water-soluble compounds of formula
(VIII) :(VIII):
dans laquelle :in which :
A2 représente -O- ou -NH- ;A 2 represents -O- or -NH-;
B2 représente -CH2CH2-, -CH2CH2CH2- ou -CH2CHOH CH2- ;B 2 represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CHOH CH 2 -;
- R28 représente H ou -CH3 ; et- R 28 represents H or -CH3; And
9 q n - R et Rou représentent chacun indépendamment ~CH3 ou une chaîne alkyle en C2-C-j_g ;9 qn - R and R or each independently represent ~CH3 or a C 2 -C- j _g alkyl chain;
(E3) les monomères hydrosolubles sulfones à insaturation éthylénique et leurs sels ;
(E3) ethylenically unsaturated sulfone water-soluble monomers and their salts;
(E4) les monomères hydrosolubles silanés à insaturation éthylénique ;(E4) water-soluble silanated ethylenically unsaturated monomers;
(E5) les monomères hydrosolubles à fonction phosphate à insaturation éthylénique ;(E5) water-soluble monomers with ethylenically unsaturated phosphate function;
(E6) les monomères hydrosolubles phosphones à insaturation éthylénique et leurs sels ;(E6) water-soluble ethylenically unsaturated phosphone monomers and their salts;
(E7) les monomères hydrosolubles ayant des groupes N-vinyle ;(E7) water-soluble monomers having N-vinyl groups;
(E8) les composés hydrosolubles de formule (IX) :(E8) the water-soluble compounds of formula (IX):
- R31 représente H ou -CH ;- R 31 represents H or -CH;
- R et R33, identiques ou différents, représentent chacun indépendamment H,. alkyle,- en ^1-5 1^ comportent- éventuellement un ou plusieurs groupes OH ou (alcoxy en C-j__5) -alkyle en C-j__5 ;- R and R 33 , identical or different, each independently represent H,. alkyl, - ^1-5 1 ^ optionally comprise one or more OH groups or (C- j __5 alkoxy) -alkyl, C- j __5;
(E9) l' acrylonitrile ;(E9) acrylonitrile;
(E10) l'allyl alcool ;(E10) allyl alcohol;
(Eli) la vinylpyridine ;(Eli) vinylpyridine;
(E12) la N-(méth)acryloyltris(hydroxyméthyl)méthyl- amine ;(E12) N-(meth)acryloyltris(hydroxymethyl)methylamine;
(E13) le 2-sulfoéthyl (méth) acrylate ; et(E13) 2-sulfoethyl (meth) acrylate; And
(E14) le 2- (acétoacétoxy) éthyl (méth) acrylate ;
(F) 0 à 50 parties en moles d'au moins un monomère hydrophobe ;(E14) 2- (acetoacetoxy) ethyl (meth) acrylate; (F) 0 to 50 mole parts of at least one hydrophobic monomer;
(II) l'hydroxypropylcellulose et l'hydroxypropylcellulose méthylée ;(II) hydroxypropylcellulose and methylated hydroxypropylcellulose;
(III) le polyvinyl méthyl éther ;(III) polyvinyl methyl ether;
(IV) le poly (N-substitué (méth) acrylamide) , le poly(N- propylacrylamide) et le poly (N-éthoxypropylacylamide) ; et les copolymères de N- (méth) acrylamide ;(IV) poly(N-substituted (meth)acrylamide), poly(N-propylacrylamide) and poly(N-ethoxypropylacylamide); and N-(meth)acrylamide copolymers;
(V) les homopolymères des composés de formule (IX) :(V) the homopolymers of the compounds of formula (IX):
CH = (IX)
CH = (IX)
dans laquelle :in which :
- R34 représente H ou CH3 ;- R 34 represents H or CH3;
- A représente -O- ou -NH- ;- A represents -O- or -NH-;
B3 représente -CH2CH2-, CH2CH2CH2- ou -CH2CHOHCH2~; et - R35 et R représentent chacun indépendamment -CH3 ou -CH2-CH3 ;B 3 represents -CH 2 CH 2 -, CH 2 CH 2 CH 2 - or -CH 2 CHOHCH 2 ~; and - R 35 and R each independently represent -CH 3 or -CH 2 -CH 3 ;
(VI) les polymères obtenus par modification hydrophile des polymères hydrophobes par des motifs polyoxyèthylénes.
(VI) polymers obtained by hydrophilic modification of hydrophobic polymers with polyoxyethylene units.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01921523A EP1412097A1 (en) | 2000-04-12 | 2001-04-09 | Method for hydrophilic modification of a substrate using a treatment in an aqueous medium with a water soluble and heat-sensitive polymer |
| AU2001248500A AU2001248500A1 (en) | 2000-04-12 | 2001-04-09 | Method for hydrophilic modification of a substrate using a treatment in an aqueous medium with a water soluble and heat-sensitive polymer |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR00/04695 | 2000-04-12 | ||
| FR0004695A FR2807771A1 (en) | 2000-04-12 | 2000-04-12 | Hydrophilic modification of various substrates using treatment in aqueous medium containing water-soluble and heat-sensitive polymer, at temperature not lower than that of critical solubility temperature of polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2001078907A1 true WO2001078907A1 (en) | 2001-10-25 |
Family
ID=8849172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR2001/001075 WO2001078907A1 (en) | 2000-04-12 | 2001-04-09 | Method for hydrophilic modification of a substrate using a treatment in an aqueous medium with a water soluble and heat-sensitive polymer |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1412097A1 (en) |
| AU (1) | AU2001248500A1 (en) |
| FR (1) | FR2807771A1 (en) |
| WO (1) | WO2001078907A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7494944B2 (en) | 2004-12-10 | 2009-02-24 | Rhodia Inc. | Method for durable hydrophilization of a hydrophobic surface |
| CN106175018A (en) * | 2016-07-08 | 2016-12-07 | 华南理工大学 | A kind of degradable disponsable hair care towel and preparation method thereof |
| CN108047377A (en) * | 2017-12-06 | 2018-05-18 | 四川警察学院 | A kind of temperature-sensitive hydrogel and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107216430B (en) * | 2017-07-21 | 2019-04-05 | 贵州铁建恒发新材料科技股份有限公司 | A kind of preparation method of temperature sensitive sequestering gel concrete inner curing agent |
| CN109487561A (en) * | 2017-09-10 | 2019-03-19 | 北京林业大学 | A kind of hydrophobic bamboo fibre and preparation method thereof based on mussel protein biomimetic modification |
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| US3976614A (en) * | 1969-03-10 | 1976-08-24 | The Dow Chemical Company | Inherrently water-dispersible, selfcrosslinking interpolymers useful as coatings |
| US4332657A (en) * | 1978-12-01 | 1982-06-01 | Kansai Paint Co., Ltd. | Emulsion composition for use in baking paint |
| EP0249949A2 (en) * | 1986-06-17 | 1987-12-23 | Warner-Lambert Company | Sustained release pharmaceutical preparations |
| JPS6420386A (en) * | 1987-07-14 | 1989-01-24 | Agency Ind Science Techn | Wet transfer printing method |
| WO1991000881A1 (en) * | 1989-07-06 | 1991-01-24 | Norsolor | New acrylic copolymers and their use for coating bituminous materials |
| JPH07331224A (en) * | 1994-06-10 | 1995-12-19 | Toyota Central Res & Dev Lab Inc | Temperature-sensitive material |
| WO1998025710A1 (en) * | 1996-12-12 | 1998-06-18 | Landec Corporation | Aqueous dispersions of crystalline polymers and uses |
| JPH1190316A (en) * | 1997-09-25 | 1999-04-06 | Kikusui Kagaku Kogyo Kk | Use of thermosensitive coating material |
-
2000
- 2000-04-12 FR FR0004695A patent/FR2807771A1/en not_active Withdrawn
-
2001
- 2001-04-09 AU AU2001248500A patent/AU2001248500A1/en not_active Abandoned
- 2001-04-09 EP EP01921523A patent/EP1412097A1/en not_active Withdrawn
- 2001-04-09 WO PCT/FR2001/001075 patent/WO2001078907A1/en not_active Application Discontinuation
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3976614A (en) * | 1969-03-10 | 1976-08-24 | The Dow Chemical Company | Inherrently water-dispersible, selfcrosslinking interpolymers useful as coatings |
| US4332657A (en) * | 1978-12-01 | 1982-06-01 | Kansai Paint Co., Ltd. | Emulsion composition for use in baking paint |
| EP0249949A2 (en) * | 1986-06-17 | 1987-12-23 | Warner-Lambert Company | Sustained release pharmaceutical preparations |
| JPS6420386A (en) * | 1987-07-14 | 1989-01-24 | Agency Ind Science Techn | Wet transfer printing method |
| WO1991000881A1 (en) * | 1989-07-06 | 1991-01-24 | Norsolor | New acrylic copolymers and their use for coating bituminous materials |
| JPH07331224A (en) * | 1994-06-10 | 1995-12-19 | Toyota Central Res & Dev Lab Inc | Temperature-sensitive material |
| WO1998025710A1 (en) * | 1996-12-12 | 1998-06-18 | Landec Corporation | Aqueous dispersions of crystalline polymers and uses |
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| XIANG-YANG SHI ET AL: "Water-solution properties of a hydrophobically modified Poly(N-isopropylacrylamide)", JOURNAL OF APPLIED POLYMER SCIENCE., vol. 75, 2000, JOHN WILEY AND SONS INC. NEW YORK., US, pages 247 - 255, XP002153887, ISSN: 0021-8995 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7494944B2 (en) | 2004-12-10 | 2009-02-24 | Rhodia Inc. | Method for durable hydrophilization of a hydrophobic surface |
| CN106175018A (en) * | 2016-07-08 | 2016-12-07 | 华南理工大学 | A kind of degradable disponsable hair care towel and preparation method thereof |
| CN108047377A (en) * | 2017-12-06 | 2018-05-18 | 四川警察学院 | A kind of temperature-sensitive hydrogel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2001248500A1 (en) | 2001-10-30 |
| EP1412097A1 (en) | 2004-04-28 |
| FR2807771A1 (en) | 2001-10-19 |
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