EP1494795A2 - Method for preparing an emulsion by diluting an emulsifiable concentrate comprising an amphiphilic copolymer - Google Patents
Method for preparing an emulsion by diluting an emulsifiable concentrate comprising an amphiphilic copolymerInfo
- Publication number
- EP1494795A2 EP1494795A2 EP03747139A EP03747139A EP1494795A2 EP 1494795 A2 EP1494795 A2 EP 1494795A2 EP 03747139 A EP03747139 A EP 03747139A EP 03747139 A EP03747139 A EP 03747139A EP 1494795 A2 EP1494795 A2 EP 1494795A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymer
- weight
- surfactant
- emulsifiable concentrate
- monomers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000004495 emulsifiable concentrate Substances 0.000 title claims abstract description 74
- 229920001577 copolymer Polymers 0.000 title claims abstract description 67
- 239000000839 emulsion Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000007865 diluting Methods 0.000 title claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 18
- 239000008346 aqueous phase Substances 0.000 claims abstract description 11
- 239000012071 phase Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 50
- -1 vinylidene halides Chemical class 0.000 claims description 47
- 239000000178 monomer Substances 0.000 claims description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- 150000007513 acids Chemical class 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 150000001412 amines Chemical group 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 229920001983 poloxamer Polymers 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 229920001567 vinyl ester resin Polymers 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 3
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 3
- 150000003626 triacylglycerols Chemical class 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 125000005227 alkyl sulfonate group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 229960000502 poloxamer Drugs 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 description 44
- 235000019198 oils Nutrition 0.000 description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 10
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 10
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- 239000011149 active material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000004480 active ingredient Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 229920000359 diblock copolymer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 235000019271 petrolatum Nutrition 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000013011 aqueous formulation Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229940117969 neopentyl glycol Drugs 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical group OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- 239000010698 whale oil Substances 0.000 description 2
- 239000012991 xanthate Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FQOWJGGXNSRNJS-YFKPBYRVSA-N (2s)-2-(2-methylprop-2-enoylamino)propanoic acid Chemical compound OC(=O)[C@H](C)NC(=O)C(C)=C FQOWJGGXNSRNJS-YFKPBYRVSA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- RXOAQHLXPJYRNS-UHFFFAOYSA-N (4-benzoylphenyl)methyl-dimethylazanium;ethyl prop-2-enoate;chloride Chemical compound [Cl-].CCOC(=O)C=C.C1=CC(C[NH+](C)C)=CC=C1C(=O)C1=CC=CC=C1 RXOAQHLXPJYRNS-UHFFFAOYSA-N 0.000 description 1
- 150000000134 (4S)-limonene derivatives Chemical class 0.000 description 1
- CKPCAYZTYMHQEX-NBVRZTHBSA-N (e)-1-(2,4-dichlorophenyl)-n-methoxy-2-pyridin-3-ylethanimine Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=N/OC)/CC1=CC=CN=C1 CKPCAYZTYMHQEX-NBVRZTHBSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical class C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- QNIRRHUUOQAEPB-UHFFFAOYSA-N 2-(prop-2-enoylamino)butane-2-sulfonic acid Chemical compound CCC(C)(S(O)(=O)=O)NC(=O)C=C QNIRRHUUOQAEPB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- NEYTXADIGVEHQD-UHFFFAOYSA-N 2-hydroxy-2-(prop-2-enoylamino)acetic acid Chemical compound OC(=O)C(O)NC(=O)C=C NEYTXADIGVEHQD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- UWNSTHYSHJNJNW-UHFFFAOYSA-N 2-methyl-6-sulfo-3-(3-sulfopropyl)hex-2-enoic acid Chemical compound OS(=O)(=O)CCCC(=C(C(O)=O)C)CCCS(O)(=O)=O UWNSTHYSHJNJNW-UHFFFAOYSA-N 0.000 description 1
- HIWGDJVTAWTBNH-UHFFFAOYSA-N 2-methylidene-5-sulfopentanoic acid Chemical compound OC(=O)C(=C)CCCS(O)(=O)=O HIWGDJVTAWTBNH-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
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- JTGHYMNAOSKRPP-UHFFFAOYSA-N n,n-dimethylmethanamine;ethyl prop-2-enoate;methyl hydrogen sulfate Chemical compound C[NH+](C)C.COS([O-])(=O)=O.CCOC(=O)C=C JTGHYMNAOSKRPP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical class C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229940055726 pantothenic acid Drugs 0.000 description 1
- 235000019161 pantothenic acid Nutrition 0.000 description 1
- 239000011713 pantothenic acid Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 description 1
- 229960000490 permethrin Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000003996 polyglycerol polyricinoleate Substances 0.000 description 1
- 235000010958 polyglycerol polyricinoleate Nutrition 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- QYMMJNLHFKGANY-UHFFFAOYSA-N profenofos Chemical compound CCCSP(=O)(OCC)OC1=CC=C(Br)C=C1Cl QYMMJNLHFKGANY-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- ZYHMJXZULPZUED-UHFFFAOYSA-N propargite Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1C(OS(=O)OCC#C)CCCC1 ZYHMJXZULPZUED-UHFFFAOYSA-N 0.000 description 1
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- NQLVQOSNDJXLKG-UHFFFAOYSA-N prosulfocarb Chemical compound CCCN(CCC)C(=O)SCC1=CC=CC=C1 NQLVQOSNDJXLKG-UHFFFAOYSA-N 0.000 description 1
- FITIWKDOCAUBQD-UHFFFAOYSA-N prothiofos Chemical compound CCCSP(=S)(OCC)OC1=CC=C(Cl)C=C1Cl FITIWKDOCAUBQD-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229960002477 riboflavin Drugs 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940008424 tetradecamethylhexasiloxane Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- OTOIBUHBRMYFLY-UHFFFAOYSA-N trimethyl-[(2,4,4,6,6-pentamethyl-1,3,5,2,4,6-trioxatrisilinan-2-yl)oxy]silane Chemical compound C[Si](C)(C)O[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 OTOIBUHBRMYFLY-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000019164 vitamin B2 Nutrition 0.000 description 1
- 239000011716 vitamin B2 Substances 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
- C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
Definitions
- the subject of the present invention is a method for preparing an emulsion by diluting an emulsifiable concentrate comprising a copolymer comprising at least one hydrophilic segment and at least one hydrophobic segment.
- emulsions are very widely developed, whether in phytosanitary fields, metal treatment, in the paper industry, paints, treatment of textile fibers (in particular textile sizing), cosmetics , etc.
- the emulsions comprise two phases, one of which is dispersed in the other, the whole being kept stable by the use of suitable surfactants.
- the emulsions include non-negligible contents of surfactants.
- the presence of surfactants in these amounts can have negative consequences limiting the use of these emulsions or making their use more complex.
- the use of large amounts of surfactants in the emulsions leads to the appearance of a phenomenon of foam which in most cases is not desired. It is therefore often necessary to incorporate an anti-foaming agent into the formulation.
- Another difficulty with the use of emulsions lies in the fact that in certain applications, we are confronted with the use of active materials reactive with respect to water.
- emulsifiable concentrates represent a very interesting alternative. They are in fact advantageous in the sense that being free of water, they provide a solution to the problem of stability of the emulsions as well as to that of the use of hydrolysable compounds. Furthermore, they are self-emulsifying formulations, which means that when they are brought into contact with the required quantity of aqueous phase, they give a direct emulsion.
- the difficulty is that in order to obtain an emulsion with suitable drop size characteristics, for example, it is necessary to use relatively high levels of surfactants. Consequently, it is not uncommon for emulsions obtained from emulsifiable concentrates also to include high levels of surfactants.
- the present invention therefore aims to remedy the drawbacks mentioned above.
- a clear emulsifiable concentrate comprising an oil phase, optionally water, and amphiphilic compounds consisting of at least one surfactant is diluted in an aqueous phase, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, with the exclusion of copolymers comprising only segments obtained from ethylene oxide and propylene oxide, optionally at least one co- surfactant and optionally at least one neutralizing agent; • the total content of amphiphilic compounds representing 1 to 40% by weight of the emulsifiable concentrate;
- Another subject of the invention consists of a clear emulsifiable concentrate comprising an oil phase, optionally water, and amphiphilic compounds consisting of at least one surfactant, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, with the exception of copolymers comprising only segments obtained from ethylene oxide and propylene oxide, optionally at least one co-surfactant and optionally at least one neutralizing agent;
- the present invention therefore relates to emulsifiable concentrates which, while having lower levels of surfactants, make it possible to obtain by dilution, emulsions whose droplet size characteristics are of the same order of magnitude as those reached by diluting emulsifiable concentrates including higher levels of usual surfactants.
- the process according to the invention makes it possible, thanks to the use of the above-mentioned amphiphilic copolymer, to substantially reduce, or even more than 10 points in certain embodiments, the content of surfactant necessary to obtain emulsion sizes. after diluting the concentrate as fine as those obtained with conventional surfactant contents, ie 10 points higher.
- the method according to the invention makes it possible to reduce the drawback associated with the appearance of foam during the dilution of the emulsifiable concentrate.
- the invention provides greater stability, over time and / or in temperature, of the emulsion obtained by diluting the emulsifiable concentrate.
- stability over time is intended to mean the period during which no phenomenon of coalescence, creaming or demixing is observed, at a given temperature. No temperature stability, we mean the temperature below which these phenomena are not observed, at a given time. It is thus possible to obtain increased stability by using as much or less surfactant, and / or equal stability by using less surfactant.
- the stability required often depends on the field of use of the emulsifiable compound.
- a stability of a few hours, at temperatures of up to about 40 ° C, is useful.
- the method according to the invention also makes it possible to be able to have formulations comprising compounds sensitive to hydrolysis without having to previously prepare derivatives of these compounds for which the reactive function with respect to water will have been masked. This is particularly the case for compositions intended for example for the preparation of formulations for paints.
- the fact of obtaining emulsions with less surfactant has the advantage of limiting the migration phenomena of surfactants often observed in films, especially paintings.
- the fact that there is less surfactant in the emulsions obtained from emulsifiable concentrates provides an additional advantage as regards the recycling of such emulsions.
- other characteristics and advantages of the present invention will appear more clearly on reading the description and the examples which follow.
- the average droplet size of the emulsion obtained from the emulsifiable concentrate corresponds to the volume median diameter (d50), that is to say the droplet diameter equal to 50% of the cumulative distribution.
- the size of the droplets is measured using a Horiba type particle size analyzer. These particle size measurements are carried out by adding the emulsifiable concentrate in water at 20 ° C. and at the desired concentration; the addition operation being carried out with stirring for 5 minutes at 200 rpm using a pale frame.
- the emulsifiable concentrate comprises an oil and optionally water.
- the emulsifiable concentrate is in the form of a single-phase composition.
- the oil is more particularly chosen from compounds whose solubility in water does not exceed 10% by weight at 20 ° C. ,
- the oil is more particularly in a liquid form at the temperature of use of the emulsion obtained from the emulsifiable concentrate.
- the operating temperature range is close to ambient temperature, that is to say approximately between 15 and 40 ° C., although higher temperatures are not excluded; the latter, however, preferably remaining below 100 ° C.
- the oil can consist of a mixture of several compounds, one of which may not be liquid at use temperature, as soon as the assembly is liquid in this temperature range.
- organic oils of animal origin mention may be made, among others, of sperm whale oil, whale oil, seal oil, sardine oil, herring oil, shark, cod liver oil. Beeswax, pork or mutton fats may also be suitable.
- organic oils of vegetable origin there may be mentioned, among others, rapeseed oil, sunflower oil, peanut oil, olive oil, oil nuts, corn oil, soybean oil, linseed oil, hemp oil, grape seed oil, coconut oil, palm oil, oil cottonseed, babassu oil, jojoba oil, sesame oil, castor oil, carnauba wax.
- mineral oils With regard to mineral oils, mention may be made, inter alia, of oils obtained from petroleum fractions such as, for example, naphthenic, paraffinic oils (petroleum jelly), hexadecane, as well as paraffin waxes.
- the products derived from the alcoholysis of the abovementioned oils can also be used. It would not be departing from the scope of the present invention to use at least one fatty acid, saturated or not, at least one fatty acid ester, saturated or not, at least one fatty alcohol, saturated or not, or mixtures thereof.
- said acids, esters or alcohols comprise at least one hydrocarbon radical having from 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and can comprise one or more carbon-carbon double bonds, conjugated or not. Furthermore, the acids, esters or alcohols can comprise one or more hydroxyl groups.
- saturated fatty acids mention may be made of palmitic, stearic, isostearic and behenic acids.
- unsaturated fatty acids there may be mentioned myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic, ricinoleic acids, as well as their mixtures.
- fatty acid esters there may be mentioned the esters of the acids previously listed, for which the part deriving from the alcohol comprises 1 to 6 carbon atoms, such as the methyl, ethyl, propyl and isopropyl esters. , etc.
- esters of the abovementioned acids and of polyols such as for example glycerol, polyglycerol (such as for example polyglycerol polyricinoleate), glycol, propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, neopentylglycol (such as
- Neopentylglycol pentaerythritol, dipentaerythritol, trimethylolpropane, sorbitol, mannitol, xylitol, mesoerythritol.
- the oil can likewise be chosen from alkyd resins (such as, for example, Coporob 3115 DE resins, sold by the company Novance), epoxy resins, masked (or advantageously unmasked) poly (isocyanates) as soon as the emulsifiable concentrate is free of water.
- the oil can also be chosen from essential oils, mono-, di- and tri-glycerides.
- the silicones can likewise be used in the emulsifiable concentrates according to the invention.
- - a is an integer from 0 to 3;
- radicals R are identical or different and represent: - a saturated or unsaturated aliphatic hydrocarbon group containing from 1 to 10 carbon atoms;
- radicals R ′ are identical or different and represent:
- silicones can optionally comprise, preferably less than 5 mol%, units of formulas T and / or Q: RSiO 32 (unit T) and / or SiO 2 (unit Q) formula in which R has the definition given above .
- alkyl preferably C ⁇ C 10 optionally halogenated alkyl, such as methyl, ethyl, octyl, trifluoropropyl;
- aryls preferably C 6 -C 13 , such as phenyl.
- polar organic groups R of: - hydroxyfunctional groups such as alkyl groups substituted by one or more hydroxy or di (hydroxyalkyl) amino groups and optionally interrupted by one or more divalent hydroxyalkylamino groups.
- alkyl is meant a hydrocarbon chain preferably C ⁇ C, more preferably C ⁇ Ce; examples of these groups are - (CH 2 ) 3 -OH; - (CH 2 ) N (CH 2 CH 2 OH) 2 ; - (CH 2 ) 3 -N (CH 2 CH 2 OH) -CH 2 -CH 2 -N (CH 2 CH 2 OH) 2 :
- radicals R ′ there may be mentioned the groups:
- - alkyl preferably CC 10 optionally halogenated alkyl, such as methyl, ethyl, octyl, trifluoropropyl;
- aryls preferably C 6 -C 13 , such as phenyl
- alkyl or aryl substituted by amino alkyl preferably being CC 6 and aryl denoting a cyclic aromatic hydrocarbon group preferably C 6 -C 13 such as phenyl; examples are ethylamino, phenylamino;
- alkylcarbonylamino where alkyl is preferably CC 6 ; examples are methylacetamido.
- T units As concrete examples of "T units”, mention may be made of: CH 3 SiO 32 ;
- silicones contain reactive and / or polar radicals R (such as
- the latter generally do not represent more than 5% by weight of the silicone, and preferably not more than 1% by weight of the silicone.
- volatile oils such as hexamethyldisiloxane, octamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylhexa siloxane; the heptaméthyl-
- non-volatile silicones such as polydimethylsiloxane oils and gums and ⁇ , ⁇ -bis (hydroxy) polydimethylsiloxanes as well as polydimethylsiloxanes, polyphenylmethylsiloxane and ⁇ , ⁇ -bis (hydroxy) poly dimethylsiloxanes gums.
- ⁇ , ⁇ -bis (trimethyl) polydimethyl siloxane oils More particularly preferred are the ⁇ , ⁇ -bis (trimethyl) polydimethyl siloxane oils, the ⁇ , ⁇ -bis (hydroxy) polydimethyl siloxane oils, and very particularly the silicones of polydimethylsiloxane (dimethicone) and diphenyldimethicone type.
- the oil may optionally include an active ingredient, unless it is itself considered as an active ingredient.
- the active ingredient if it is different from the oil, is in a form miscible with oil or even dissolved in an organic solvent miscible with oil.
- the active ingredient is chosen from compounds whose solubility in water does not exceed 10% by weight, at 20 ° C.
- silicone oils belonging for example to the family of dimethicones
- lipophilic vitamins such as vitamin A and its derivatives, in particular its esters such as acetate, palmitate, propionate, vitamin B2, pantothenic acid, vitamin D and vitamin E.
- the phytosanitary active materials can be chosen from the family of ⁇ -cyano-phenoxybenzyl carboxylates or ⁇ -cyano-halogenophenoxy-carboxylates, the family of N-methylcarbonates comprising aromatic substituents, the active materials such as AIdrin, Azinphos-methyl, Benfluralin, Bifenthrin, Chlorphoxim, Chlorpyrifos, Fluchloralin, Fluroxypyr, Dichlorvos, Malathion, Molinate, Parathion, Permethrin, Profenofos, Propiconazole, Prothiofos, Pyrifenox, Butriflorazin, Metollorin , Heptopargil, Mecarbam, Propargite, Prosulfocarb, Bromophos-ethyl, Carbophenothion, Cyhalothrin.
- AIdrin Azinphos-methyl
- Benfluralin Benfluralin
- Bifenthrin Chlorpho
- Said active ingredients mentioned above can optionally be in a form dissolved in a suitable solvent, for example xylene, Solvesso®.
- the active ingredient is usually an oil, an oil derivative or a fatty acid ester.
- the active material can also be chosen from organic solvents or mixtures of such solvents which are not or only slightly miscible in water, such as in particular those used for cleaning or pickling, such as petroleum cuts.
- aromatic, terpene compounds such as D- or L-limonenes, as well as solvents such as Solvesso®.
- solvents such as Solvesso®.
- aliphatic esters such as methyl esters of a mixture of acetic, succinic and glutaric acids (mixture of acids by-product of the synthesis of Nylon), hydrocarbon oils such as petroleum jelly, and chlorinated solvents.
- an active ingredient other than the oil is present, its content is usually less than or equal to 50% by weight of oil, preferably between 10 and 50% by weight of oil.
- the total oil content in the emulsifiable concentrate including, where appropriate, the active material, advantageously represents from 60 to 95% by weight of the emulsifiable concentrate.
- the emulsifiable concentrate comprises water
- its content is such that the emulsifiable concentrate remains clear in the sense indicated above.
- the content varies according to the various constituent elements of the emulsifiable concentrate and remains easily determinable by a person skilled in the art.
- the water content in the emulsifiable concentrate if it is present, is less than or equal to 10% by weight of the concentrate.
- the emulsifiable concentrate further comprises amphiphilic compounds consisting of at least one surfactant, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, optionally at least one co-surfactant and optionally at least one neutralizing agent.
- the assembly comprising the surfactant, optionally the co-surfactant and optionally the neutralizing agent is soluble in oil, at ambient temperature (approximately 20 ° C.).
- the surfactant (s) are chosen from surfactants soluble in oil at the concentrations used in the invention.
- the surfactants are chosen from nonionic or anionic surfactants.
- the surfactant (s) are chosen from nonionic surfactants.
- alkoxylated fatty alcohols more particularly comprising from 6 to 22 carbon atoms; alkoxylated mono-, di- and tri-glycerides; - alkoxylated fatty acids, more particularly comprising from 6 to 22 carbon atoms; alkoxylated sorbitan esters (cyclized fatty acid sorbitol esters having 10 to 20 carbon atoms); alkoxylated fatty amines, more particularly comprising from 6 to 22 carbon atoms;
- Alkoxylated alkylphenols more particularly comprising one or two alkyl groups, linear or branched, having 4 to 12 carbon atoms; - alkylpolyglucosides; polyoxyalkylenated surfactants, such as for example the compounds sold under the Pluronic or Poloxamer range by the company BASF;
- the surfactant (s) are chosen from anionic surfactants in acid form or associated (s) with a multivalent counter ion.
- the multivalent counterion is preferably an alkaline earth metal such as magnesium, calcium, alone or in combination.
- alkyl esters sulfonates for example of formula R-CH (SO 3 M) -CH2COOR ', where R represents a C 8 -C 20 , preferably C 10 -C 16 hydrocarbon radical, optionally carrying one or more unsaturations, R 'a C1-C6 alkyl radical, preferably in CC 3 and M a hydrogen atom or an alkaline-earth cation. Mention may very particularly be made of methyl ester sulfonates whose radical R is C 14 -C 16 ;
- alkyl esters sulfates for example of formula R-CH (OSO 3 M) -CH2COOR ', where R represents a C 8 -C 2 o, preferably C 10 -C 16 hydrocarbon radical, optionally bearing one or several unsaturations, R ′ an alkyl radical in C C ⁇ , preferably in C ⁇ Cs and M a hydrogen atom or an alkaline earth cation; alkylbenzenesulfonates, more particularly C 9 -C 20 , primary or secondary alkylsulfonates, especially C ⁇ -C 22 , alkylglycerol sulfonates; alkyl sulphates, for example of formula ROSO 3 M, in which R represents a C 10 -C 24 , preferably C 12 -C 20 , alkyl or hydroxyalkyl radical; M a hydrogen atom or a cation of the same definition as above; alkyl ether sulfates for example of formula RO (AO)
- RCONHR'OSO 3 M where R represents a C 2 -C 22 , preferably C 6 -C 20 , alkyl radical, R 'a radical C 2 -C 3 alkyl, M representing a hydrogen atom or a cation of the same definition as above, as well as their polyalkoxylated derivatives (ethoxylated and / or propoxylated); the salts of saturated or unsaturated fatty acids, for example such as those in C 8 - C 24 , preferably in C 14 -C 20 and of an alkaline-earth cation, N-acyl N-alkyltau rates, alkylisethionates, alkylsuccinamates and alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, polyethoxycarboxylates; and the mono and di phosphat
- amphiphilic compounds present in the emulsifiable concentrate there are copolymers having at least one hydrophilic segment and at least one hydrophobic segment, with the exception of copolymers comprising only segments obtained from ethylene oxide and oxide propylene.
- amphiphilic compound is chosen so that all of the amphiphilic compounds are soluble in oil, if necessary, in the presence of a small amount of water.
- said amphiphilic compound is chosen from compounds soluble in oil.
- hydrophobic segment of the copolymer this can be obtained from one or more of the following monomers: the esters of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation, and optionally carrying a hydroxyl group; ⁇ -ethylenically unsaturated nitriles, vinyl ethers, vinyl esters, vinyl aromatic monomers, vinyl or vinylidene halides, linear or branched hydrocarbon monomers, aromatic or not, comprising at least one ethylenic unsaturation, oxide of propylene, butylene oxide, alone or in mixtures, as well as the macromonomers derived from such monomers.
- hydrophobic monomers capable of entering into the preparation of the hydrophobic segment (s) of the amphiphilic segmented copolymer mention may be made of:
- the preferred monomers are the esters of acrylic acid with linear or branched C1-C4 alcohols such as methyl, ethyl, propyl and butyl acrylate, vinyl esters such as vinyl acetate, styrene, ⁇ -methylstyrene.
- the hydrophilic segment of the amphiphilic copolymer the latter can be obtained from one or more monomers having an anionic or anionizable function.
- the functions of the anionic segment or segments of the copolymer are in an at least partially ionized (dissociated) form. More particularly, at least 10 mol% of the functions of the segment or segments are in ionized form.
- the determination of this value poses no problem to those skilled in the art; it is in particular a function of the pKa of the ionizable functions of the units of the copolymer and of the number of these functions (ie of the number of moles of monomer carrying ionizable functions used during the preparation of the copolymer).
- More particularly comprising at least one carboxylic, sulfonic, sulfuric, phosphonic, phosphoric, sulfosuccinic function, their salts, as well as the corresponding macromonomers.
- the anionic or anionizable monomer (s) can be chosen from the following: linear, branched, cyclic or aromatic mono- or polycarboxylic acids, N-substituted derivatives of such acids; monoesters of polycarboxylic acids, comprising at least one ethylenic unsaturation; linear, branched, cyclic or aromatic vinyl carboxylic acids; amino acids comprising one or more ethylenic unsaturations; alone or as mixtures, their precursors, their sulfonic or phosphonic counterparts, their salts, as well as the macromonomers derived from such monomers or from their salts.
- anionic / anionizable monomers there may be mentioned without intending to be limited thereto: acrylic acid, methacrylic acid, fumaric acid, itaconic acid, citraconic acid, acid maleic, acrylamido glycolic acid, 2-propene 1-sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, ⁇ -acrylamido methylpropane sulfonic acid, 2-sulfoethylene methacylate, sulfopropyl acrylic acid , bis-sulfopropyl acrylic acid, bis-sulfopropyl methacrylic acid, sulfatoethyl methacrylic acid, hydroxyethyl methacrylic acid phosphate ester, as well as alkali metal salts, such as sodium, potassium, or ammonium; vinyl sulfonic acid, vinylbenzene sulfonic acid, vinyl phosphonic acid, vinylidene phosphonic acid
- monomers which are precursors of those which have just been mentioned.
- these monomers have units which, once incorporated in the polymer chain, can be transformed, in particular by a chemical treatment such as hydrolysis, to restore the above-mentioned anionic / anionizable species.
- the fully or partially esterified monomers of the aforementioned monomers can be used to be, subsequently, completely or partially hydrolyzed.
- the hydrophilic segment or segments can be obtained from one or more monomers having a cationic or cationizable function.
- aminoalkyl (meth) acrylates aminoalkyl (meth) acrylamides; monomers comprising at least one secondary, tertiary or quaternary amine function, or a heterocyclic group containing a nitrogen atom, vinylamine, ethylene;
- the - diallyldialkyl ammonium salts alone or in mixtures, or the corresponding salts; as well as the macromonomers derived from such monomers. If they are in the form of salts, the latter are preferably chosen such that the counterion is a halide such as, for example, a chloride, or a sulfate, a hydrosulfate, an alkylsulfate, a phosphate, a citrate, a formate, an acetate.
- the ammonium function comprises at least one alkyl or aryl radical optionally carrying one or more alkyl radicals, having from 1 to 6 carbon atoms, preferably methyl, ethyl.
- Suitable cationic monomers include the following monomers: - dimethyl amino ethyl (meth) acrylate, dimethyl amino propyl (meth) acrylate ditertiobutyl aminoethyl (meth) acrylate, dimethyl amino methyl (meth) acrylamide, dimethyl amino propyl (meth) acrylamide; ethylene imine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; - trimethylammonium ethyl (meth) acrylate chloride, trimethylammonium ethyl acrylate methyl sulfate, benzyl dimethylammonium ethyl (meth) acrylate chloride, 4-benzoylbenzyl dimethyl ammonium ethyl acrylate chloride, trimethyl ammonium ethyl (meth) chloride acrylamido, trimethyl ammonium chloride, vinylbenzyl; diallyldimethyl ammonium chloride; alone or
- hydrophilic segment or segments of the amphiphilic copolymer can be obtained from nonionic hydrophilic monomer (s).
- amphiphilic copolymers can be block polymers and comprise at least two blocks, one being hydrophilic, the other hydrophobic. Recall that such copolymers are linear.
- the copolymers used are diblock or triblock copolymers.
- a copolymer is used, the backbone of which is hydrophilic and the pendant groups are hydrophobic, or vice versa.
- non-ionic hydrophilic monomers mention may be made of ethylene oxide; amides of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation or derivatives; hydrophilic esters derived from (meth) acrylic acid; vinyl esters making it possible to obtain polyvinyl alcohol blocks after hydrolysis; vinypyrrolidone; sugar type monomers such as (meth) acrylates oligosaccharides or oligoholosides, as well as the macromonomers derived from these monomers.
- nonionic hydrophilic monomers mention may be made very particularly of (meth) acrylamide, N-methyloI (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, vinyl esters making it possible to obtain blocks polyvinyl alcohol after hydrolysis, such as vinyl acetate, vinyl Versatate®, vinyl propionate.
- hydrophobic segment of the copolymer can comprise one or more hydrophilic units, likewise the hydrophilic segment can comprise one or more hydrophobic units.
- the distribution of the latter within the segment may be statistical, block or according to a concentration gradient.
- the copolymers which can be used in the context of the invention can be prepared by carrying out polymerizations by the anionic route, by the cationic route, by the so-called living or controlled radical route. It is likewise possible to carry out, depending on the monomers used, a group transfer polymerization (called “group transfer”) or else a cycle opening polymerization (in particular case of polymerization from the N-carboxy anhydride cycle) , or also by a polymerization involving a transesterification of terminal groups.
- group transfer group transfer polymerization
- cycle opening polymerization in particular case of polymerization from the N-carboxy anhydride cycle
- the polymers are obtained by implementing at least one step of living radical polymerization.
- living or controlled polymerization processes reference may in particular be made to: radical polymerization controlled by xanthates according to the teaching of application WO 98/58974, radical polymerization controlled by dithioesters according to teaching of the application WO 98/01478,
- polymers bearing grafts they can in particular be obtained by various methods, such as for example a copolymerization of a monomer with a macromonomer. More particularly, this method firstly implements the grafting at the end of the segment of a radical polymerizable function. This grafting can be carried out by usual methods of organic chemistry. Then, in a second step, the macromonomer thus obtained is polymerized with the monomer chosen to form the skeleton and a so-called "comb" polymer is obtained.
- Comb polymers can also be obtained by polymerization of a monomer followed by grafting onto the skeleton thus obtained.
- the grafting of the lateral polymer segments onto a skeleton polymer segment can be carried out according to conventional techniques familiar to those skilled in the art (European Polymer Journal 4, 343 (1968) for example). Among these conventional techniques, mention may be made in particular of those known as direct grafting.
- segment copolymers comprising repeating units having one or more silicon atoms
- copolymers used in the composition of the emulsifiable concentrate more particularly have a molar mass by weight of at most 50,000 g / mol, preferably at most 20,000 g / mol.
- the weight-average molar mass of the copolymer is advantageously at least 2500 g / mol, preferably at least 5000 g / mol.
- the content of copolymer is such that when this copolymer is added to a mixture comprising the oil, the surfactant (s), optionally the co-surfactant, optionally the neutralizing agent, there is a clear solution in the sense indicated above, possibly by adding water, in the case where the oil and the active agent which it possibly contains, are not sensitive to hydrolysis.
- the content of amphiphilic copolymer represents from 0.1 to 25% by weight of said amphiphilic compounds as defined above.
- the proportion by weight of copolymer relative to the surfactant is preferably between 0.5 and 10% by weight.
- the emulsifiable concentrate used in the process according to the invention can optionally comprise at least one co-surfactant.
- a co-surfactant or a mixture of co-surfactants soluble in oil is chosen.
- this is chosen from primary alcohols comprising at least one aliphatic radical, linear or branched, saturated or not, comprising from 4 to 22 carbon atoms, or at least one aromatic radical, preferably comprising 6 carbon atoms , optionally carrying one or more alkyl substituents comprising 1 to 10 carbon atoms.
- alcohols capable of entering into the composition of the emulsifiable concentrates is suitable in particular isopropanol, ethylhexanol, dodecanol, hexadecanol, benzyl alcohol, alone or in mixtures.
- the weight ratio of co-surfactant / surfactant is preferably between 0 excluded and 50% by weight, preferably between 5 and 40% by weight.
- the emulsifiable concentrate can also optionally comprise at least one neutralizing agent.
- a neutralizing agent is used which is soluble in the emulsifiable concentrate between 15 and 40 ° C. or a compound which, once heated beyond its melting point in the presence of oil, then cooled, remains soluble in oil.
- the neutralizing agent is chosen from compounds soluble in the oil phase and carrying at least one amine or carboxylic function.
- amines comprising one to three radicals, identical or not, comprising 1 to 10 carbon atoms, optionally carrying a hydroxyl radical, are suitable for this purpose.
- ethylenediamine triethylamine, dimethylbutylamine, diimethylisopropylamine, dimethylcyclohexylamine, tripropylamine, monoethanolamine, diethanolamine, aminoethylethanolamine, Paminomethylpropanolamine can be used as neutralizing agent.
- surfactant comprises a compound which can be ionized under the pH conditions of the final emulsion.
- the neutralizing agent is used in an amount such that the proportion by weight of neutralizing agent / surfactant is between 0 excluded and 50% by weight, preferably between 5 and 40% by weight.
- the emulsifiable concentrate can comprise a co-surfactant and / or a neutralizing agent.
- the emulsifiable concentrate comprises either a co-surfactant or a neutralizing agent.
- the total content of amphiphilic compounds in the emulsifiable concentrate represents from 1 to 40% by weight of the emulsifiable concentrate.
- the total content of amphiphilic compounds is between 5 and 30% by weight of the emulsifiable concentrate.
- the emulsifiable concentrate is obtained by a simple mixture of the various constituent elements which have just been detailed.
- the temperature at which this mixing is carried out is generally such that all of the compounds are in liquid form.
- this temperature is above the melting point of each of the compounds.
- the emulsion is obtained by diluting the emulsifiable concentrate in an aqueous phase.
- This emulsion is a direct emulsion, that is to say for which the continuous phase is an aqueous phase.
- the aqueous phase with which the emulsifiable concentrate is diluted is in itself a formulation usable in a particular field.
- said aqueous phase comprises the usual additives in the field of use.
- the dilution of the emulsifiable concentrate leads to the production of an emulsion for which at least 75% by volume of the droplets has an average size (ds) less than or equal to 1 ⁇ m.
- the average size of the droplets of the emulsion thus obtained is less than that of an emulsion obtained by dilution of an emulsifiable concentrate devoid of the copolymer detailed previously; the total concentration of amphiphilic compounds being the same in both cases.
- the average size of the droplets of the emulsion obtained according to the method according to the invention is therefore less than or equal to 1 ⁇ m, more particularly between 0.2 and 1 ⁇ m.
- the dilution of the emulsifiable concentrate is preferably carried out by adding the emulsifiable concentrate to the aqueous phase.
- the content of emulsifiable concentrate in the final formulation is very variable depending on the field of use of the concentrate.
- the content of emulsifiable concentrate represents 0.1 to 40% by weight of the final aqueous formulation, preferably 0.1 to 30% by weight of the final aqueous formulation.
- the dilution operation conventionally takes place with slight agitation, in particular by means of a pale frame.
- the emulsion thus obtained can be used in many fields, depending on the nature of the oil, if any, of the active ingredient present, forming part of the composition of the emulsifiable concentrate.
- the emulsifiable concentrate can be used in the field of phytosanitary formulations.
- the preparation of the emulsion is made by the user before applying it to the plants or fields to be treated.
- the emulsions can likewise be used in the field of cosmetics.
- the emulsions can likewise be used in the field of paints, varnishes, adhesives.
- They can also be used in metal transformation and deformation processes, and in particular as a cutting fluid.
- the emulsions obtained according to the invention can also be used in the field of the paper industry where emulsions of relatively fine size are sought.
- Step 1 Synthesis of the monoblock p (ABu) 10 o 0 Composition of the reaction mixture:
- AIBN Azo-bis-isobutyronitrile
- Ethanol, butyl acrylate, azo-bis-isobutyronitrile (AIBN) and S-ethylpropionyl O-ethyldithiocarbonate are introduced into a 100 ml flask fitted with a condenser and a magnetic stirrer.
- the reaction medium is brought to 70 ° C. and is maintained at this temperature for 3 hours.
- Polymer samples are taken regularly to check the conversion.
- the solid content is 30.2% at the end of the reaction.
- Step 2 Synthesis of the diblock p (ABu -b-pfAA nn Composition of the reaction mixture:
- AIBN Azo-bis-isobutyronitrile
- the above ingredients are loaded into a dry container under a dry nitrogen atmosphere for 20 minutes, then transferred to the polymerization reactor, comprising the polymer from the previous step, using a syringe with two tips. .
- reaction mixture is then heated to 60 ° C. and kept at this temperature for 20 hours.
- Polymer samples are taken from time to time to check the conversion.
- the solid content is 30% at the end of the reaction.
- reaction mixture is allowed to cool and the solvents are removed using a rotary evaporator.
- the solid content is 30% at the end of the reaction.
- the number-average molar mass of the copolymer is 5000 g / mol (theoretical value).
- AIBN Azo-bis-isobutyronitrile 0.44 g
- the above-mentioned ingredients are introduced into a 100 ml flask fitted with a condenser and a magnetic stirrer.
- the reaction medium is brought to 70 ° C. and is maintained at this temperature for 3 hours.
- a sample is then taken and analyzed by steric exclusion chromatography and the molar mass in number is of the order of 3100 g / mol.
- Step 2 Synthesis of the diblock p (ABu) 3ooo-bp (VP) 6 ooo Composition of the reaction mixture:
- Ethanol, N-vinyl pyrrolidone and AIBN are introduced. The reaction is maintained for 6 hours from the time when the reagents are introduced.
- composition of the emulsifiable concentrate is a composition of the emulsifiable concentrate:
- the emulsifiable concentrate is prepared by mixing the required quantities of hexadecane (AIdrich), Synperonic® L7 (ICI) and dodecanol (Prolabo) previously heated to 50 ° C in a shaking flask, as well as the polymer P1.
- the copolymer P1 is introduced from a 16% aqueous solution at neutral pH.
- the emulsification is carried out by rapidly introducing the emulsifiable concentrate into the purified water with gentle mechanical stirring with a pale frame at 200 rpm and stirring for 5 minutes.
- the water content of the emulsion is 90%.
- the size distribution of the oil droplets is determined by laser diffraction (Horiba LA-910).
- composition of the emulsifiable concentrate is a composition of the emulsifiable concentrate:
- the amphiphilic / oil ratio is the same as in Example 3.
- composition of the emulsifiable concentrate is a composition of the emulsifiable concentrate:
- the copolymer is introduced from a 16% aqueous solution.
- composition of emulsifiable concentrates Composition of emulsifiable concentrates:
- Géronol FF4 and FF6 products marketed by Rhodia, mixtures of ethoxylated tristyrylphenol and calcium dodecyl benzene sulfonate in isobutanol ** :
- P3 is a diblock copolymer polystyrene - poly acrylic acid with a molecular weight by weight of 3800 - 1200 g / mol (p (St) 38 oo-bp (AA) 12 oo).
- the emulsifiable concentrates are prepared at 20 ° C. by mixing the required quantities of xylene (Prolabo), Geronol FF4 and FF6, as well as the polymer P3, in a shaking flask.
- the copolymer P3 is introduced in dry form.
- the emulsification is carried out by introducing into a cylindrical test tube 9.5 mL city water then 0.5 mL of emulsifiable concentrate, and then making 20 turns.
Abstract
The invention concerns a method for preparing a direct emulsion, which consists in diluting in an aqueous phase a clear emulsifiable concentrate comprising an oil phase, optionally water, and amphiphilic compounds consisting of at least one surfactant, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, optionally at least one co-surfactant and optionally at least one neutralizing agent; the total content in amphiphilic compounds representing 1 to 40 wt. % of the emulsifiable concentrate; the copolymer content representing at least 0,1 to 25 wt. % of said amphiphilic compounds; more than 75 wt. % of the emulsion droplets have an average size not more than 1 mu m; the average size of the droplets of an emulsion obtained by diluting a emulsifiable concentrate free of said copolymer; the total concentration in amphiphilic compounds being the same in both cases.
Description
PROCEDE DE PREPARATION D'UNE EMULSION PROCESS FOR THE PREPARATION OF AN EMULSION
PAR DILUTION D'UN CONCENTRE EMULSIONNABLEBY DILUTION OF AN EMULSIONABLE CONCENTRATE
COMPRENANT UN COPOLYMERE AMPHIPHILECOMPRISING AN AMPHIPHILIC COPOLYMER
La présente invention a pour objet un procédé de préparation d'une emulsion par dilution d'un concentré émulsionnable comprenant un copolymère comprenant au moins un segment hydrophile et au moins un segment hydrophobe.The subject of the present invention is a method for preparing an emulsion by diluting an emulsifiable concentrate comprising a copolymer comprising at least one hydrophilic segment and at least one hydrophobic segment.
L'emploi d'émulsions est très largement développé, que ce soit dans les domaines phytosanitaires, du traitement du métal, dans l'industrie papetière, des peintures, du traitement des fibres textiles (en particulier l'ensimage textile), de la cosmétique, etc.The use of emulsions is very widely developed, whether in phytosanitary fields, metal treatment, in the paper industry, paints, treatment of textile fibers (in particular textile sizing), cosmetics , etc.
Les émulsions comprennent deux phases dont l'une est dispersée dans l'autre, l'ensemble étant maintenu stable grâce à l'emploi de tensioactifs appropriés.The emulsions comprise two phases, one of which is dispersed in the other, the whole being kept stable by the use of suitable surfactants.
L'une des difficultés rencontrées avec les émulsions est que ce sont des systèmes qui ne sont pas à l'équilibre thermodynamique, à la différence des microémulsions qui, elles, le sont. Ainsi, les émulsions, au bout d'un temps plus ou moins long conduiront à une séparation des deux phases.One of the difficulties encountered with emulsions is that these are systems which are not in thermodynamic equilibrium, unlike microemulsions which are. Thus, the emulsions, after a more or less long time will lead to a separation of the two phases.
Par ailleurs, pour atteindre un degré de stabilité satisfaisant, les émulsions comprennent des teneurs non négligeables de tensioactifs. Or la présence de tensioactifs à ces quantités, peut avoir des conséquences négatives limitant l'emploi de ces émulsions ou rendant leur usage plus complexe. En effet, l'utilisation de quantités importantes de tensioactifs dans les émulsions entraîne l'apparition d'un phénomène de mousse qui dans la plupart des cas n'est pas souhaité. Il est donc bien souvent nécessaire d'incorporer dans la formulation, un agent anti-mousse. Une autre difficulté avec la mise en œuvre d'émulsions réside dans le fait que dans certaines applications, on est confronté à l'utilisation de matières actives réactives vis-à-vis de l'eau. Deux possibilités sont alors envisageables, soit empêcher la réaction de la matière active avec l'eau, en masquant la fonction sensible à l'hydrolyse, et prévoir, au moment de l'application de l'émulsion par exemple, l'ajout d'un composé qui débloque la fonction et permette sa réaction avec un composé présent dans la formulation ou introduit à cet effet, possédant des fonctions hydroxyles par exemple. Il est clair que cette méthode est loin d'être applicable à toutes les substances concernées.Furthermore, to achieve a satisfactory degree of stability, the emulsions include non-negligible contents of surfactants. However, the presence of surfactants in these amounts can have negative consequences limiting the use of these emulsions or making their use more complex. Indeed, the use of large amounts of surfactants in the emulsions leads to the appearance of a phenomenon of foam which in most cases is not desired. It is therefore often necessary to incorporate an anti-foaming agent into the formulation. Another difficulty with the use of emulsions lies in the fact that in certain applications, we are confronted with the use of active materials reactive with respect to water. Two possibilities can then be envisaged, either preventing the reaction of the active material with water, by masking the function sensitive to hydrolysis, and providing, at the time of application of the emulsion for example, the addition of a compound which unblocks the function and allows its reaction with a compound present in the formulation or introduced for this purpose, having hydroxyl functions for example. It is clear that this method is far from being applicable to all the substances concerned.
Ainsi, il est nécessaire d'améliorer les propriétés des émulsions et/ou d'en trouver des alternatives qui seraient plus stables au stockage que les émulsions, qui faciliteraient la mise en œuvre de composés réactifs sans avoir à les masquer.Thus, it is necessary to improve the properties of the emulsions and / or to find alternatives which would be more stable on storage than the emulsions, which would facilitate the use of reactive compounds without having to mask them.
Et à ces divers titres, les concentrés émulsionnables représentent une alternative très intéressante.
Ils sont en effet avantageux en ce sens qu'étant exempts d'eau, ils apportent une solution au problème de stabilité des émulsions ainsi qu'à celui de l'emploi de composés hydrolysables. Par ailleurs, ce sont des formulations auto-émulsionnables, ce qui signifie que lorsqu'elles sont mises en contact avec la quantité requise de phase aqueuse, elles donnent une emulsion directe. La difficulté est que pour arriver à obtenir une emulsion dont les caractéristiques de taille des gouttelettes par exemple sont appropriées, il est nécessaire d'employer des teneurs relativement élevées en tensioactifs. Par conséquent, il n'est pas rare que les émulsions issues de concentrés émulsionnables comprennent, elles aussi, des teneurs importantes en tensioactifs. La présente invention a donc pour but de remédier aux inconvénients mentionnés ci-dessus.And for these various titles, emulsifiable concentrates represent a very interesting alternative. They are in fact advantageous in the sense that being free of water, they provide a solution to the problem of stability of the emulsions as well as to that of the use of hydrolysable compounds. Furthermore, they are self-emulsifying formulations, which means that when they are brought into contact with the required quantity of aqueous phase, they give a direct emulsion. The difficulty is that in order to obtain an emulsion with suitable drop size characteristics, for example, it is necessary to use relatively high levels of surfactants. Consequently, it is not uncommon for emulsions obtained from emulsifiable concentrates also to include high levels of surfactants. The present invention therefore aims to remedy the drawbacks mentioned above.
Ainsi, elle a pour objet un procédé de préparation d'une emulsion directe, dans lequel on dilue dans une phase aqueuse un concentré émulsionnable limpide comprenant une phase huile, éventuellement de l'eau, et des composés amphiphiles consistant en au moins un tensioactif, au moins un copolymère possédant au moins un segment hydrophile et au moins un segment hydrophobe, à l'exclusion de copolymères ne comprenant que des segments obtenus à partir d'oxyde d'éthylène et d'oxyde de propylène, éventuellement au moins un co-tensioactif et éventuellement au moins un agent neutralisant ; • la teneur totale en composés amphiphiles représentant 1 à 40 % en poids du concentré émulsionnable ;Thus, its subject is a process for preparing a direct emulsion, in which a clear emulsifiable concentrate comprising an oil phase, optionally water, and amphiphilic compounds consisting of at least one surfactant is diluted in an aqueous phase, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, with the exclusion of copolymers comprising only segments obtained from ethylene oxide and propylene oxide, optionally at least one co- surfactant and optionally at least one neutralizing agent; • the total content of amphiphilic compounds representing 1 to 40% by weight of the emulsifiable concentrate;
• la teneur en copolymère représentant 0,1 à 25 % en poids desdits composés amphiphiles ;• the content of copolymer representing 0.1 to 25% by weight of said amphiphilic compounds;
• plus de 75 % en volume des gouttelettes de l'émulsion ont une taille moyenne inférieure ou égale à 1 μm ;• more than 75% by volume of the droplets of the emulsion have an average size less than or equal to 1 μm;
• la taille moyenne des gouttelettes d'une emulsion obtenue par dilution dudit concentré étant inférieure à celle d'une emulsion obtenue par dilution d'un concentré émulsionnable dépourvu dudit copolymère ; la concentration totale en composés amphiphiles étant la même dans les deux cas. Un autre objet de l'invention est constitué par un concentré émulsionnable limpide comprenant une phase huile, éventuellement de l'eau, et des composés amphiphiles consistant en au moins un tensioactif, au moins un copolymère possédant au moins un segment hydrophile et au moins un segment hydrophobe, à l'exclusion de copolymères ne comprenant que des segments obtenus à partir d'oxyde d'éthylène et d'oxyde de propylène, éventuellement au moins un co-tensioactif et éventuellement au moins un agent neutralisant ;• the average droplet size of an emulsion obtained by diluting said concentrate being less than that of an emulsion obtained by diluting an emulsifiable concentrate devoid of said copolymer; the total concentration of amphiphilic compounds being the same in both cases. Another subject of the invention consists of a clear emulsifiable concentrate comprising an oil phase, optionally water, and amphiphilic compounds consisting of at least one surfactant, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, with the exception of copolymers comprising only segments obtained from ethylene oxide and propylene oxide, optionally at least one co-surfactant and optionally at least one neutralizing agent;
• la teneur totale en composés amphiphiles représentant 1 à 40 % en poids du concentré émulsionnable ;
* la teneur en copolymère représentant 0,1 à 25 % en poids desdits composés amphiphiles. • the total content of amphiphilic compounds representing 1 to 40% by weight of the emulsifiable concentrate; * the content of copolymer representing 0.1 to 25% by weight of said amphiphilic compounds.
La présente invention a donc pour objet des concentrés émulsionnables qui, tout en ayant des teneurs moins élevées en tensioactifs, permettent d'obtenir par dilution, des émulsions dont les caractéristiques de taille des gouttelettes sont du même ordre de grandeur que celles atteintes en diluant des concentrés émulsionnables comprenant les teneurs en tensioactifs usuelles plus élevées.The present invention therefore relates to emulsifiable concentrates which, while having lower levels of surfactants, make it possible to obtain by dilution, emulsions whose droplet size characteristics are of the same order of magnitude as those reached by diluting emulsifiable concentrates including higher levels of usual surfactants.
Ainsi, le procédé selon l'invention permet, grâce à l'utilisation du copolymère amphiphile précité, de baisser de manière substantielle, voire de plus de 10 points dans certains modes de réalisation, la teneur en tensioactif nécessaire pour obtenir des tailles d'émulsion après dilution du concentré aussi fines que celles obtenues avec des teneurs classiques en tensioactifs, soit 10 points plus importantes.Thus, the process according to the invention makes it possible, thanks to the use of the above-mentioned amphiphilic copolymer, to substantially reduce, or even more than 10 points in certain embodiments, the content of surfactant necessary to obtain emulsion sizes. after diluting the concentrate as fine as those obtained with conventional surfactant contents, ie 10 points higher.
En conséquence, le procédé selon l'invention permet de réduire l'inconvénient lié à l'apparition de mousse lors de la dilution du concentré émulsionnable. De plus l'invention procure une plus grande stabilité, dans le temps et/ou en température, de l'émulsion obtenue par dilution du concentré émulsionnable. Par stabilité dans le temps, on entend la durée pendant laquelle on n'observe pas de phénomène de coalescence, de crémage ou de démixtion, à une température donnée. Pas stabilité en température, on entend la , température en dessous de laquelle on n'observe pas ces phénomènes, à une durée donnée. On peut ainsi obtenir une stabilité accrue en utilisant autant ou moins de tensioactif, et/ou une stabilité égale en utilisant moins de tensioactif. On note que la stabilité requise dépend souvent du domaine d'utilisation du composé émulsionnable. Dans le domaines des formulations phytosanitaires, pour les formulations préparées directement dans une exploitation agricole (tank-mix), une stabilité de quelques heures, à des températures de pouvant atteindre environ 40°C, s'avère utile.Consequently, the method according to the invention makes it possible to reduce the drawback associated with the appearance of foam during the dilution of the emulsifiable concentrate. In addition, the invention provides greater stability, over time and / or in temperature, of the emulsion obtained by diluting the emulsifiable concentrate. The term “stability over time” is intended to mean the period during which no phenomenon of coalescence, creaming or demixing is observed, at a given temperature. No temperature stability, we mean the temperature below which these phenomena are not observed, at a given time. It is thus possible to obtain increased stability by using as much or less surfactant, and / or equal stability by using less surfactant. It is noted that the stability required often depends on the field of use of the emulsifiable compound. In the field of phytosanitary formulations, for formulations prepared directly on a farm (tank-mix), a stability of a few hours, at temperatures of up to about 40 ° C, is useful.
Le procédé selon l'invention permet aussi de pouvoir disposer de formulations comprenant des composés sensibles à l'hydrolyse sans avoir à préparer auparavant des dérivés de ces composés pour lesquels la fonction réactive vis-à-vis de l'eau aura été masquée. C'est notamment le cas de compositions destinées par exemple à la préparation de formulations pour peintures. Outre l'avantage de ne pas avoir à mettre en œuvre de système de masquage et de libération de la fonction réactive, le fait d'obtenir des émulsions avec moins de tensioactif présente l'avantage de limiter les phénomènes de migration de tensioactifs observés souvent dans les films, notamment de peintures. Le fait qu'il y ait moins de tensioactif dans les émulsions obtenues à partir des concentrés émulsionnables apporte un avantage supplémentaire quant au recyclage de telles émulsions.
Mais d'autres caractéristiques et avantages de la présente invention apparaîtront plus clairement à la lecture de la description et des exemples qui vont suivre.The method according to the invention also makes it possible to be able to have formulations comprising compounds sensitive to hydrolysis without having to previously prepare derivatives of these compounds for which the reactive function with respect to water will have been masked. This is particularly the case for compositions intended for example for the preparation of formulations for paints. In addition to the advantage of not having to use a masking system and releasing the reactive function, the fact of obtaining emulsions with less surfactant has the advantage of limiting the migration phenomena of surfactants often observed in films, especially paintings. The fact that there is less surfactant in the emulsions obtained from emulsifiable concentrates provides an additional advantage as regards the recycling of such emulsions. However, other characteristics and advantages of the present invention will appear more clearly on reading the description and the examples which follow.
Tout d'abord, par limpide, on désigne un fluide dont la transmittance est de 100 % ; la mesure étant faite à 20°C, au moyen d'un spectromètre UV-visible mesurant l'intensité transmise à la longueur d'onde donnée (λ = 500 nm).First of all, by clear, we mean a fluid whose transmittance is 100%; the measurement being made at 20 ° C., using a UV-visible spectrometer measuring the intensity transmitted at the given wavelength (λ = 500 nm).
De plus, la taille moyenne des gouttelettes de l'émulsion obtenue à partir du concentré émulsionnable correspond au diamètre médian en volume (d50), c'est-à-dire au diamètre de gouttelette égal à 50 % de la distribution cumulative. La taille des gouttelettes est mesurée au moyen d'un granulomètre de type Horiba. Ces mesures de granulométrie sont effectuées en ajoutant à 20CC, et à la concentration souhaitée, le concentré émulsionnable dans de l'eau ; l'opération d'addition étant mise en œuvre sous agitation pendant 5 minutes à 200 tr/min au moyen d'une pâle-cadre.In addition, the average droplet size of the emulsion obtained from the emulsifiable concentrate corresponds to the volume median diameter (d50), that is to say the droplet diameter equal to 50% of the cumulative distribution. The size of the droplets is measured using a Horiba type particle size analyzer. These particle size measurements are carried out by adding the emulsifiable concentrate in water at 20 ° C. and at the desired concentration; the addition operation being carried out with stirring for 5 minutes at 200 rpm using a pale frame.
Comme indiqué précédemment, le concentré émulsionnable comprend une huile et éventuellement de l'eau. Conformément à un mode de réalisation de l'invention, le concentré émulsionnable se présente sous la forme d'une composition monophasique.As indicated previously, the emulsifiable concentrate comprises an oil and optionally water. According to one embodiment of the invention, the emulsifiable concentrate is in the form of a single-phase composition.
L'huile est plus particulièrement choisie parmi les composés dont la solubilité dans l'eau ne dépasse pas 10 % en poids à 20°C. ,The oil is more particularly chosen from compounds whose solubility in water does not exceed 10% by weight at 20 ° C. ,
En outre, l'huile se trouve plus particulièrement sous une forme liquide à la température d'utilisation de l'émulsion obtenue à partir du concentré émulsionnable. Généralement, le domaine de température d'utilisation est proche de la température ambiante, soit environ entre 15 et 40°C, bien que des températures plus élevées ne soient pas exclues ; ces dernières restant toutefois de préférence, inférieures à 100°C. Il est à noter que l'huile peut consister en un mélange de plusieurs composés dont l'un peut ne pas être liquide à température d'utilisation, dès l'instant que l'ensemble est liquide dans cette gamme de température.In addition, the oil is more particularly in a liquid form at the temperature of use of the emulsion obtained from the emulsifiable concentrate. Generally, the operating temperature range is close to ambient temperature, that is to say approximately between 15 and 40 ° C., although higher temperatures are not excluded; the latter, however, preferably remaining below 100 ° C. It should be noted that the oil can consist of a mixture of several compounds, one of which may not be liquid at use temperature, as soon as the assembly is liquid in this temperature range.
Ainsi, comme huiles organiques d'origine animale, on peut citer en autres, l'huile de cachalot, l'huile de baleine, l'huile de phoque, l'huile de sardine, l'huile de hareng, l'huile de squale, l'huile de foie de morue. La cire d'abeille, les graisses de porc ou mouton, peuvent de même convenir.Thus, as organic oils of animal origin, mention may be made, among others, of sperm whale oil, whale oil, seal oil, sardine oil, herring oil, shark, cod liver oil. Beeswax, pork or mutton fats may also be suitable.
A titres d'exemples d'huiles organiques d'origine végétale, on peut mentionner, entre autres, l'huile de colza, l'huile de tournesol, l'huile d'arachide, l'huile d'olive, l'huile de noix, l'huile de maïs, l'huile de soja, l'huile de lin, l'huile de chanvre, l'huile de pépins de raisin, l'huile de coprah, l'huile de palme, l'huile de graines de coton, l'huile de babassu, l'huile de jojoba, l'huile de sésame, l'huile de ricin, la cire de carnauba.As examples of organic oils of vegetable origin, there may be mentioned, among others, rapeseed oil, sunflower oil, peanut oil, olive oil, oil nuts, corn oil, soybean oil, linseed oil, hemp oil, grape seed oil, coconut oil, palm oil, oil cottonseed, babassu oil, jojoba oil, sesame oil, castor oil, carnauba wax.
En ce qui concerne les huiles minérales, on peut citer entre autres les huiles issues de coupes pétrolières comme par exemple les huiles naphténiques, paraffiniques (vaseline), l'hexadécane, ainsi que les cires de paraffine.
Les produits issus de l'alcoolyse des huiles précitées peuvent aussi être utilisés. On ne sortirait du cadre de la présente invention en mettant en œuvre au moins un acide gras, saturé ou non, au moins un ester d'acide gras, saturé ou non, au moins un alcool gras, saturé ou non, ou leurs mélanges. Plus particulièrement, lesdits acides, esters ou alcools comprennent au moins un radical hydrocarboné présentant de 10 à 40 atomes de carbone, plus particulièrement 18 à 40 atomes de carbone, et peuvent comprendre une ou plusieurs doubles liaisons carbone-carbone, conjuguées ou non. Par ailleurs, les acides, esters ou alcools, peuvent comprendre un ou plusieurs groupements hydroxyles. Comme exemples d'acides gras saturés, on peut citer les acides palmitique, stéarique, isostéarique, béhénique.With regard to mineral oils, mention may be made, inter alia, of oils obtained from petroleum fractions such as, for example, naphthenic, paraffinic oils (petroleum jelly), hexadecane, as well as paraffin waxes. The products derived from the alcoholysis of the abovementioned oils can also be used. It would not be departing from the scope of the present invention to use at least one fatty acid, saturated or not, at least one fatty acid ester, saturated or not, at least one fatty alcohol, saturated or not, or mixtures thereof. More particularly, said acids, esters or alcohols comprise at least one hydrocarbon radical having from 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and can comprise one or more carbon-carbon double bonds, conjugated or not. Furthermore, the acids, esters or alcohols can comprise one or more hydroxyl groups. As examples of saturated fatty acids, mention may be made of palmitic, stearic, isostearic and behenic acids.
Comme exemples d'acides gras insaturés, on peut citer les acides myristoléique, palmitoléique, oléique, érucique, linoléique, linolénique, arachidonique, ricinoléique, ainsi que leurs mélanges. Comme esters d'acides gras, on peut citer les esters des acides précédemment listés, pour lesquels la partie dérivant de l'alcool comprend 1 à 6 atomes de carbone, comme les esters de méthyle, d'éthyle, de propyle, d'isopropyle, etc.As examples of unsaturated fatty acids, there may be mentioned myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic, ricinoleic acids, as well as their mixtures. As fatty acid esters, there may be mentioned the esters of the acids previously listed, for which the part deriving from the alcohol comprises 1 to 6 carbon atoms, such as the methyl, ethyl, propyl and isopropyl esters. , etc.
Comme exemple d'alcools, on peut citer ceux correspondants aux acides précités.As an example of alcohols, mention may be made of those corresponding to the abovementioned acids.
Il est de même envisageable de mettre en œuvre les esters des acides précités et de polyols, comme par exemple de glycérol, de polyglycérol (comme par exemple le polyricinoléate de polyglycérol), de glycol, de propylène glycol, d'éthylène glycol, de polyéthylène glycol, de polypropylène glycol, de néopentylglycol (comme par exemple leIt is likewise conceivable to use the esters of the abovementioned acids and of polyols, such as for example glycerol, polyglycerol (such as for example polyglycerol polyricinoleate), glycol, propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, neopentylglycol (such as
Phydroxypivalate de néopentylglycol), de pentaérythritol, de dipentaérythritol, de triméthylolpropane, de sorbitol, de mannitol, de xylitol, de mésoérythritol. L'huile peut de même être choisie parmi les résines alkydes (comme par exemple les résines Coporob 3115 DE, commercialisées par la société Novance), les résines époxy, les (poly)isocyanates masqués ou, avantageusement non masqués dès l'instant que le concentré émulsionnable est exempt d'eau.Neopentylglycol), pentaerythritol, dipentaerythritol, trimethylolpropane, sorbitol, mannitol, xylitol, mesoerythritol. The oil can likewise be chosen from alkyd resins (such as, for example, Coporob 3115 DE resins, sold by the company Novance), epoxy resins, masked (or advantageously unmasked) poly (isocyanates) as soon as the emulsifiable concentrate is free of water.
L'huile peut aussi être choisie parmi les huiles essentielles, les mono-, di- et tri- glycérides.The oil can also be chosen from essential oils, mono-, di- and tri-glycerides.
Les silicones peuvent de même être utilisées dans les concentrés émulsionnables selon l'invention. Sont susceptibles de convenir les silicones constituées en tout ou partie de motifs de formules :The silicones can likewise be used in the emulsifiable concentrates according to the invention. Are likely to be suitable silicones made up in whole or in part of formula motifs:
R'3.aRaSiO1/2 (motif M) et ou R2SiO (motif D) formules où :R ' 3 . a R a SiO 1/2 (motif M) and or R 2 SiO (motif D) formulas where:
- a est un entier de 0 à 3 ;- a is an integer from 0 to 3;
- les radicaux R sont identiques ou différents et représentent :
- un groupe hydrocarboné aliphatique saturé ou insaturé contenant de 1 à 10 atomes de carbone ;- the radicals R are identical or different and represent: - a saturated or unsaturated aliphatic hydrocarbon group containing from 1 to 10 carbon atoms;
- un groupe hydrocarboné aromatique contenant de 6 à 13 atomes de carbone ;- an aromatic hydrocarbon group containing from 6 to 13 carbon atoms;
- un groupe organique polaire lié au silicium par une liaison Si-C ou Si-O-C ; - les radicaux R' sont identiques ou différents et représentent :- a polar organic group linked to silicon by a Si-C or Si-O-C bond; - the radicals R ′ are identical or different and represent:
- un groupe hydrocarboné aliphatique saturé ou insaturé contenant de 1 à 10 atomes de carbone ;- a saturated or unsaturated aliphatic hydrocarbon group containing from 1 to 10 carbon atoms;
- un groupe hydrocarboné aromatique contenant de 6 à 13 atomes de carbone ;- an aromatic hydrocarbon group containing from 6 to 13 carbon atoms;
- une fonction -OH ; - un groupe amino- ou amido-fonctionnel contenant de 1 à 6 atomes de carbone, lié au silicium par une liaison Si-N. De préférence au moins 80% des radicaux R représentent un groupe méthyle. Ces silicones peuvent éventuellement comprendre, de préférence moins de 5 % molaire, des motifs de formules T et/ou Q : RSiO32 (motif T) et/ou SiO2 (motif Q) formule dans laquelle R a la définition donnée ci-dessus.- an -OH function; - an amino- or amido-functional group containing from 1 to 6 carbon atoms, linked to silicon by an Si-N bond. Preferably at least 80% of the radicals R represent a methyl group. These silicones can optionally comprise, preferably less than 5 mol%, units of formulas T and / or Q: RSiO 32 (unit T) and / or SiO 2 (unit Q) formula in which R has the definition given above .
A titre d'exemples de radicaux hydrocarbonés aliphatiques ou aromatiques R, on peut citer les groupes :As examples of aliphatic or aromatic hydrocarbon radicals R, mention may be made of the groups:
- alkyle, de préférence alkyle en Cι C10 éventuellement halogène, tels que méthyle, éthyle, octyle, trifluoropropyle ;- alkyl, preferably C ι C 10 optionally halogenated alkyl, such as methyl, ethyl, octyl, trifluoropropyl;
- alcoxyalkylène, plus particulièrement en C2-C10, de préférence en C2-C6, tels que -CH -CH2-O-CH3 j- alkoxyalkylene, more particularly C 2 -C 10 , preferably C 2 -C 6 , such as -CH -CH 2 -O-CH 3 j
- alcényles, de préférence alcényle en C2-C10, tels que vinyle, allyle, hexényle, décényle, décadiényle ; - alcényloxyalkylène tels que -(CH2)3-O-CH2-CH=CH2, ou alcényloxyalcoxy alkyle tels que -(CH2)3-OCH2-CH2-O-CH=CH2 dans lesquels les parties alkyle sont de préférence en C^C^ et les parties alcényles sont de préférence en C2-C10 ;- alkenyls, preferably C 2 -C 10 alkenyl, such as vinyl, allyl, hexenyl, decenyl, decadienyl; - alkenyloxyalkylene such as - (CH 2 ) 3 -O-CH 2 -CH = CH 2 , or alkenyloxyalkoxy alkyl such as - (CH 2 ) 3 -OCH 2 -CH 2 -O-CH = CH 2 in which the alkyl parts are preferably C ^ C ^ and the alkenyl parts are preferably C 2 -C 10 ;
- aryles, de préférence en C6-C13, tels que phényle.- aryls, preferably C 6 -C 13 , such as phenyl.
A titre d'exemples de groupes organiques polaires R, on peut citer les groupes : - hydroxyfonctionnels tels que des groupes alkyle substitués par un ou plusieurs groupes hydroxy ou di(hydroxyalkyl)amino et éventuellement interrompu par un ou plusieurs groupes bivalents hydroxyalkylamino. Par alkyle on entend une chaîne hydrocarbonée de préférence en C^C , mieux encore en C^C-e; des exemples de ces groupes sont -(CH2)3-OH ; -(CH2) N(CH2CH2OH)2 ; -(CH2)3-N(CH2CH2OH)-CH2-CH2-N(CH2CH2OH)2 :Mention may be made, as examples of polar organic groups R, of: - hydroxyfunctional groups such as alkyl groups substituted by one or more hydroxy or di (hydroxyalkyl) amino groups and optionally interrupted by one or more divalent hydroxyalkylamino groups. By alkyl is meant a hydrocarbon chain preferably C ^ C, more preferably C ^ Ce; examples of these groups are - (CH 2 ) 3 -OH; - (CH 2 ) N (CH 2 CH 2 OH) 2 ; - (CH 2 ) 3 -N (CH 2 CH 2 OH) -CH 2 -CH 2 -N (CH 2 CH 2 OH) 2 :
- aminofonctionnels tels que alkyle substitué par un ou plusieurs groupes amino ou aminoalkylamino où alkyle est tel que défini ci-dessus ; des exemples en sont -(CH2)3-NH2 ; (CH2)3-NH-(CH2)2NH2 ;
- amidofonctionnels tels que alkyle substitué par un ou plusieurs groupes acylamino et éventuellement interrompu par un ou plusieurs groupes bivalents alkyl-CO-N< où alkyle est tel que défini ci-dessus et acyle représente alkylcarbonyle ; un exemple est le groupe -(CH2)3-N(COCH3)-(CH2)2NH(COCH3); - carboxyfonctionnels tels que carboxyalkyle éventuellement interrompu par un ou plusieurs atomes d'oxygène ou de soufre où alkyle est tel que défini ci-dessus ; un exemple est le groupe -CH2-CH2-S-CH2-COOH. A titre d'exemples de radicaux R', on peut citer les groupes :- aminofunctional such as alkyl substituted by one or more amino or aminoalkylamino groups where alkyl is as defined above; examples are - (CH 2 ) 3 -NH 2 ; (CH 2 ) 3 -NH- (CH 2 ) 2 NH 2 ; - amidofunctional such as alkyl substituted by one or more acylamino groups and optionally interrupted by one or more bivalent alkyl-CO-N <groups where alkyl is as defined above and acyl represents alkylcarbonyl; an example is the group - (CH 2 ) 3 -N (COCH 3 ) - (CH 2 ) 2 NH (COCH3); - functional carboxy such as carboxyalkyl optionally interrupted by one or more oxygen or sulfur atoms where alkyl is as defined above; an example is the group -CH 2 -CH 2 -S-CH 2 -COOH. As examples of radicals R ′, there may be mentioned the groups:
- alkyle, de préférence alkyle en C C10 éventuellement halogène, tels que méthyle, éthyle, octyle, trifluoropropyle ;- alkyl, preferably CC 10 optionally halogenated alkyl, such as methyl, ethyl, octyl, trifluoropropyl;
- aryles, de préférence en C6-C13, tels que phényle ;- aryls, preferably C 6 -C 13 , such as phenyl;
- aminofonctionnels tels que alkyle ou aryle substitué par amino, alkyle étant de préférence en C C6 et aryle désignant un groupe aromatique cyclique hydrocarboné de préférence en C6-C13 tel que phényle ; des exemples en sont éthylamino, phénylamino ;- aminofunctional such as alkyl or aryl substituted by amino, alkyl preferably being CC 6 and aryl denoting a cyclic aromatic hydrocarbon group preferably C 6 -C 13 such as phenyl; examples are ethylamino, phenylamino;
- amidofonctionnels tels que alkylcarbonylamino où alkyle est de préférence en C C6 ; des exemples en sont méthylacétamido.- amidofunctional such as alkylcarbonylamino where alkyl is preferably CC 6 ; examples are methylacetamido.
A titre d'exemples concrets de "motifs D" on peut citer : (CH3)2SiO ;As concrete examples of "D units", mention may be made of: (CH 3 ) 2 SiO;
CH3(CH=CH2)SiO ; CH3(C6H5)SiO ; (C6H5)2SiO ; CH3(CH2-CH2-CH2OH)SiO. A titre d'exemples concrets de "motifs M", on peut citer : (CH3)3SiO 2 ;CH 3 (CH = CH 2 ) SiO; CH 3 (C 6 H 5 ) SiO; (C 6 H 5 ) 2 SiO; CH 3 (CH 2 -CH 2 -CH 2 OH) SiO. As concrete examples of "M units", there may be mentioned: (CH 3 ) 3 SiO 2 ;
(CH3)2(OH)SiO1/2 ; (CH3)2(CH=CH2)SiO1/2 ; (OCH3)3SiO1/2 : [O-C(CH3)=CH2]3SiO1/2 :(CH 3 ) 2 (OH) SiO 1/2 ; (CH 3 ) 2 (CH = CH 2 ) SiO 1/2 ; (OCH 3 ) 3 SiO 1/2 : [OC (CH 3 ) = CH 2 ] 3 SiO 1/2 :
[ON=C(CH3)]3SiO1/2 ; (NH-CH3)3SiO1/2 ; (NH-CO-CH3)3SiO1/2.[ON = C (CH 3 )] 3 SiO 1/2 ; (NH-CH 3 ) 3 SiO 1/2 ; (NH-CO-CH 3 ) 3 SiO 1/2 .
A titre d'exemples concrets de "motifs T", on peut citer : CH3SiO32 ;As concrete examples of "T units", mention may be made of: CH 3 SiO 32 ;
(CH=CH2)SiO3/2. Lorsque les silicones contiennent des radicaux R réactifs et/ou polaires (tels que(CH = CH 2 ) SiO 3/2 . When the silicones contain reactive and / or polar radicals R (such as
OH, vinyle, allyle, héxényle, aminoalkyles ....), ces derniers ne représentent généralement pas plus de 5% du poids de la silicone, et de préférence pas plus de 1 % du poids de la silicone.OH, vinyl, allyl, hexenyl, aminoalkyls, etc.), the latter generally do not represent more than 5% by weight of the silicone, and preferably not more than 1% by weight of the silicone.
Peuvent être utilisés des huiles volatiles comme l'hexaméthyldisiloxane, l'octaméthyldisiloxane, le décaméthyltétrasiloxane, le dodécaméthylpentasiloxane, le tétradécaméthylhexasiloxane, l'hexadécaméthylhexa siloxane ; l'heptaméthyl-May be used volatile oils such as hexamethyldisiloxane, octamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylhexa siloxane; the heptaméthyl-
3[(triméthyl-silyl)oxy]trisiloxane, l'hexaméthyl-3,3 bis[(triméthyl-silyl)oxy]trisiloxane ; l'hexaméthylcyclotrisiloxane, l'octaméthylcyclotétrasiloxane, le décaméthylcyclopenta siloxane, le dodécaméthylcyclohexasiloxane, le pentaméthyl[(tri-méthylsilyl)oxy] cyclotrisiloxane.3 [(trimethyl-silyl) oxy] trisiloxane, 3,3-hexamethyl bis [(trimethyl-silyl) oxy] trisiloxane; hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopenta siloxane, dodecamethylcyclohexasiloxane, pentamethyl [(tri-methylsilyl) oxy] cyclotrisiloxane.
On peut de même mettre en œuvre des silicones non volatiles comme les huiles et gommes polydimethylsiloxanes et α,ω-bis(hydroxy) polydimethylsiloxanes ainsi que
les gommes polydimethylsiloxanes, polyphénylméthylsiloxane et α,ω-bis(hydroxy)poly diméthylsiloxanes.It is likewise possible to use non-volatile silicones such as polydimethylsiloxane oils and gums and α, ω-bis (hydroxy) polydimethylsiloxanes as well as polydimethylsiloxanes, polyphenylmethylsiloxane and α, ω-bis (hydroxy) poly dimethylsiloxanes gums.
On préfère plus particulièrement les huiles α,ω-bis(triméthyl)polydiméthyl siloxanes, les huiles α,ω-bis(hydroxy)polydiméthyl siloxanes, et tout particulièrement les silicones de type polydiméthylsiloxane (diméthicone) et diphényldiméthicone.More particularly preferred are the α, ω-bis (trimethyl) polydimethyl siloxane oils, the α, ω-bis (hydroxy) polydimethyl siloxane oils, and very particularly the silicones of polydimethylsiloxane (dimethicone) and diphenyldimethicone type.
L'huile peut éventuellement comprendre une matière active, à moins qu'elle ne soit elle-même considérée comme matière active.The oil may optionally include an active ingredient, unless it is itself considered as an active ingredient.
La matière active, si elle est différente de l'huile, se présente sous une forme miscible à l'huile ou encore solubilisée dans un solvant organique miscible à l'huile. De plus, la matière active est choisie parmi les composés dont la solubilité dans l'eau ne dépasse pas 10 % en poids, à 20°C.The active ingredient, if it is different from the oil, is in a form miscible with oil or even dissolved in an organic solvent miscible with oil. In addition, the active ingredient is chosen from compounds whose solubility in water does not exceed 10% by weight, at 20 ° C.
A titre d'exemple de matières actives dans le domaine de la cosmétique on peut citer les huiles silicones appartenant par exemple à la famille des diméthicones ; les vitamines lipophiles, comme la vitamine A et ses dérivés notamment ses esters comme l'acétate, le palmitate, le propionate, la vitamine B2, l'acide pantothénique, la vitamine D et la vitamine E.By way of example of active materials in the field of cosmetics, mention may be made of silicone oils belonging for example to the family of dimethicones; lipophilic vitamins, such as vitamin A and its derivatives, in particular its esters such as acetate, palmitate, propionate, vitamin B2, pantothenic acid, vitamin D and vitamin E.
Dans le domaine de l'agrochimie, les matières actives phytosanitaires peuvent être choisies parmi la famille des α-cyano-phénoxybenzyl carboxylates ou des α-cyano- halogénophénoxy-carboxylates, la famille des N-méthylcarbonates comprenant des substituants aromatiques, les matières actives telles que AIdrin, Azinphos-methyl, Benfluralin, Bifenthrin, Chlorphoxim, Chlorpyrifos, Fluchloralin, Fluroxypyr, Dichlorvos, Malathion, Molinate, Parathion, Permethrin, Profenofos, Propiconazole, Prothiofos, Pyrifenox, Butachlor, Metolachlor, Chlorimephos, Diazinon, Fluazifop-P-butyl, Heptopargil, Mecarbam, Propargite, Prosulfocarb, Bromophos-ethyl, Carbophenothion, Cyhalothrin.In the field of agrochemicals, the phytosanitary active materials can be chosen from the family of α-cyano-phenoxybenzyl carboxylates or α-cyano-halogenophenoxy-carboxylates, the family of N-methylcarbonates comprising aromatic substituents, the active materials such as AIdrin, Azinphos-methyl, Benfluralin, Bifenthrin, Chlorphoxim, Chlorpyrifos, Fluchloralin, Fluroxypyr, Dichlorvos, Malathion, Molinate, Parathion, Permethrin, Profenofos, Propiconazole, Prothiofos, Pyrifenox, Butriflorazin, Metollorin , Heptopargil, Mecarbam, Propargite, Prosulfocarb, Bromophos-ethyl, Carbophenothion, Cyhalothrin.
Lesdites matières actives mentionnées ci-dessus peuvent éventuellement être sous une forme solubilisée dans un solvant approprié, par exemple le xylène, le Solvesso®.Said active ingredients mentioned above can optionally be in a form dissolved in a suitable solvent, for example xylene, Solvesso®.
On peut mentionner en tant que matières actives possibles les anti-mousses silicones ou organiques, utilisés dans de nombreux domaines, comme celui de la détergence par exemple.Mention may be made, as possible active materials, of silicone or organic antifoams, used in many fields, such as detergency for example.
Il est de même possible d'utiliser des matières actives telles que celles entrant dans la composition de lubrifiants pour le travail ou la déformation des matériaux. La matière active est habituellement une huile, un dérivé d'une huile ou encore un ester d'acide gras.It is likewise possible to use active materials such as those used in the composition of lubricants for working or deformation of materials. The active ingredient is usually an oil, an oil derivative or a fatty acid ester.
La matière active peut aussi être choisie parmi les solvants organiques ou les mélanges de tels solvants pas ou peu miscibles dans l'eau, comme notamment ceux mis en œuvre pour le nettoyage ou le décapage, tels que les coupes pétrolières
aromatiques, les composés terpéniques comme les D- ou L- limonènes, ainsi que les solvants comme le Solvesso®. Conviennent aussi comme solvants, les esters aliphatiques, comme les esters méthyliques d'un mélange d'acides acétique, succinique et glutarique (mélange d'acides sous-produit de la synthèse du Nylon), les huiles hydrocarbonées comme l'huile de vaseline, et les solvants chlorés.The active material can also be chosen from organic solvents or mixtures of such solvents which are not or only slightly miscible in water, such as in particular those used for cleaning or pickling, such as petroleum cuts. aromatic, terpene compounds such as D- or L-limonenes, as well as solvents such as Solvesso®. Also suitable as solvents, aliphatic esters, such as methyl esters of a mixture of acetic, succinic and glutaric acids (mixture of acids by-product of the synthesis of Nylon), hydrocarbon oils such as petroleum jelly, and chlorinated solvents.
Si une matière active différente de l'huile est présente, sa teneur est habituellement inférieure ou égale à 50 % en poids d'huile, de préférence comprise entre 10 et 50 % en poids d'huile.If an active ingredient other than the oil is present, its content is usually less than or equal to 50% by weight of oil, preferably between 10 and 50% by weight of oil.
La teneur totale en huile dans le concentré émulsionnable, y compris le cas échéant la matière active, représente de manière avantageuse de 60 à 95 % en poids du concentré émulsionnable.The total oil content in the emulsifiable concentrate, including, where appropriate, the active material, advantageously represents from 60 to 95% by weight of the emulsifiable concentrate.
Au cas où le concentré émulsionnable comprend de l'eau, sa teneur est telle que le concentré émulsionnable reste limpide au sens indiqué auparavant. La teneur varie en fonction des divers éléments constitutifs du concentré émulsionnable et reste facilement déterminable par l'homme du métier.If the emulsifiable concentrate comprises water, its content is such that the emulsifiable concentrate remains clear in the sense indicated above. The content varies according to the various constituent elements of the emulsifiable concentrate and remains easily determinable by a person skilled in the art.
A titre d'illustration, la teneur en eau dans la concentré émulsionnable, si elle est présente, est inférieure ou égale à 10 % en poids du concentré.By way of illustration, the water content in the emulsifiable concentrate, if it is present, is less than or equal to 10% by weight of the concentrate.
Le concentré émulsionnable comprend de plus des composés amphiphiles consistant en au moins un tensioactif, au moins un copolymère possédant au moins un segment hydrophile et au moins un segment hydrophobe, éventuellement au moins un co-tensioactif et éventuellement au moins un agent neutralisant.The emulsifiable concentrate further comprises amphiphilic compounds consisting of at least one surfactant, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, optionally at least one co-surfactant and optionally at least one neutralizing agent.
Il est précisé que l'ensemble comprenant le tensioactif, éventuellement le co- tensioactif et éventuellement l'agent neutralisant est soluble dans l'huile, à température ambiante (environ 20 °C). De préférence, le ou les tensioactifs sont choisis parmi les tensioactifs solubles dans l'huile aux concentrations mises en œuvre dans l'invention.It is specified that the assembly comprising the surfactant, optionally the co-surfactant and optionally the neutralizing agent is soluble in oil, at ambient temperature (approximately 20 ° C.). Preferably, the surfactant (s) are chosen from surfactants soluble in oil at the concentrations used in the invention.
Avantageusement, les tensioactifs sont choisis parmi les tensioactifs non ioniques ou anioniques.Advantageously, the surfactants are chosen from nonionic or anionic surfactants.
Selon une première variante, le ou les tensioactifs sont choisis parmi les tensioactifs non ioniques.According to a first variant, the surfactant (s) are chosen from nonionic surfactants.
A titre d'illustration, conviennent notamment, seuls ou en mélange : - les alcools gras alcoxylés, plus particulièrement comprenant de 6 à 22 atomes de carbone ; les mono-, di- et tri-glycérides alcoxylés ; - les acides gras alcoxylés, plus particulièrement comprenant de 6 à 22 atomes de carbone ; les esters de sorbitan alcoxylés (des esters du sorbitol cyclisés d'acide gras comprenant de 10 à 20 atomes de carbone) ;
les aminés grasses alcoxylées, plus particulièrement comprenant de 6 à 22 atomes de carbone ;By way of illustration, the following are particularly suitable, alone or as a mixture: - alkoxylated fatty alcohols, more particularly comprising from 6 to 22 carbon atoms; alkoxylated mono-, di- and tri-glycerides; - alkoxylated fatty acids, more particularly comprising from 6 to 22 carbon atoms; alkoxylated sorbitan esters (cyclized fatty acid sorbitol esters having 10 to 20 carbon atoms); alkoxylated fatty amines, more particularly comprising from 6 to 22 carbon atoms;
- les alkylphénols alcoxylés, plus particulièrement comprenant un ou deux groupes alkyles, linéaires ou ramifiés, ayant 4 à 12 atomes de carbone ; - les alkylpolyglucosides ; les tensioactifs polyoxyalkylénés, comme par exemple les composés commercialisés sous la gamme Pluronic ou Poloxamer par la société BASF ;- Alkoxylated alkylphenols, more particularly comprising one or two alkyl groups, linear or branched, having 4 to 12 carbon atoms; - alkylpolyglucosides; polyoxyalkylenated surfactants, such as for example the compounds sold under the Pluronic or Poloxamer range by the company BASF;
- les mono- et di- alcanolamides alcoxylés ; seuls ou en mélanges. Selon une deuxième variante, le ou les tensioactifs sont choisis parmi les tensioactifs anioniques sous forme acide ou associé(s) à un contre ion multivalent.- alkoxylated mono- and di-alkanolamides; alone or in mixtures. According to a second variant, the surfactant (s) are chosen from anionic surfactants in acid form or associated (s) with a multivalent counter ion.
Le contre-ion multivalent est de préférence un métal alcalino-terreux comme le magnésium, le calcium, seuls ou combinés.The multivalent counterion is preferably an alkaline earth metal such as magnesium, calcium, alone or in combination.
Quant aux tensioactifs, les composés listés de manière non exhaustive ci- dessous, peuvent être mis en œuvre :As for the surfactants, the compounds listed in a non-exhaustive manner below can be used:
- les alkylesters sulfonates, par exemple de formule R-CH(SO3M)-CH2COOR', où R représente un radical hydrocarboné en C8-C20, de préférence en C10-C16, éventuellement porteur d'une ou plusieurs insaturations, R' un radical alkyle en Ci-Ce, de préférence en C C3 et M un atome d'hydrogène ou un cation alcalino-terreux. On peut citer tout particulièrement les méthyl ester sulfonates dont le radical R est en C14-C16 ;- the alkyl esters sulfonates, for example of formula R-CH (SO 3 M) -CH2COOR ', where R represents a C 8 -C 20 , preferably C 10 -C 16 hydrocarbon radical, optionally carrying one or more unsaturations, R 'a C1-C6 alkyl radical, preferably in CC 3 and M a hydrogen atom or an alkaline-earth cation. Mention may very particularly be made of methyl ester sulfonates whose radical R is C 14 -C 16 ;
- les alkylesters sulfates, par exemple de formule R-CH(OSO3M)-CH2COOR', où R représente un radical hydrocarboné en C8-C2o, de préférence en C10-C16, éventuellement porteur d'une ou plusieurs insaturations, R' un radical alkyle en C Cβ, de préférence en C^Cs et M un atome d'hydrogène ou un cation alcalino-terreux ; les alkylbenzènesulfonates, plus particulièrement en C9-C20, les alkylsulfonates primaires ou secondaires, notamment en Cβ-C22, les alkylglycérol sulfonates ; les alkylsulfates par exemple de formule ROSO3M, où R représente un radical alkyle ou hydroxyalkyle en C10-C24, de préférence en C12-C20 ; M un atome d'hydrogène ou un cation de même définition que ci-dessus ; les alkyléthersulfates par exemple de formule RO(AO)nSO3M où R représente un radical alkyle ou hydroxyalkyle en C10-C24, de préférence en C12-C20 ; OA représentant un groupement éthoxylé et ou propoxylé ; M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, n variant généralement de 1 à 4, comme par exemple le laurylethersulfate avec n = 2 ;- the alkyl esters sulfates, for example of formula R-CH (OSO 3 M) -CH2COOR ', where R represents a C 8 -C 2 o, preferably C 10 -C 16 hydrocarbon radical, optionally bearing one or several unsaturations, R ′ an alkyl radical in C Cβ, preferably in C ^ Cs and M a hydrogen atom or an alkaline earth cation; alkylbenzenesulfonates, more particularly C 9 -C 20 , primary or secondary alkylsulfonates, especially Cβ-C 22 , alkylglycerol sulfonates; alkyl sulphates, for example of formula ROSO 3 M, in which R represents a C 10 -C 24 , preferably C 12 -C 20 , alkyl or hydroxyalkyl radical; M a hydrogen atom or a cation of the same definition as above; alkyl ether sulfates for example of formula RO (AO) n SO 3 M where R represents a C 10 -C 24 , preferably C 12 -C 20 , alkyl or hydroxyalkyl radical; OA representing an ethoxylated and or propoxylated group; M representing a hydrogen atom or a cation of the same definition as above, n generally varying from 1 to 4, such as for example laurylethersulfate with n = 2;
- les alkylamides sulfates, par exemple de formule RCONHR'OSO3M où R représente un radical alkyle en C2-C22, de préférence en C6-C20, R' un radical
alkyle en C2-C3, M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérivés polyalcoxylés (éthoxylés et/ou propoxylés) ; les sels d'acides gras saturés ou insaturés, par exemple comme ceux en C8- C24, de préférence en C14-C20 et d'un cation alcalino-terreux, les N-acyl N- alkyltau rates, les alkyliséthionates, les alkylsuccinamates et alkylsulfosuccinates, les monoesters ou diesters de sulfosuccinates, les N-acyl sarcosinates, les polyéthoxycarboxylates ; et les mono et di esters phosphates, par exemple de formule suivante : (RO)x-P(=O)(OM)x ou R représente un radical alkyle, alkylaryle, arylalkyle, aryle, éventuellement polyalcoxylés, x et x' étant égaux à 1 ou 2, à la condition que la somme de x et x' soit égale à 3, M représentant un atome d'hydrogène ou un cation alcalino-terreux ; seuls ou en mélanges. La teneur en tensioactif dans le concentré émulsionnable est telle que la teneur en totale en amphiphiles soit comprise entre 1 et 40 % en poids du concentré émulsionnable.- the sulphate alkylamides, for example of formula RCONHR'OSO 3 M where R represents a C 2 -C 22 , preferably C 6 -C 20 , alkyl radical, R 'a radical C 2 -C 3 alkyl, M representing a hydrogen atom or a cation of the same definition as above, as well as their polyalkoxylated derivatives (ethoxylated and / or propoxylated); the salts of saturated or unsaturated fatty acids, for example such as those in C 8 - C 24 , preferably in C 14 -C 20 and of an alkaline-earth cation, N-acyl N-alkyltau rates, alkylisethionates, alkylsuccinamates and alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, polyethoxycarboxylates; and the mono and di phosphate esters, for example of the following formula: (RO) x -P (= O) (OM) x or R represents an alkyl, alkylaryl, arylalkyl, aryl radical, optionally polyalkoxylated, x and x ′ being equal to 1 or 2, provided that the sum of x and x 'is equal to 3, M representing a hydrogen atom or an alkaline earth cation; alone or in mixtures. The surfactant content in the emulsifiable concentrate is such that the total content of amphiphiles is between 1 and 40% by weight of the emulsifiable concentrate.
Parmi les composés amphiphiles présents dans le concentré émulsionnable, figurent les copolymères possédant au moins un segment hydrophile et au moins un segment hydrophobe, à l'exclusion de copolymères ne comprenant que des segments obtenus à partir d'oxyde d'éthylène et d'oxyde de propylène.Among the amphiphilic compounds present in the emulsifiable concentrate, there are copolymers having at least one hydrophilic segment and at least one hydrophobic segment, with the exception of copolymers comprising only segments obtained from ethylene oxide and oxide propylene.
Le composé amphiphile est choisi de telle sorte que l'ensemble des composés amphiphiles soit soluble dans l'huile, le cas échéant, en présence d'une faible quantité d'eau. De préférence, ledit composé amphiphile est choisi parmi les composés solubles dans l'huile.The amphiphilic compound is chosen so that all of the amphiphilic compounds are soluble in oil, if necessary, in the presence of a small amount of water. Preferably, said amphiphilic compound is chosen from compounds soluble in oil.
En ce qui concerne plus spécialement le segment hydrophobe du copolymère, celui-ci peut être obtenu à partir de l'un ou plusieurs des monomères suivants : les esters des acides mono- ou poly- carboxyliques, linéaires, ramifiés, cycliques ou aromatiques, comprenant au moins une insaturation éthylénique, et éventuellement porteurs d'un groupement hydroxyle ; les nitriles αβ-éthyléniquement insaturés, les éthers vinyliques, les esters vinyliques, les monomères vinylaromatiques, les halogénures de vinyle ou de vinylidène, les monomères hydrocarbonés, linéaires ou ramifiés, aromatiques ou non, comprenant au moins une insaturation éthylénique, l'oxyde de propylène, l'oxyde de butylène, seuls ou en mélanges, ainsi que les macromonomères dérivant de tels monomères.
A titre d'exemples particuliers de monomères hydrophobes susceptibles d'entrer dans la préparation du ou des segments hydrophobes du copolymère amphiphile à segments, on peut citer :As regards more particularly the hydrophobic segment of the copolymer, this can be obtained from one or more of the following monomers: the esters of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation, and optionally carrying a hydroxyl group; αβ-ethylenically unsaturated nitriles, vinyl ethers, vinyl esters, vinyl aromatic monomers, vinyl or vinylidene halides, linear or branched hydrocarbon monomers, aromatic or not, comprising at least one ethylenic unsaturation, oxide of propylene, butylene oxide, alone or in mixtures, as well as the macromonomers derived from such monomers. As specific examples of hydrophobic monomers capable of entering into the preparation of the hydrophobic segment (s) of the amphiphilic segmented copolymer, mention may be made of:
- les esters d'acide (méth)acrylique avec un alcool comprenant 1 à 12 atomes de carbone comme le (méth)acrylate de méthyle, le (méth)acrylate d'éthyle, le- (meth) acrylic acid esters with an alcohol comprising 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate,
(méth)acrylate de propyle, le (méth)acrylate de n-butyle, le (méth)acrylate de t- butyle, le (méth)acrylate d'isobutyle, l'acrylate de 2-éthylhexyl ; l'acétate de vinyle, le Versatate® de vinyle, le propionate de vinyle, le chlorure de vinyle, le chlorure de vinylidène, le méthyl vinyléther, l'éthyl vinyléther ; - les nitriles vinyliques incluent plus particulièrement ceux ayant de 3 àpropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl acrylate; vinyl acetate, vinyl Versatate®, vinyl propionate, vinyl chloride, vinylidene chloride, methyl vinyl ether, ethyl vinyl ether; - vinyl nitriles more particularly include those having from 3 to
12 atomes de carbone, comme en particulier l'acrylonitrile et le méthacrylonitrile ; le styrène, l'α-méthylstyrène, le vinyltoluène, le butadiène, l'isoprène, le chloroprène ; - l'oxyde de propylène, l'oxyde de butylène, seuls ou en mélanges, ainsi que les macromonomères dérivant de tels monomères.12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile; styrene, α-methylstyrene, vinyltoluene, butadiene, isoprene, chloroprene; - propylene oxide, butylene oxide, alone or in mixtures, as well as the macromonomers derived from such monomers.
Les monomères préférés sont les esters de l'acide acrylique avec les alcools linéaires ou ramifiés en C1-C4 tels que l'acrylate de méthyle, d'éthyle, de propyle et de butyle, les esters vinyliques comme l'acétate de vinyle, le styrène, l'α-méthylstyrène. Pour ce qui a trait au segment hydrophile du copolymère amphiphile, ce dernier peut être obtenu à partir d'un ou de plusieurs monomères présentant une fonction anionique ou anionisable.The preferred monomers are the esters of acrylic acid with linear or branched C1-C4 alcohols such as methyl, ethyl, propyl and butyl acrylate, vinyl esters such as vinyl acetate, styrene, α-methylstyrene. As regards the hydrophilic segment of the amphiphilic copolymer, the latter can be obtained from one or more monomers having an anionic or anionizable function.
Il est précisé que dans les conditions de pH d'utilisation du copolymère, les fonctions du ou des segments anioniques du copolymère se trouvent sous une forme au moins partiellement ionisée (dissociée). Plus particulièrement, au moins 10 % en mole des fonctions du ou des segments sont sous forme ionisée. La détermination de cette valeur ne pose pas de problème à l'homme de l'art ; elle est notamment fonction du pKa des fonctions ionisables des motifs du copolymère et du nombre de ces fonctions (soit du nombre de moles de monomère portant des fonctions ionisables mis en œuvre lors de la préparation du copolymère).It is specified that under the conditions of pH of use of the copolymer, the functions of the anionic segment or segments of the copolymer are in an at least partially ionized (dissociated) form. More particularly, at least 10 mol% of the functions of the segment or segments are in ionized form. The determination of this value poses no problem to those skilled in the art; it is in particular a function of the pKa of the ionizable functions of the units of the copolymer and of the number of these functions (ie of the number of moles of monomer carrying ionizable functions used during the preparation of the copolymer).
Plus particulièrement comprenant au moins une fonction carboxylique, sulfonique, sulfurique, phosphonique, phosphorique, sulfosuccinique, leurs sels, ainsi que les macromonomères correspondants.More particularly comprising at least one carboxylic, sulfonic, sulfuric, phosphonic, phosphoric, sulfosuccinic function, their salts, as well as the corresponding macromonomers.
Plus précisément, le ou les monomères anioniques ou anionisables peuvent être choisis parmi les suivants : les acides mono- ou poly- carboxyliques linéaires, ramifiés, cycliques ou aromatiques, les dérivés N-substitués de tels acides ; les monoesters d'acides polycarboxyliques, comprenant au moins une insaturation éthylénique ;
les acides vinyl carboxyliques linéaires, ramifiés, cycliques ou aromatiques ; les aminoacides comprenant une ou plusieurs insaturations éthyléniques ; seuls ou en mélanges, leurs précurseurs, leurs homologues sulfoniques ou phosphoniques, leurs sels, ainsi que les macromonomères dérivant de tels monomères ou de leurs sels.More specifically, the anionic or anionizable monomer (s) can be chosen from the following: linear, branched, cyclic or aromatic mono- or polycarboxylic acids, N-substituted derivatives of such acids; monoesters of polycarboxylic acids, comprising at least one ethylenic unsaturation; linear, branched, cyclic or aromatic vinyl carboxylic acids; amino acids comprising one or more ethylenic unsaturations; alone or as mixtures, their precursors, their sulfonic or phosphonic counterparts, their salts, as well as the macromonomers derived from such monomers or from their salts.
A titre d'exemples de monomères anioniques/anionisables, on peut citer sans intention de s'y limiter : l'acide acrylique, l'acide méthacrylique, l'acide fumarique, l'acide itaconique, l'acide citraconique, l'acide maléique, l'acide acrylamido glycolique, l'acide 2- propène 1-sulfonique, l'acide méthallyl sulfonique, l'acide styrène sulfonique, l'acide α-acrylamido méthylpropane sulfonique, le 2-sulfoéthylène méthacylate, l'acide sulfopropyl acrylique, l'acide bis-sulfopropyl acrylique, l'acide bis- sulfopropyl méthacrylique, l'acide sulfatoéthyl méthacrylique, le monoester phosphate d'acide hydroxyéthyl méthacrylique, ainsi que les sels de métal alcalin, comme le sodium, le potassium, ou d'ammonium ; l'acide vinyl sulfonique, l'acide vinylbenzène sulfonique, l'acide vinyl phosphonique, l'acide vinylidène phosphonique, l'acide vinyl benzoïque, ainsi que les sels de métal alcalin, comme le sodium, le potassium, ou d'ammonium ; le N-méthacryloyl alanine, le N-acryloy -hydroxy-glycine ; seuls ou en mélanges, ainsi que les macromonomères dérivant de tels monomères.As examples of anionic / anionizable monomers, there may be mentioned without intending to be limited thereto: acrylic acid, methacrylic acid, fumaric acid, itaconic acid, citraconic acid, acid maleic, acrylamido glycolic acid, 2-propene 1-sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, α-acrylamido methylpropane sulfonic acid, 2-sulfoethylene methacylate, sulfopropyl acrylic acid , bis-sulfopropyl acrylic acid, bis-sulfopropyl methacrylic acid, sulfatoethyl methacrylic acid, hydroxyethyl methacrylic acid phosphate ester, as well as alkali metal salts, such as sodium, potassium, or ammonium; vinyl sulfonic acid, vinylbenzene sulfonic acid, vinyl phosphonic acid, vinylidene phosphonic acid, vinyl benzoic acid, as well as alkali metal salts, such as sodium, potassium, or ammonium; N-methacryloyl alanine, N-acryloy-hydroxy-glycine; alone or in mixtures, as well as the macromonomers derived from such monomers.
On ne sortirait pas du cadre de la présente invention en mettant en œuvre des monomères précurseurs de ceux qui viennent d'être cités. En d'autres termes, ces monomères présentent des motifs qui, une fois incorporés dans la chaîne polymère, peuvent être transformés, notamment par un traitement chimique tel que l'hydrolyse, pour redonner les espèces anioniques / anionisables précitées. Par exemple, les monomères totalement ou partiellement estérifiés des monomères précités peuvent être mis en œuvre pour être, par la suite, hydrolyses totalement ou en partie.It would not be departing from the scope of the present invention to use monomers which are precursors of those which have just been mentioned. In other words, these monomers have units which, once incorporated in the polymer chain, can be transformed, in particular by a chemical treatment such as hydrolysis, to restore the above-mentioned anionic / anionizable species. For example, the fully or partially esterified monomers of the aforementioned monomers can be used to be, subsequently, completely or partially hydrolyzed.
Selon une autre possibilité, le ou les segments hydrophiles peuvent être obtenus à partir d'un ou de plusieurs monomères présentant une fonction cationique ou cationisable.According to another possibility, the hydrophilic segment or segments can be obtained from one or more monomers having a cationic or cationizable function.
A ce titre, peuvent être mis en œuvre :As such, the following can be implemented:
- les (méth)acrylates d'aminoalkyle, les (méth)acrylamides d'aminoalkyle ; les monomères comprenant au moins une fonction aminé secondaire, tertiaire ou quaternaire, ou un groupe hétérocyclique contenant un atome d'azote, la vinylamine, l'éthylène i ine ;- aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides; monomers comprising at least one secondary, tertiary or quaternary amine function, or a heterocyclic group containing a nitrogen atom, vinylamine, ethylene;
- les sels d'ammonium de diallyldialkyl ; seuls ou en mélanges, ou les sels correspondants ; ainsi que les macromonomères dérivant de tels monomères.
S'ils se présentent sous la forme de sels, ces derniers sont de préférence choisis de telle sorte que le contre-ion soit un halogénure comme par exemple un chlorure, ou un sulfate, un hydrosulfate, un alkylsulfate, un phosphate, un citrate, un formiate, un acétate. De plus, la fonction ammonium comprend au moins un radical alkyle ou aryle éventuellement porteur d'un ou plusieurs radicaux alkyles, possédant de 1 à 6 atomes de carbone, de préférence méthyle, éthyle.- diallyldialkyl ammonium salts; alone or in mixtures, or the corresponding salts; as well as the macromonomers derived from such monomers. If they are in the form of salts, the latter are preferably chosen such that the counterion is a halide such as, for example, a chloride, or a sulfate, a hydrosulfate, an alkylsulfate, a phosphate, a citrate, a formate, an acetate. In addition, the ammonium function comprises at least one alkyl or aryl radical optionally carrying one or more alkyl radicals, having from 1 to 6 carbon atoms, preferably methyl, ethyl.
A titre d'exemples de monomères cationiques convenables figurent les monomères suivants : - diméthyl amino éthyl (méth)acrylate, diméthyl amino propyl (méth)acrylate le ditertiobutyl aminoéthyl (méth)acrylate, le diméthyl amino méthyl (méth)acrylamide, le diméthyl amino propyl (méth)acrylamide ; l'éthylène imine, la vinylamine, la 2-vinylpyridine, la 4-vinylpyridine ; - le chlorure de triméthylammonium éthyl (méth)acrylate, le méthyl sulfate de triméthylammonium éthyl acrylate, le chlorure de benzyl diméthylammonium éthyl (méth)acrylate, le chlorure de 4-benzoylbenzyl diméthyl ammonium éthyl acrylate, le chlorure de triméthyl ammonium éthyl (méth)acrylamido, le chlorure de triméthyl ammonium de vinylbenzyle ; le chlorure d'ammonium de diallyldiméthyle ; seuls ou en mélanges, ou leurs sels correspondants.Examples of suitable cationic monomers include the following monomers: - dimethyl amino ethyl (meth) acrylate, dimethyl amino propyl (meth) acrylate ditertiobutyl aminoethyl (meth) acrylate, dimethyl amino methyl (meth) acrylamide, dimethyl amino propyl (meth) acrylamide; ethylene imine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; - trimethylammonium ethyl (meth) acrylate chloride, trimethylammonium ethyl acrylate methyl sulfate, benzyl dimethylammonium ethyl (meth) acrylate chloride, 4-benzoylbenzyl dimethyl ammonium ethyl acrylate chloride, trimethyl ammonium ethyl (meth) chloride acrylamido, trimethyl ammonium chloride, vinylbenzyl; diallyldimethyl ammonium chloride; alone or in mixtures, or their corresponding salts.
Enfin, le ou les segments hydrophiles du copolymère amphiphile peuvent être obtenus à partir de monomère(s) hydrophiles non ioniques.Finally, the hydrophilic segment or segments of the amphiphilic copolymer can be obtained from nonionic hydrophilic monomer (s).
Précision que les copolymères amphiphiles peuvent être des polymères à blocs et comprendre au moins deux blocs, l'un étant hydrophile, l'autre hydrophobe. Rappelons que de tels copolymères sont linéaires. Avantageusement, les copolymères mis en œuvre sont des copolymères diblocs ou triblocs.Note that the amphiphilic copolymers can be block polymers and comprise at least two blocks, one being hydrophilic, the other hydrophobic. Recall that such copolymers are linear. Advantageously, the copolymers used are diblock or triblock copolymers.
Il est de même envisageable de mettre en œuvre un copolymère peigne, dont l'un des segments est hydrophile, l'autre hydrophobe.It is likewise conceivable to use a comb copolymer, one of the segments of which is hydrophilic, the other hydrophobic.
Conformément à ce mode de réalisation, on met indifféremment en œuvre un copolymère dont le squelette est hydrophile et les groupements pendants sont hydrophobes ou l'inverse.In accordance with this embodiment, a copolymer is used, the backbone of which is hydrophilic and the pendant groups are hydrophobic, or vice versa.
A titre d'exemples de monomères hydrophiles non ioniques, on peut mentionner l'oxyde d'éthylène ; les amides des acides mono- ou poly- carboxyliques, linéaires, ramifiés, cycliques ou aromatiques, comprenant au moins une insaturation éthylénique ou dérivés ; les esters hydrophiles dérivant de l'acide (méth)acrylique ; les esters vinyliques permettant d'obtenir des blocs alcool polyvinylique après hydrolyse ; la vinypyrrolidone ; les monomères du type des sucres tels que les (méth)acrylates
d'oligosaccharides ou d'oligoholosides, ainsi que les macromonomères dérivant de ces monomères.As examples of non-ionic hydrophilic monomers, mention may be made of ethylene oxide; amides of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation or derivatives; hydrophilic esters derived from (meth) acrylic acid; vinyl esters making it possible to obtain polyvinyl alcohol blocks after hydrolysis; vinypyrrolidone; sugar type monomers such as (meth) acrylates oligosaccharides or oligoholosides, as well as the macromonomers derived from these monomers.
En ce qui concerne les monomères hydrophiles non ioniques préférés, on peut citer tout particulièrement le (méth)acrylamide, le N-méthyloI (méth)acrylamide, le (méth)acrylate de 2-hydroxyéthyle, les esters vinyliques permettant d'obtenir des blocs alcool polyvinylique après hydrolyse, comme l'acétate de vinyle, le Versatate® de vinyle, le propionate de vinyle.As regards the preferred nonionic hydrophilic monomers, mention may be made very particularly of (meth) acrylamide, N-methyloI (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, vinyl esters making it possible to obtain blocks polyvinyl alcohol after hydrolysis, such as vinyl acetate, vinyl Versatate®, vinyl propionate.
De tels monomères peuvent être utilisés seuls ou en mélanges, ainsi que sous la forme de macromonomères. II est précisé que le segment hydrophobe du copolymère peut comprendre un ou plusieurs motifs hydrophiles, de même le segment hydrophile peut comprendre un ou plusieurs motifs hydrophobes.Such monomers can be used alone or in mixtures, as well as in the form of macromonomers. It is specified that the hydrophobic segment of the copolymer can comprise one or more hydrophilic units, likewise the hydrophilic segment can comprise one or more hydrophobic units.
Il est précisé qu'au cas où un segment du copolymère serait constitué de plusieurs monomères, la répartition de ces derniers au sein du segment peut être statistique, bloc ou selon un gradient de concentration.It is specified that in the event that a segment of the copolymer is made up of several monomers, the distribution of the latter within the segment may be statistical, block or according to a concentration gradient.
Les copolymères utilisables dans le cadre de l'invention peuvent être préparés en mettant en œuvre des polymérisations par voie anionique, par voie cationique, par voie radicalaire dite vivante ou contrôlée. Il est de même possible de mettre en œuvre, selon les monomères employés, une polymérisation par transfert de groupe (dite "group transfert") ou bien une polymérisation par ouverture de cycle (cas notamment de polymérisation à partir de cycle N-carboxy anhydride), ou encore par une polymérisation mettant en jeu une transestérification de groupements terminaux.The copolymers which can be used in the context of the invention can be prepared by carrying out polymerizations by the anionic route, by the cationic route, by the so-called living or controlled radical route. It is likewise possible to carry out, depending on the monomers used, a group transfer polymerization (called "group transfer") or else a cycle opening polymerization (in particular case of polymerization from the N-carboxy anhydride cycle) , or also by a polymerization involving a transesterification of terminal groups.
De préférence, les polymères sont obtenus en mettant en œuvre au moins une étape de polymérisation radicalaire vivante. A titre d'exemple de procédés de polymérisation dite vivante ou contrôlée, on peut notamment se référer à : la polymérisation radicalaire contrôlée par les xanthates selon l'enseignement de la demande WO 98/58974, la polymérisation radicalaire contrôlée par les dithioesters selon l'enseignement de la demande WO 98/01478,Preferably, the polymers are obtained by implementing at least one step of living radical polymerization. By way of example of so-called living or controlled polymerization processes, reference may in particular be made to: radical polymerization controlled by xanthates according to the teaching of application WO 98/58974, radical polymerization controlled by dithioesters according to teaching of the application WO 98/01478,
- la polymérisation à l'aide de précurseurs nitroxydes selon l'enseignement de la demande WO 99/03894,- polymerization using nitroxide precursors according to the teaching of application WO 99/03894,
- la polymérisation radicalaire contrôlée par les dithiocarbamates selon l'enseignement de la demande WO 99/31144, - la polymérisation radicalaire par transfert d'atome (ATRP) selon l'enseignement de la demande WO 96/30421. Dans le cas de polymères portant des greffons (polymères peignes), ils peuvent notamment être obtenus par diverses méthodes, comme par exemple une
copolymérisation d'un monomère avec un macromonomère. Plus particulièrement, cette méthode en met en œuvre dans un premier temps le greffage à l'extrémité du segment d'une fonction polymérisable par voie radicalaire. Ce greffage peut être réalisé par des méthodes usuelles de chimie organique. Puis, dans un second temps, le macromonomère ainsi obtenu est polymérisé avec le monomère choisi pour former le squelette et on obtient un polymère dit "peigne".- radical polymerization controlled by the dithiocarbamates according to the teaching of application WO 99/31144, - radical polymerization by atom transfer (ATRP) according to the teaching of application WO 96/30421. In the case of polymers bearing grafts (comb polymers), they can in particular be obtained by various methods, such as for example a copolymerization of a monomer with a macromonomer. More particularly, this method firstly implements the grafting at the end of the segment of a radical polymerizable function. This grafting can be carried out by usual methods of organic chemistry. Then, in a second step, the macromonomer thus obtained is polymerized with the monomer chosen to form the skeleton and a so-called "comb" polymer is obtained.
On peut de même obtenir des polymères peigne par polymérisation d'un monomère suivie d'un greffage sur le squelette ainsi obtenu. Le greffage des segments polymériques latéraux sur un segment polymérique squelette peut être effectué selon des techniques classiques et familières à l'homme de l'art (European Polymer Journal 4, 343 (1968) par exemple). Parmi ces techniques classiques, on peut notamment citer celles dites de greffage direct.Comb polymers can also be obtained by polymerization of a monomer followed by grafting onto the skeleton thus obtained. The grafting of the lateral polymer segments onto a skeleton polymer segment can be carried out according to conventional techniques familiar to those skilled in the art (European Polymer Journal 4, 343 (1968) for example). Among these conventional techniques, mention may be made in particular of those known as direct grafting.
Dans le cadre plus particulier de copolymères à segments comprenant des unités de répétition présentant un ou plusieurs atomes de silicium, on pourra se reporter à la description de la demande WO 02/08307 publiée le 31/01/02, détaillant un procédé d'obtention de tels copolymères.In the more specific context of segment copolymers comprising repeating units having one or more silicon atoms, reference may be made to the description of application WO 02/08307 published on 31/01/02, detailing a process for obtaining such copolymers.
En outre, dans cette dernière catégorie de copolymères, on ne sortirait pas du cadre de l'invention en utilisant des composés du type des copolymères à blocs polydiméthylsiloxane greffé polyéther polyalkyle (Tegopren® - commercialisés par Goldschmidt).In addition, in this latter category of copolymers, it would not depart from the scope of the invention to use compounds of the type of polyalkyl polyether alkyl grafted polydimethylsiloxane block copolymers (Tegopren® - sold by Goldschmidt).
Les copolymères entrant dans la composition du concentré émulsionnable présentent plus spécialement une masse molaire en poids d'au plus 50000 g/mol, de préférence d'au plus 20000 g/mol.The copolymers used in the composition of the emulsifiable concentrate more particularly have a molar mass by weight of at most 50,000 g / mol, preferably at most 20,000 g / mol.
Par ailleurs, la masse molaire moyenne en poids du copolymère est avantageusement d'au moins 2500 g/mol, de préférence d'au moins 5000 g/mol.Furthermore, the weight-average molar mass of the copolymer is advantageously at least 2500 g / mol, preferably at least 5000 g / mol.
Selon une caractéristique de l'invention, la teneur en copolymère est telle que lorsque l'on ajoute ce copolymère à un mélange comprenant l'huile, le ou les tensioactifs, éventuellement le co-tensioactif, éventuellement l'agent neutralisant, on ait une solution limpide au sens indiqué précédemment, éventuellement en ajoutant de l'eau, dans le cas où l'huile et l'actif qu'elle contient éventuellement, soient non sensibles à l'hydrolyse.According to one characteristic of the invention, the content of copolymer is such that when this copolymer is added to a mixture comprising the oil, the surfactant (s), optionally the co-surfactant, optionally the neutralizing agent, there is a clear solution in the sense indicated above, possibly by adding water, in the case where the oil and the active agent which it possibly contains, are not sensitive to hydrolysis.
Généralement, la teneur en copolymère amphiphile représente de 0,1 à 25 % en poids desdits composés amphiphiles tels que définis auparavant.Generally, the content of amphiphilic copolymer represents from 0.1 to 25% by weight of said amphiphilic compounds as defined above.
En outre, la proportion pondérale de copolymère par rapport au tensioactif est de préférence comprise entre 0,5 et 10 % en poids.In addition, the proportion by weight of copolymer relative to the surfactant is preferably between 0.5 and 10% by weight.
Le concentré émulsionnable mis en œuvre dans le procédé selon l'invention peut éventuellement comprendre au moins un co-tensioactif.
De préférence, et s'il est employé, on choisit un co-tensioactif ou un mélange de co-tensioactifs solubles dans l'huile.The emulsifiable concentrate used in the process according to the invention can optionally comprise at least one co-surfactant. Preferably, and if it is used, a co-surfactant or a mixture of co-surfactants soluble in oil is chosen.
Plus particulièrement, celui-ci est choisi parmi les alcools primaires comprenant au moins un radical aliphatique, linéaire ou ramifié, saturé ou non, comprenant de 4 à 22 atomes de carbone, ou au moins un radical aromatique, de préférence comprenant 6 atomes de carbone, éventuellement porteur d'un ou plusieurs substituants alkyle comprenant 1 à 10 atomes de carbone.More particularly, this is chosen from primary alcohols comprising at least one aliphatic radical, linear or branched, saturated or not, comprising from 4 to 22 carbon atoms, or at least one aromatic radical, preferably comprising 6 carbon atoms , optionally carrying one or more alkyl substituents comprising 1 to 10 carbon atoms.
Parmi les alcools susceptibles d'entrer dans la composition des concentrés émulsionnables, conviennent notamment l'isopropanol, l'éthylhexanol, le dodécanol, l'hexadécanol, l'alcool benzylique, seuls ou en mélanges.Among the alcohols capable of entering into the composition of the emulsifiable concentrates, is suitable in particular isopropanol, ethylhexanol, dodecanol, hexadecanol, benzyl alcohol, alone or in mixtures.
Si un co-tensioactif est présent, la proportion pondérale co-tensioactif / tensioactif est de préférence comprise entre 0 exclu et 50 % en poids, de préférence entre 5 et 40 % en poids.If a co-surfactant is present, the weight ratio of co-surfactant / surfactant is preferably between 0 excluded and 50% by weight, preferably between 5 and 40% by weight.
Le concentré émulsionnable peut encore éventuellement comprendre au moins un agent neutralisant.The emulsifiable concentrate can also optionally comprise at least one neutralizing agent.
De préférence, s'il est présent, on met en œuvre un agent neutralisant soluble dans le concentré émulsionnable entre 15 et 40°C ou un composé qui, une fois chauffé au-delà de sa température de fusion en présence d'huile, puis refroidi, reste soluble dans l'huile. Avantageusement, l'agent neutralisant est choisi parmi les composés solubles dans la phase huile et portant au moins une fonction aminé ou carboxylique.Preferably, if it is present, a neutralizing agent is used which is soluble in the emulsifiable concentrate between 15 and 40 ° C. or a compound which, once heated beyond its melting point in the presence of oil, then cooled, remains soluble in oil. Advantageously, the neutralizing agent is chosen from compounds soluble in the oil phase and carrying at least one amine or carboxylic function.
Par exemple, les aminés comprenant un à trois radicaux, identiques ou non, comprenant 1 à 10 atomes de carbone, éventuellement porteur d'un radical hydroxyle, conviennent dans ce but. A titre d'exemple de telles aminés, on peut citer notamment l'éthylènediamine, la triéthylamine, diméthylbutylamine, diiméthylisopropylamine, diméthylcyclohexylamine, tripropylamine, monoéthanolamine, la diéthanolamine, l'aminoéthyléthanolamine, Paminométhylpropanolamine peuvent être utilisées comme agent neutralisant.For example, amines comprising one to three radicals, identical or not, comprising 1 to 10 carbon atoms, optionally carrying a hydroxyl radical, are suitable for this purpose. By way of example of such amines, mention may in particular be made of ethylenediamine, triethylamine, dimethylbutylamine, diimethylisopropylamine, dimethylcyclohexylamine, tripropylamine, monoethanolamine, diethanolamine, aminoethylethanolamine, Paminomethylpropanolamine can be used as neutralizing agent.
Concernant les composés possédant au moins une fonction carboxylique, on peut mentionner l'acide acétique, etc.As regards the compounds having at least one carboxylic function, mention may be made of acetic acid, etc.
Cette variante est avantageusement mise en œuvre lorsque le tensioactif comprend un composé ionisable dans les conditions de pH de l'émulsion finale.This variant is advantageously implemented when the surfactant comprises a compound which can be ionized under the pH conditions of the final emulsion.
S'il est présent, l'agent neutralisant est utilisé en quantité telle que la proportion pondérale agent neutralisant / tensioactif est comprise entre 0 exclu et 50 % en poids, de préférence entre 5 et 40 % en poids.If present, the neutralizing agent is used in an amount such that the proportion by weight of neutralizing agent / surfactant is between 0 excluded and 50% by weight, preferably between 5 and 40% by weight.
Il est précisé que le concentré émulsionnable peut comprendre un co-tensioactif et/ou un agent neutralisant. De préférence le concentré émulsionnable comprend soit un co-tensioactif, soit un agent neutralisant.
Enfin, selon une caractéristique de l'invention, la teneur totale en composés amphiphiles dans le concentré émulsionnable représente de 1 à 40 % en poids du concentré émulsionnable. De préférence, la teneur totale en composés amphiphiles est comprise entre 5 et 30 % en poids du concentré émulsionnable. Le concentré émulsionnable est obtenu par un simple mélange des divers éléments constitutifs qui viennent d'être détaillés.It is specified that the emulsifiable concentrate can comprise a co-surfactant and / or a neutralizing agent. Preferably, the emulsifiable concentrate comprises either a co-surfactant or a neutralizing agent. Finally, according to a characteristic of the invention, the total content of amphiphilic compounds in the emulsifiable concentrate represents from 1 to 40% by weight of the emulsifiable concentrate. Preferably, the total content of amphiphilic compounds is between 5 and 30% by weight of the emulsifiable concentrate. The emulsifiable concentrate is obtained by a simple mixture of the various constituent elements which have just been detailed.
La température à laquelle on effectue ce mélange est en général telle que l'ensemble des composés se trouve sous forme liquide. Avantageusement cette température est au-dessus du point de fusion de chacun des composés. Comme précisé plus haut, l'émulsion est obtenue en diluant le concentré émulsionnable dans une phase aqueuse. Cette emulsion est une emulsion directe, c'est-à-dire pour laquelle la phase continue est une phase aqueuse.The temperature at which this mixing is carried out is generally such that all of the compounds are in liquid form. Advantageously, this temperature is above the melting point of each of the compounds. As specified above, the emulsion is obtained by diluting the emulsifiable concentrate in an aqueous phase. This emulsion is a direct emulsion, that is to say for which the continuous phase is an aqueous phase.
Il n'est pas exclu que la phase aqueuse avec laquelle est dilué le concentré émulsionnable soit en elle-même une formulation utilisable dans un domaine particulier. En ce cas, ladite phase aqueuse comprend les additifs usuels du domaine d'utilisation.It is not excluded that the aqueous phase with which the emulsifiable concentrate is diluted is in itself a formulation usable in a particular field. In this case, said aqueous phase comprises the usual additives in the field of use.
Selon une caractéristique de l'invention, la dilution du concentré émulsionnable conduit à l'obtention d'une emulsion pour laquelle au moins 75% en volume des gouttelettes présente une taille moyenne (ds ) inférieure ou égale à 1 μm.According to a characteristic of the invention, the dilution of the emulsifiable concentrate leads to the production of an emulsion for which at least 75% by volume of the droplets has an average size (ds) less than or equal to 1 μm.
Il est à noter que selon une caractéristique de l'invention, la taille moyenne des gouttelettes de l'émulsion ainsi obtenue est inférieure à celle d'une emulsion obtenue par dilution d'un concentré émulsionnable dépourvu du copolymère détaillé auparavant ; la concentration totale en composés amphiphiles étant la même dans les deux cas.It should be noted that according to a characteristic of the invention, the average size of the droplets of the emulsion thus obtained is less than that of an emulsion obtained by dilution of an emulsifiable concentrate devoid of the copolymer detailed previously; the total concentration of amphiphilic compounds being the same in both cases.
La taille moyenne des gouttelettes de l'émulsion obtenue conformément au procédé selon l'invention est donc inférieure ou égale à 1 μm, plus particulièrement comprise entre 0,2 et 1 μm.The average size of the droplets of the emulsion obtained according to the method according to the invention is therefore less than or equal to 1 μm, more particularly between 0.2 and 1 μm.
La dilution du concentré émulsionnable est réalisée de préférence en ajoutant le concentré émulsionnable à la phase aqueuse.The dilution of the emulsifiable concentrate is preferably carried out by adding the emulsifiable concentrate to the aqueous phase.
La teneur en concentré émulsionnable dans la formulation finale est très variable selon le domaine d'utilisation du concentré. A titre purement illustratif, la teneur en concentré émulsionnable représente 0,1 à 40 % en poids de la formulation aqueuse finale, de préférence 0,1 à 30 % en poids de la formulation aqueuse finale.The content of emulsifiable concentrate in the final formulation is very variable depending on the field of use of the concentrate. For purely illustrative purposes, the content of emulsifiable concentrate represents 0.1 to 40% by weight of the final aqueous formulation, preferably 0.1 to 30% by weight of the final aqueous formulation.
L'opération de dilution a classiquement lieu sous une légère agitation, notamment au moyen d'une pâle cadre.The dilution operation conventionally takes place with slight agitation, in particular by means of a pale frame.
L'émulsion ainsi obtenue peut être utilisée dans de nombreux domaines, selon la nature de l'huile, le cas échéant de l'actif présent, entrant dans la composition du concentré émulsionnable.
Par exemple, le concentré émulsionnable peuvent être utilisés dans le domaine des formulations phytosanitaires. Dans ce cas, la préparation de l'émulsion est faite par l'utilisateur avant de l'appliquer sur les plantes ou champs à traiter.The emulsion thus obtained can be used in many fields, depending on the nature of the oil, if any, of the active ingredient present, forming part of the composition of the emulsifiable concentrate. For example, the emulsifiable concentrate can be used in the field of phytosanitary formulations. In this case, the preparation of the emulsion is made by the user before applying it to the plants or fields to be treated.
Les émulsions peuvent de même être utilisées dans le domaine de la cosmétique. Les émulsions peuvent de même être utilisées dans le domaine des peintures, vernis, colles.The emulsions can likewise be used in the field of cosmetics. The emulsions can likewise be used in the field of paints, varnishes, adhesives.
Elles peuvent être utilisées dans le domaine des anti-mousses silicones ou organiques.They can be used in the field of silicone or organic anti-foaming agents.
Elles peuvent aussi être utilisées dans les procédés de transformation et déformation de métaux, et notamment en tant que fluide de coupe.They can also be used in metal transformation and deformation processes, and in particular as a cutting fluid.
Les émulsions obtenues selon l'invention peuvent aussi être employées dans le domaine de l'industrie papetiere où l'on recherche des émulsions de taille relativement fine.The emulsions obtained according to the invention can also be used in the field of the paper industry where emulsions of relatively fine size are sought.
Des exemples concrets mais non limitatifs de l'invention vont maintenant être présentés.Concrete but nonlimiting examples of the invention will now be presented.
EXEMPLESEXAMPLES
EXEMPLE 1 : Synthèse du copolymère P1 dibloc p(ABu)1ooo-b-p(AA)40o0 EXAMPLE 1 Synthesis of the P1 diblock copolymer p (ABu) 1 ooo-bp (AA) 40 o 0
A) Etape 1 : Synthèse du monobloc p(ABu)10o0 Composition du mélange réactionnel :A) Step 1: Synthesis of the monoblock p (ABu) 10 o 0 Composition of the reaction mixture:
Ethanol 23,00 gEthanol 23.00 g
Acrylate de butyle (ABu) 8,00 g S-éthylpropionyl O-éthyldithiocarbonate 1 ,664 gButyl acrylate (ABu) 8.00 g S-ethylpropionyl O-ethyldithiocarbonate 1, 664 g
AIBN (Azo-bis-isobutyronitrile) 0,263 g.AIBN (Azo-bis-isobutyronitrile) 0.263 g.
Dans un ballon de 100 ml muni d'un réfrigérant et d'une agitation magnétique, sont introduits l'éthanol, l'acrylate de butyle, l'azo-bis-isobutyronitrile (AIBN) et le S- éthylpropionyl O-éthyldithiocarbonate. Le milieu réactionnel est porté à 70°C et est maintenu à cette température pendant 3 heures.Ethanol, butyl acrylate, azo-bis-isobutyronitrile (AIBN) and S-ethylpropionyl O-ethyldithiocarbonate are introduced into a 100 ml flask fitted with a condenser and a magnetic stirrer. The reaction medium is brought to 70 ° C. and is maintained at this temperature for 3 hours.
Des échantillons de polymères sont prélevés régulièrement pour contrôler la conversion.Polymer samples are taken regularly to check the conversion.
La teneur en solides est de 30,2% en fin de réaction.The solid content is 30.2% at the end of the reaction.
B) Etape 2: Synthèse du dibloc p(ABu -b-pfAA nn Composition du mélange réactionnel :B) Step 2: Synthesis of the diblock p (ABu -b-pfAA nn Composition of the reaction mixture:
Ethanol 93,00 g
Acide acrylique (AA) 32,00 gEthanol 93.00 g Acrylic acid (AA) 32.00 g
AIBN (Azo-bis-isobutyronitrile) 0,263 gAIBN (Azo-bis-isobutyronitrile) 0.263 g
Les ingrédients ci-dessus sont chargés dans un récipient sec sous atmosphère d'azote sec pendant 20 minutes, puis transférés dans le réacteur de polymérisation, comprenant le polymère issu de l'étape précédente, à l'aide d'une seringue à deux embouts.The above ingredients are loaded into a dry container under a dry nitrogen atmosphere for 20 minutes, then transferred to the polymerization reactor, comprising the polymer from the previous step, using a syringe with two tips. .
A la fin du transfert, le mélange réactionnel est ensuite chauffé à 60°C et maintenu à cette température pendant 20 heures.At the end of the transfer, the reaction mixture is then heated to 60 ° C. and kept at this temperature for 20 hours.
Des échantillons de polymères sont prélevés de temps en temps pour contrôler la conversion. La teneur en matière solide est de 30% en fin de réaction.Polymer samples are taken from time to time to check the conversion. The solid content is 30% at the end of the reaction.
Le mélange réactionnel est laissé refroidir et les solvants sont éliminés à l'aide d'un évaporateur rotatif.The reaction mixture is allowed to cool and the solvents are removed using a rotary evaporator.
La teneur en solides est de 30 % en fin de réaction.The solid content is 30% at the end of the reaction.
La masse molaire en nombre du copolymère est de 5000 g/mol (valeur théorique).The number-average molar mass of the copolymer is 5000 g / mol (theoretical value).
EXEMPLE 2 : Synthèse d'un copolymère P2 dibloc p(ABu)3ooo-b-p(VP)60oo A) Etape 1 : Synthèse du monobloc p(ABu)3oo0 Composition du mélange réactionnel :EXAMPLE 2 Synthesis of a copolymer P2 diblock p (ABu) 3 ooo-bp (VP) 60 oo A) Step 1: Synthesis of the monoblock p (ABu) 3 oo 0 Composition of the reaction mixture:
Ethanol 6,48 g Acrylate de butyle (ABu) 4,00 gEthanol 6.48 g Butyl acrylate (ABu) 4.00 g
AIBN (Azo-bis-isobutyronitrile) 0,44 gAIBN (Azo-bis-isobutyronitrile) 0.44 g
O-éthyl-S-(1-méthoxycarbonyl)éthyl xanthate 0,278 gO-ethyl-S- (1-methoxycarbonyl) ethyl xanthate 0.278 g
Dans un ballon de 100 ml muni d'un réfrigérant et d'une agitation magnétique, on introduit les ingrédients mentionnés ci-dessus. Le milieu réactionnel est porté à 70°C et est maintenu à cette température pendant 3 heures.The above-mentioned ingredients are introduced into a 100 ml flask fitted with a condenser and a magnetic stirrer. The reaction medium is brought to 70 ° C. and is maintained at this temperature for 3 hours.
Un échantillon est alors prélevé et analysé par chromatographie d'exclusion stérique et la masse molaire en nombre est de l'ordre de 3100 g/mol.A sample is then taken and analyzed by steric exclusion chromatography and the molar mass in number is of the order of 3100 g / mol.
B) Etape 2: Synthèse du dibloc p(ABu)3ooo-b-p(VP)6ooo Composition du mélange réactionnel :B) Step 2: Synthesis of the diblock p (ABu) 3ooo-bp (VP) 6 ooo Composition of the reaction mixture:
Ethanol : 24,2 gEthanol: 24.2 g
N-vinylpyrrolidone (VP) 16 gN-vinylpyrrolidone (VP) 16 g
AIBN 0,131 mg Le milieu réactionnel décrit dans la première partie de l'exemple et maintenu en température à 70°C.AIBN 0.131 mg The reaction medium described in the first part of the example and maintained at temperature at 70 ° C.
On introduit l'éthanol, la N-vinyl pyrrolidone et l'AIBN.
La réaction est maintenue pendant 6 heures à partir du moment où les réactifs sont introduits.Ethanol, N-vinyl pyrrolidone and AIBN are introduced. The reaction is maintained for 6 hours from the time when the reagents are introduced.
En fin de réaction, l'éthanol est évaporé sous vide. Le copolymère dibloc résultant est ensuite dissous dans l'eau. Une solution limpide de copolymère est alors obtenue.At the end of the reaction, the ethanol is evaporated in vacuo. The resulting diblock copolymer is then dissolved in water. A clear copolymer solution is then obtained.
EXEMPLE 3 : préparation d'un concentré émulsionnable comprenant P1EXAMPLE 3 Preparation of an emulsifiable concentrate comprising P1
Composition du concentré émulsionnable :Composition of the emulsifiable concentrate:
Hexadécane 81 ,8% Synperonic® L7 11 ,4%Hexadecane 81.8% Synperonic® L7 11.4%
Dodecanol 2,3%Dodecanol 2.3%
P1 (poids sec) 0,7%P1 (dry weight) 0.7%
Eau qsp 100%Water qs 100%
Le concentré émulsionnable est préparé en mélangeant dans un flacon sous agitation les quantités requises d'hexadécane (AIdrich), de Synperonic® L7 (ICI) et de dodecanol (Prolabo) préalablement chauffés à 50°C, ainsi que le polymère P1.The emulsifiable concentrate is prepared by mixing the required quantities of hexadecane (AIdrich), Synperonic® L7 (ICI) and dodecanol (Prolabo) previously heated to 50 ° C in a shaking flask, as well as the polymer P1.
Le copolymère P1 est introduit à partir d'une solution aqueuse à 16% à pH neutre.The copolymer P1 is introduced from a 16% aqueous solution at neutral pH.
L'émulsification est réalisée en introduisant rapidement le concentré émulsionnable dans l'eau épurée sous faible agitation mécanique avec une pâle cadre à 200 tours/min et en agitant pendant 5 minutes.The emulsification is carried out by rapidly introducing the emulsifiable concentrate into the purified water with gentle mechanical stirring with a pale frame at 200 rpm and stirring for 5 minutes.
La teneur en eau de l'émulsion est de 90%.The water content of the emulsion is 90%.
La distribution en taille des gouttelettes d'huile est déterminée par diffraction laser (Horiba LA- 910).The size distribution of the oil droplets is determined by laser diffraction (Horiba LA-910).
L'émulsion présente les caractéristiques suivantes : d50 = 0,51 μmThe emulsion has the following characteristics: d50 = 0.51 μm
84 % en volume des gouttelettes présentent une taille inférieure à 1 μm84% by volume of the droplets have a size of less than 1 μm
EXEMPLE 4 comparatif : préparation d'un concentré émulsionnable exempt de copolymèreComparative Example 4: Preparation of an Emulsifiable Concentrate Free of Copolymer
Composition du concentré émulsionnable :Composition of the emulsifiable concentrate:
Hexadécane 85%Hexadecane 85%
Synperonic® L7 12,5% Dodecanol 2,5%Synperonic® L7 12.5% Dodecanol 2.5%
Le rapport amphiphile/huile est le même que dans l'exemple 3.
L'émulsion préparée selon le protocole décrit dans l'exemple 3 présente ici les caractéristiques suivantes : d50 = 24 μm 5% en volume des gouttelettes présentent une taille inférieure à 1 μm.The amphiphilic / oil ratio is the same as in Example 3. The emulsion prepared according to the protocol described in Example 3 has the following characteristics here: d50 = 24 μm 5% by volume of the droplets have a size less than 1 μm.
EXEMPLE 5 : préparation d'un concentré émulsionnable comprenant P2EXAMPLE 5 Preparation of an emulsifiable concentrate comprising P2
Composition du concentré émulsionnable :Composition of the emulsifiable concentrate:
Hexadécane 81 ,8%Hexadecane 81.8%
Synperonic L7 11 ,4%Synperonic L7 11, 4%
Dodecanol 2,3%Dodecanol 2.3%
P2 (poids sec) 0,7%P2 (dry weight) 0.7%
Eau qsp 100%Water qs 100%
Le copolymère est introduit à partir d'une solution aqueuse à 16%.The copolymer is introduced from a 16% aqueous solution.
L'émulsion préparée selon le protocole décrit dans l'exemple 3 présente ici les caractéristiques suivantes : d50 = 0,50μm 76% en volume des gouttelettes présentent une taille inférieure à 1 μm.The emulsion prepared according to the protocol described in Example 3 here has the following characteristics: d50 = 0.50 μm 76% by volume of the droplets have a size of less than 1 μm.
EXEMPLES 6-10: StabilitéEXAMPLES 6-10: Stability
Composition des concentrés émulsionnables:Composition of emulsifiable concentrates:
* . Géronol FF4 et FF6 : produits commercialisés par Rhodia, mélanges de tristyrylphénol éthoxylés et de dodécyl benzène sulfonate de calcium dans l'isobutanol **: P3 est un copolymère dibloc polystyrène - poly acide acrylique de masse molaire en poids de 3800 - 1200 g/mol (p(St)38oo-b-p(AA)12oo). * . Géronol FF4 and FF6: products marketed by Rhodia, mixtures of ethoxylated tristyrylphenol and calcium dodecyl benzene sulfonate in isobutanol ** : P3 is a diblock copolymer polystyrene - poly acrylic acid with a molecular weight by weight of 3800 - 1200 g / mol (p (St) 38 oo-bp (AA) 12 oo).
Les concentrés émulsionnables sont préparés à 20°C en mélangeant dans un flacon sous agitation les quantités requises de xylène (Prolabo), de Géronol FF4 et FF6, ainsi que le polymère P3. Le copolymère P3 est introduit sous forme sèche.The emulsifiable concentrates are prepared at 20 ° C. by mixing the required quantities of xylene (Prolabo), Geronol FF4 and FF6, as well as the polymer P3, in a shaking flask. The copolymer P3 is introduced in dry form.
L'émulsification est réalisée en introduisant dans une éprouvette cylindrique 9.5 mL
d'eau de ville puis 0.5 mL de concentré émulsionnable, et en effectuant ensuite 20 retournements.The emulsification is carried out by introducing into a cylindrical test tube 9.5 mL city water then 0.5 mL of emulsifiable concentrate, and then making 20 turns.
L'évolution des émulsions au stockage à 30°C est suivie en mesurant le cremage et la coalescence (coal.). Le cremage et la coalescence sont exprimés en % du volume total de l'émulsion.The evolution of the emulsions in storage at 30 ° C. is followed by measuring the creaming and the coalescence (coal). Creaming and coalescence are expressed as% of the total volume of the emulsion.
Claims
1. Procédé de préparation d'une emulsion directe, caractérisé en ce que l'on dilue dans une phase aqueuse un concentré émulsionnable limpide comprenant une phase huile, éventuellement de l'eau, et des composés amphiphiles consistant en au moins un tensioactif, au moins un copolymère possédant au moins un segment hydrophile et au moins un segment hydrophobe, à l'exclusion de copolymères ne comprenant que des segments obtenus à partir d'oxyde d'éthylène et d'oxyde de propylène, éventuellement au moins un co-tensioactif et éventuellement au moins un agent neutralisant ;1. A method for preparing a direct emulsion, characterized in that a clear emulsifiable concentrate comprising an oil phase, optionally water, and amphiphilic compounds consisting of at least one surfactant is diluted in an aqueous phase. at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, excluding copolymers comprising only segments obtained from ethylene oxide and propylene oxide, optionally at least one co-surfactant and optionally at least one neutralizing agent;
• la teneur totale en composés amphiphiles représentant 1 à 40 % en poids du concentré émulsionnable ;• the total content of amphiphilic compounds representing 1 to 40% by weight of the emulsifiable concentrate;
• la teneur en copolymère représentant 0,1 à 25 % en poids desdits composés amphiphiles ; • plus de 75 % en volume des gouttelettes de l'émulsion ont une taille moyenne inférieure ou égale à 1 μm ;• the content of copolymer representing 0.1 to 25% by weight of said amphiphilic compounds; • more than 75% by volume of the droplets of the emulsion have an average size less than or equal to 1 μm;
• la taille moyenne des gouttelettes d'une emulsion obtenue par dilution dudit concentré étant inférieure à celle d'une emulsion obtenue par dilution d'un concentré émulsionnable dépourvu dudit copolymère ; la concentration totale en composés amphiphiles étant la même dans les deux cas.• the average droplet size of an emulsion obtained by diluting said concentrate being less than that of an emulsion obtained by diluting an emulsifiable concentrate devoid of said copolymer; the total concentration of amphiphilic compounds being the same in both cases.
2. Procédé selon la revendication précédente, caractérisé en ce que le segment hydrophobe du copolymère est obtenu à partir de l'un ou plusieurs des monomères suivants : - les esters des acides mono- ou poly- carboxyliques, linéaires, ramifiés, cycliques ou aromatiques, comprenant au moins une insaturation éthylénique, les nitriles β-éthyléniquement insaturés, les éthers vinyliques, les esters vinyliques, les monomères vinylaromatiques, les halogénures de vinyle ou de vinylidène, - les monomères hydrocarbonés, linéaires ou ramifiés, aromatiques ou non, comprenant au moins une insaturation éthylénique, - oxyde de propylène, oxyde de butylène, seuls ou en mélanges, ainsi que les macromonomères dérivant de tels monomères.2. Method according to the preceding claim, characterized in that the hydrophobic segment of the copolymer is obtained from one or more of the following monomers: - the esters of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic , comprising at least one ethylenic unsaturation, β-ethylenically unsaturated nitriles, vinyl ethers, vinyl esters, vinyl aromatic monomers, vinyl or vinylidene halides, - hydrocarbon monomers, linear or branched, aromatic or not, comprising at least minus ethylenic unsaturation, - propylene oxide, butylene oxide, alone or in mixtures, as well as the macromonomers deriving from such monomers.
3. Procédé selon l'une des revendications précédentes, caractérisé en ce que le segment hydrophile du copolymère est obtenu à partir d'un ou de plusieurs des monomères comprenant au moins une fonction carboxylique, sulfonique, sulfurique, phosphonique, phosphorique, sulfosuccinique, leurs sels, ainsi que les macromonomères correspondants.3. Method according to one of the preceding claims, characterized in that the hydrophilic segment of the copolymer is obtained from one or more of the monomers comprising at least one carboxylic, sulfonic, sulfuric function, phosphonic, phosphoric, sulfosuccinic, their salts, as well as the corresponding macromonomers.
4. Procédé selon la revendication précédente, caractérisé en ce que le segment hydrophile du copolymère est obtenu à partir de l'un ou plusieurs des monomères suivants : les acides mono- ou poly- carboxyliques linéaires, ramifiés, cycliques ou aromatiques, les dérivés N-substitués de tels acides ; les monoesters d'acides polycarboxyliques, comprenant au moins une insaturation éthylénique ; - les acides vinyl carboxyliques linéaires, ramifiés, cycliques ou aromatiques ; les aminoacides comprenant une ou plusieurs insaturations éthyléniques ; seuls ou en mélanges, leurs précurseurs, leurs homologues sulfoniques ou phosphoniques, leurs sels, ainsi que les macromonomères dérivant de tels monomères ou de leurs sels.4. Method according to the preceding claim, characterized in that the hydrophilic segment of the copolymer is obtained from one or more of the following monomers: linear, branched, cyclic or aromatic mono- or polycarboxylic acids, N derivatives -substituted for such acids; monoesters of polycarboxylic acids, comprising at least one ethylenic unsaturation; - linear, branched, cyclic or aromatic vinyl carboxylic acids; amino acids comprising one or more ethylenic unsaturations; alone or as mixtures, their precursors, their sulfonic or phosphonic counterparts, their salts, as well as the macromonomers derived from such monomers or from their salts.
5. Procédé selon l'une des revendications précédentes, caractérisé en ce que le segment hydrophile du copolymère est obtenu à partir de l'un ou plusieurs des monomères suivants : les (méth)acrylates d'aminoalkyle, les (méth)acrylamides d'aminoalkyle ; - les monomères comprenant au moins une fonction aminé secondaire, tertiaire ou quaternaire, ou un groupe hétérocyclique contenant un atome d'azote, la vinylamine, l'éthylène imine ; les sels d'ammonium de diallyldialkyl ; seuls ou en mélanges, ou les sels correspondants ; ainsi que les macromonomères dérivant de tels monomères.5. Method according to one of the preceding claims, characterized in that the hydrophilic segment of the copolymer is obtained from one or more of the following monomers: aminoalkyl (meth) acrylates, (meth) acrylamides aminoalkyl; - the monomers comprising at least one secondary, tertiary or quaternary amine function, or a heterocyclic group containing a nitrogen atom, vinylamine, ethylene imine; diallyldialkyl ammonium salts; alone or in mixtures, or the corresponding salts; as well as the macromonomers derived from such monomers.
6. Procédé selon l'une des revendications précédentes, caractérisé en ce que le segment hydrophile du copolymère est obtenu à partir de l'un ou plusieurs des monomères suivants : oxyde d'éthylène ; amides des acides mono- ou poly- carboxyliques, linéaires, ramifiés, cycliques ou aromatiques, comprenant au moins une insaturation éthylénique ou dérivés ; esters hydrophiles dérivant de l'acide (méth)acrylique ; esters vinyliques permettant d'obtenir des blocs alcool polyvinylique après hydrolyse ; vinypyrrolidone ; monomères du type des sucres, ainsi que les macromonomères dérivant de tels monomères.6. Method according to one of the preceding claims, characterized in that the hydrophilic segment of the copolymer is obtained from one or more of the following monomers: ethylene oxide; amides of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation or derivatives; hydrophilic esters derived from (meth) acrylic acid; vinyl esters making it possible to obtain polyvinyl alcohol blocks after hydrolysis; vinypyrrolidone; sugar-type monomers, as well as macromonomers derived from such monomers.
Procédé selon l'une des revendications précédentes, caractérisé en ce que le segment hydrophobe peut comprendre un ou plusieurs motifs hydrophiles. Method according to one of the preceding claims, characterized in that the hydrophobic segment can comprise one or more hydrophilic units.
8. Procédé selon l'une des revendications précédentes, caractérisé en ce que le segment hydrophile peut comprendre un ou plusieurs motifs hydrophobes.8. Method according to one of the preceding claims, characterized in that the hydrophilic segment can comprise one or more hydrophobic units.
9. Procédé selon l'une des revendications précédentes, caractérisé en ce que le copolymère présente une masse molaire en poids d'au plus 50000 g/mol, de préférence d'au plus 20000 g/mol.9. Method according to one of the preceding claims, characterized in that the copolymer has a molar mass by weight of at most 50,000 g / mol, preferably at most 20,000 g / mol.
10. Procédé selon l'une des revendications précédentes, caractérisé en ce que le copolymère présente une masse molaire en poids d'au moins 2500 g/mol, de préférence d'au moins 5000 g/mol.10. Method according to one of the preceding claims, characterized in that the copolymer has a molar mass by weight of at least 2500 g / mol, preferably at least 5000 g / mol.
11. Procédé selon l'une des revendications précédentes, caractérisé en ce que le copolymère présente une structure à blocs, plus particulièrement dibloc ou tribloc.11. Method according to one of the preceding claims, characterized in that the copolymer has a block structure, more particularly diblock or triblock.
12. Procédé selon l'une des revendications précédentes, caractérisé en ce que le copolymère présente une structure peigne.12. Method according to one of the preceding claims, characterized in that the copolymer has a comb structure.
13. Procédé selon l'une des revendications précédentes, caractérisé en ce que le ou les tensioactifs sont choisis parmi les tensioactifs non ioniques ou anioniques solubles dans l'huile.13. Method according to one of the preceding claims, characterized in that the surfactant (s) are chosen from nonionic or anionic surfactants soluble in oil.
14. Procédé selon l'une des revendications précédentes, caractérisé en ce que le ou les tensioactifs sont choisis parmi les tensioactifs non ioniques suivants :14. Method according to one of the preceding claims, characterized in that the surfactant (s) are chosen from the following nonionic surfactants:
- les alcools gras alcoxylés, plus particulièrement comprenant de 6 à 22 atomes de carbone ;- alkoxylated fatty alcohols, more particularly comprising from 6 to 22 carbon atoms;
- les mono-, di- et tri-glycérides alcoxylés ; les acides gras alcoxylés, plus particulièrement comprenant de 6 à 22 atomes de carbone ;- alkoxylated mono-, di- and tri-glycerides; alkoxylated fatty acids, more particularly comprising from 6 to 22 carbon atoms;
- les esters de sorbitan alcoxylés (des esters du sorbitol cyclisés d'acide gras comprenant de 10 à 20 atomes de carbone) ; les aminés grasses alcoxylées, plus particulièrement comprenant de 6 à 22 atomes de carbone ;- alkoxylated sorbitan esters (fatty acid cyclized sorbitol esters comprising from 10 to 20 carbon atoms); alkoxylated fatty amines, more particularly comprising from 6 to 22 carbon atoms;
- les alkylphénols alcoxylés, plus particulièrement comprenant un ou deux groupes alkyles, linéaires ou ramifiés, ayant 4 à 12 atomes de carbone ; - les alkylpolyglucosides ;- Alkoxylated alkylphenols, more particularly comprising one or two alkyl groups, linear or branched, having 4 to 12 carbon atoms; - alkylpolyglucosides;
- les tensioactifs polyoxyalkylénés, comme par exemple les composés commercialisés sous la gamme Pluronic ou Poloxamer par la société BASF ; les mono- et di- alcanolamides alcoxylés ; seuls ou en mélanges.- polyoxyalkylenated surfactants, such as for example the compounds sold under the Pluronic or Poloxamer range by the company BASF; alkoxylated mono- and di-alkanolamides; alone or in mixtures.
15. Procédé selon l'une des revendications précédentes, caractérisé en ce que le ou les tensioactifs sont choisis parmi les tensioactifs anioniques suivants, sous forme acide ou associé(s) à un contre ion multivalent :15. Method according to one of the preceding claims, characterized in that the surfactant (s) are chosen from the following anionic surfactants, in acid form or associated (s) with a multivalent counter ion:
- les alkylesters sulfonates, les alkylesters sulfates ;- alkyl esters sulfonates, alkyl esters sulfates;
- les alkylbenzènesulfonates, les alkylsulfonates primaires ou secondaires, les alkylglycérol sulfonates ;- alkylbenzenesulfonates, primary or secondary alkylsulfonates, alkylglycerol sulfonates;
- les alkylsulfates ; - les alkyléthersulfates ;- alkyl sulfates; - alkyl ether sulfates;
- les alkylamides sulfates ;- alkylamide sulfates;
- les sels d'acides gras saturés ou insaturés, les N-acyl N-alkyltaurates, les alkyliséthionates, les alkylsuccinamates et alkylsulfosuccinates, les monoesters ou diesters de sulfosuccinates, les N-acyl sarcosinates, les polyéthoxy- carboxylates ; et- the salts of saturated or unsaturated fatty acids, N-acyl N-alkyltaurates, alkylisethionates, alkylsuccinamates and alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, polyethoxycarboxylates; and
- les phosphates esters d'alkyle et/ou d'alkyléther et/ou d'alkylaryléther ; seuls ou en mélanges.- alkyl and / or alkyl ether and / or alkylaryl ether ester phosphates; alone or in mixtures.
16. Procédé selon l'une des revendications: précédentes, caractérisé en ce que la proportion pondérale de copolymère par rapport au tensioactif est comprise entre16. Method according to one of the preceding claims, characterized in that the proportion by weight of copolymer relative to the surfactant is between
0,5 et 10 % en poids.0.5 and 10% by weight.
17. Procédé selon l'une des revendications précédentes, caractérisé en ce que le co- tensioactif est choisi parmi les alcools primaires comprenant au moins un radical aliphatique, linéaire ou ramifié, saturé ou non, comprenant de 4 à 22 atomes de carbone, ou au moins un radical aromatique, de préférence comprenant 6 atomes de carbone, éventuellement porteur d'un ou plusieurs substituants alkyle comprenant 1 à 10 atomes de carbone.17. Method according to one of the preceding claims, characterized in that the co-surfactant is chosen from primary alcohols comprising at least one aliphatic radical, linear or branched, saturated or not, comprising from 4 to 22 carbon atoms, or at least one aromatic radical, preferably comprising 6 carbon atoms, optionally bearing one or more alkyl substituents comprising 1 to 10 carbon atoms.
18. Procédé selon l'une des revendications précédentes, caractérisé en ce que la proportion pondérale co-tensioactif / tensioactif est comprise entre 0 exclu et 50 % en poids, de préférence entre 5 et 40 % en poids.18. Method according to one of the preceding claims, characterized in that the weight ratio of co-surfactant / surfactant is between 0 excluded and 50% by weight, preferably between 5 and 40% by weight.
19. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'agent neutralisant est choisi parmi les composés solubles dans la phase huile et portant au moins une fonction aminé ou carboxylique. 19. Method according to one of the preceding claims, characterized in that the neutralizing agent is chosen from compounds soluble in the oil phase and carrying at least one amine or carboxylic function.
20. Procédé selon l'une des revendications précédentes, caractérisé en ce que la proportion pondérale agent neutralisant / tensioactif est comprise entre 0 exclu et 50 % en poids, de préférence entre 5 et 40 % en poids.20. Method according to one of the preceding claims, characterized in that the proportion by weight of neutralizing agent / surfactant is between 0 excluded and 50% by weight, preferably between 5 and 40% by weight.
21. Procédé selon l'une des revendications précédentes, caractérisé en ce que la teneur en amphiphile totale est comprise entre 5 et 30 % en poids du concentré émulsionnable.21. Method according to one of the preceding claims, characterized in that the total amphiphilic content is between 5 and 30% by weight of the emulsifiable concentrate.
22. Procédé selon l'une des revendications précédentes, caractérisé en ce que la quantité d'eau est telle que le concentré émulsionnable est limpide, de préférence inférieure ou égale à 10 % en poids.22. Method according to one of the preceding claims, characterized in that the amount of water is such that the emulsifiable concentrate is clear, preferably less than or equal to 10% by weight.
23. Procédé selon l'une des revendications précédentes, caractérisé en ce que la teneur en concentré émulsionnable représente 0,1 à 40 % en poids de la phase aqueuse, de préférence 0,1 à 30 % en poids de la phase aqueuse.23. Method according to one of the preceding claims, characterized in that the content of emulsifiable concentrate represents 0.1 to 40% by weight of the aqueous phase, preferably 0.1 to 30% by weight of the aqueous phase.
24. Concentré émulsionnable limpide comprenant une phase huile, éventuellement de l'eau, et des composés amphiphiles consistant en au moins un tensioactif, au moins un copolymère possédant au moins un segment hydrophile et au moins un segment hydrophobe, à l'exclusion de copolymères ne comprenant que des segments obtenus à partir d'oxyde d'éthylène et d'oxyde de propylène, éventuellement au moins un co-tensioactif et éventuellement au moins un agent neutralisant ; * la teneur totale en composés amphiphiles représentant 1 à 40 % en poids du concentré émulsionnable ; * la teneur en copolymère représentant 0,1 à 25 % en poids desdits composés amphiphiles. 24. Clear emulsifiable concentrate comprising an oil phase, optionally water, and amphiphilic compounds consisting of at least one surfactant, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, excluding copolymers comprising only segments obtained from ethylene oxide and propylene oxide, optionally at least one co-surfactant and optionally at least one neutralizing agent; * the total content of amphiphilic compounds representing 1 to 40% by weight of the emulsifiable concentrate; * the content of copolymer representing 0.1 to 25% by weight of said amphiphilic compounds.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0204860A FR2838653B1 (en) | 2002-04-18 | 2002-04-18 | PROCESS FOR PREPARING EMULSION DILUTION OF EMULSIFIABLE CONCENTRATE COMPRISING AN AMPHIPHILIC COPOLYMER |
| FR0204860 | 2002-04-18 | ||
| PCT/FR2003/001153 WO2003090916A2 (en) | 2002-04-18 | 2003-04-11 | Method for preparing an emulsion by diluting an emulsifiable concentrate comprising an amphiphilic copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1494795A2 true EP1494795A2 (en) | 2005-01-12 |
Family
ID=28686156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03747139A Withdrawn EP1494795A2 (en) | 2002-04-18 | 2003-04-11 | Method for preparing an emulsion by diluting an emulsifiable concentrate comprising an amphiphilic copolymer |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20050245650A1 (en) |
| EP (1) | EP1494795A2 (en) |
| AU (1) | AU2003246819A1 (en) |
| FR (1) | FR2838653B1 (en) |
| WO (1) | WO2003090916A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2880024B1 (en) * | 2004-12-23 | 2007-02-02 | Arkema Sa | USE OF COMPOSITE GRADIENT COPOLYMERS AS STABILIZERS IN EMULSION RADICULAR POLYMERIZATION |
| FR2885367B1 (en) * | 2005-05-03 | 2007-07-27 | Rhodia Chimie Sa | ORGANOSOL STABILIZED BY AMPHIPHILIC SEQUENCE POLYMERS |
| US8500474B2 (en) | 2011-08-09 | 2013-08-06 | Ck Technologies, Inc. | Cable/harness test connector |
| US20190100715A1 (en) * | 2017-09-29 | 2019-04-04 | Pilot Chemical Corp. | Emulsions having oil phase surfactants and water phase additive blends |
| FR3129080A1 (en) | 2021-11-15 | 2023-05-19 | Farevacare | EMULSIFIABLE CONCENTRATED COSMETIC COMPOSITION TO DILUTE |
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|---|---|---|---|---|
| US5508035A (en) * | 1988-09-01 | 1996-04-16 | Dowelanco | Stable concentrates and emulsions of water-insoluble organic pesticides |
| US5753248A (en) * | 1993-07-02 | 1998-05-19 | The Dow Chemical Company | Amphipathic graft copolymer pesticide formulation compositions and methods of their use |
| US5744155A (en) * | 1993-08-13 | 1998-04-28 | Friedman; Doron | Bioadhesive emulsion preparations for enhanced drug delivery |
| GB9319112D0 (en) * | 1993-09-15 | 1993-11-03 | Allied Colloids Ltd | Stabilisation and use of heterogeneous liquid composition |
| FR2710552B1 (en) * | 1993-09-30 | 1995-12-22 | Lvmh Rech | Use of acrylic block copolymers as wetting agents and / or dispersants of solid particles and resulting dispersions. |
| CA2192666A1 (en) * | 1994-06-24 | 1996-01-04 | Craig J. Bott | Novel amphipathic graft copolymers, their preparation, compositions thereof, and methods of their use |
| US5981625A (en) * | 1995-06-23 | 1999-11-09 | Videojet Systems International, Inc. | Non-rub off printing inks |
| GB9519468D0 (en) * | 1995-09-23 | 1995-11-22 | Smithkline Beecham Plc | Novel process |
| DE19704714A1 (en) * | 1996-01-25 | 1997-07-31 | Basf Ag | Water-soluble amphiphilic block copolymers useful as non-migrating dispersants for polymer dispersions |
| US6826173B1 (en) * | 1999-12-30 | 2004-11-30 | At&T Corp. | Enhanced subscriber IP alerting |
| US6355675B1 (en) * | 2001-05-15 | 2002-03-12 | Isp Investments Inc. | Emulsifiable concentrate of a water-insoluble fungicide |
-
2002
- 2002-04-18 FR FR0204860A patent/FR2838653B1/en not_active Expired - Fee Related
-
2003
- 2003-04-11 WO PCT/FR2003/001153 patent/WO2003090916A2/en not_active Application Discontinuation
- 2003-04-11 AU AU2003246819A patent/AU2003246819A1/en not_active Abandoned
- 2003-04-11 EP EP03747139A patent/EP1494795A2/en not_active Withdrawn
- 2003-04-11 US US10/511,701 patent/US20050245650A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO03090916A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003090916A2 (en) | 2003-11-06 |
| US20050245650A1 (en) | 2005-11-03 |
| WO2003090916A3 (en) | 2004-04-01 |
| FR2838653B1 (en) | 2005-02-18 |
| FR2838653A1 (en) | 2003-10-24 |
| AU2003246819A1 (en) | 2003-11-10 |
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