WO1994000508A1 - Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides - Google Patents
Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides Download PDFInfo
- Publication number
- WO1994000508A1 WO1994000508A1 PCT/GB1993/001335 GB9301335W WO9400508A1 WO 1994000508 A1 WO1994000508 A1 WO 1994000508A1 GB 9301335 W GB9301335 W GB 9301335W WO 9400508 A1 WO9400508 A1 WO 9400508A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- formula
- group
- alkyl
- water
- Prior art date
Links
- 239000004094 surface-active agent Substances 0.000 title abstract description 33
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 title abstract 2
- 210000002268 wool Anatomy 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 71
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- -1 alkali metal cation Chemical class 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 12
- 239000007762 w/o emulsion Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 239000004166 Lanolin Substances 0.000 claims description 8
- 235000019388 lanolin Nutrition 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 238000009991 scouring Methods 0.000 abstract description 16
- 239000000839 emulsion Substances 0.000 abstract description 10
- 150000002148 esters Chemical class 0.000 abstract description 6
- 150000001408 amides Chemical class 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 125000003342 alkenyl group Chemical group 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229940014800 succinic anhydride Drugs 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920001515 polyalkylene glycol Polymers 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 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 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 3
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000847 nonoxynol Polymers 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000011044 succinic acid Nutrition 0.000 description 2
- 150000003444 succinic acids Chemical class 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000004297 Draba Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229920001400 block copolymer Chemical group 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005604 random copolymer Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000002730 succinyl group Chemical group C(CCC(=O)*)(=O)* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000007056 transamidation reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- C09K23/22—Amides or hydrazides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
-
- 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
- C09K23/16—Amines or polyamines
-
- 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
- C09K23/34—Higher-molecular-weight carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B11/00—Recovery or refining of other fatty substances, e.g. lanolin or waxes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01C—CHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
- D01C3/00—Treatment of animal material, e.g. chemical scouring of wool
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
Definitions
- This invention relates to surfactants and in particular to novel surfactants based on derivatives of substituted succinic acids and to particular end uses for these surfactants.
- EP 0107199 B relates to polvoxyalkylene glycol hemi-esters of CQ to C12 alk(en)yl substituted succinic acids and their salts. These materials are described as anionic surfactants with particular utility at acidic pHs and having hard water tolerance.
- This invention is based on the discovery of compounds which can be derived from alkenyl succinic anhydrides having particularly C14 to C22 alk(en)yl groups and/or substituents of functional groups elsewhere around the molecule give materials which have significantly and surprisingly different properties. In particular they perform well as non-ionic surfactants, particularly in aqueous systems, having unexpected cloud point properties indicating good performance at elevated temperatures and have good behaviour in alkaline conditions. Also the surfactants of this invention have good biodegradation properties.
- the present invention accordingly provides a compound of the formulae (I) or (II):
- R and R 1 is C5 to C22 alkenyl or alkyl and the other is hydrogen;
- A is - 0 - or - R ⁇ -; where R ⁇ is hydrogen or Ci to C alkyl, particularly methyl or ethyl; n is 2 to 100 (and as it is an average it may be non-integral); m is 2 or 3 (and may vary along the polvoxyalkylene chain); R 2 is hydrogen or C]_ to C5 alkyl; A 1 is - 0 -, - 0- or -NR 4 - where R 4 is hydrogen or C*
- Y is a cation, particularly H + , and alkali metal cation especially a sodium or potassium cation, or an ammonium ion (especially NHz,-* " , an amine ammonium or an alkanolamine ammonium ion); and when A 1 is - 0 - or -NR 4 -:
- Y is a C*_ to Cs alkyl group (R 3 ) or a group of the formula (C m H2m°)n- ⁇ where m, n and R 2 are independently as defined above; provided that when A is - 0 - or A 1 is - 0 ⁇ the total number of carbon atoms in the groups R, R 1 and any groups R 2 and R 3 is at least 13, and is desirably 13 to 50; or
- the free acid forms of compounds of the formulae (I) and (II) in are defined with Y as a H + cation.
- Y a H + cation.
- this includes both the ionised form of the free acid that will typically predominate at relatively alkaline pHs and the non-ionised form, that will typically predominate at relatively acidic pHs.
- a and A 1 are desirably both - 0 -, both - NR 4 -, particularly - NH -, or A is - NR 4 -, particularly - NH -, and A 1 is - 0 -. Accordingly, the following particular sub-groups of compounds of the formula (I) form specific aspects of the invention (see also below about R and R**-).
- Y, m, n and R 2 are as defined above formula (I); and R and R 1 are as defined above for formula (I), but particularly where one of R and R 1 is a C1 to C22- especially a C1 to C20» alkenyl or alkyl group and the other is hydrogen.
- the compounds of the general formula (II) can be considered as di(substituted succinyl) functional derivatives of a polyoxyalkylene moiety.
- the respective groups A and A 1 and Y will be the same.
- both groups A are - 0 - or - NR 4 -, particularly - NH -, and both groups A 1 are - 0" with Y being a cation.
- the alk(en)yl groups in the groups R and R**- will usually be the same.
- Y is a cation, it is desirably H + , an alkali metal cation or an ammonium cation, particularly H + , an amine ammonium cation, such as tetramethylammonium or an alkanolamine ammonium ion e.g. H0.CH2CH .NH3 + ; where Y is a Ci to C5 alkyl group, it is particularly a methyl, ethyl or (straight or branched) butyl group.
- R 2 in formulae (I) and (II) is desirably either H or a methyl, ethyl, propyl or butyl (including branched propyl and butyl) group. Where R 2 is H, the products tend to be relatively more
- the compounds of the invention include at least one polyoxyalkylene chain made up of residues of ethylene glycol and/or
- the chain may be a homopolymer chain of either ethylene glycol residues or of propylene glycol residues or a block or random copolymer chain containing both ethylene glycol and propylene glycol residues. In compounds including more than one polyoxyalkylene chain, the chains can be the same or different.
- polyoxyalkylene chain defined as the group (C m H2mO) n in formula (I) (including la, lb and Ic) and (II).
- the chain length of this group i.e. the value of the parameter n, will generally be chosen to provide the desired properties in the intended product.
- the polyoxyalkylene chain is a
- polyethylene glycol chain it will usually have 3 to 50, particularly 3 to 35 e.g. 10 to 35, ethylene glycol residues and where it is a polyoxypropylene chain it will usually have 10 to 50 and more preferably 12 to 20 propylene glycol residues.
- the chain is a block or random copolymer of ethylene and propylene glycol residues
- the chain length chosen will typically correspond to the above ranges but numerically according to the proportion of ethylene and propylene glycol residues in the chain. Of course, numerical values of the > repeat length of the polyoxyalkylene chain are average values. As is common to surfactants containing a polyoxyalkylene chain, the longer
- compounds where the group R or R 1 is an alkenyl group are more desirable than those where the group is alkyl.
- Compounds where the group R or R 1 is an alkenyl group, particularly a C14 to C20 alkenyl group form a specific aspect of the invention.
- the compounds of this invention, and particularly those where the group R or R 1 is a C1 to C22 alkenyl or alkyl group have properties that are entirely unexpected in that the cloud point tends to rise with increasing length of the chain R or R , particularly where this chain is an alkenyl chain. The step from C12 to £3.4 chains is often particularly notable.
- the cloud point may tend to fall back somewhat, but often stays significantly above that for compounds with a chain length of say C ⁇ _2. This trend in cloud point indicates increasing water solubility of the compounds with increasing chain length which is completely unexpected and runs counter to previous experience with surfactants. However, at longer chain lengths the compounds tend to be less effective wetters, which is consistent with the increasingly hydrophobic nature of the group R/R 1 .
- surfactants are usually most effective at or near their cloud points.
- Higher cloud points indicate materials that are likely to be effective at comparably higher temperatures and surfactants are often used at moderately superambient temperatures.
- the longer chain lengths are linked with increased oil solubility so the cloud point behaviour indicates that better oil , solubility is likely to be linked to higher effective temperatures.
- the product is typically a mixture of isomers corresponding to the two senses of the anhydride ring opening reaction.
- the alkenyl or alkyl chain seems to have a minor steric effect on the isomer ratio with the isomer ration being typically about 60:40, the major isomer arising from nucleophilic attack at the anhydride carbonyl group remote from the alkenyl or alkyl group.
- Y is a different cation
- Y is an alkali metal or ammonium cation formation of the salts is straightforward by reaction with the corresponding base e.g. alkali metal such as sodium or potassium, hydroxide or carbonate, ammonia or amine, including alkanolamines such as ethanolamine.
- alkali metal such as sodium or potassium
- hydroxide or carbonate ammonia or amine
- alkanolamines such as ethanolamine.
- a 1 is other than -0 ⁇ i.e. Y is other than a cation
- further reaction is by preparation of an ester, particularly an ester with a C_ to C5 or polyalkylene glycol alkyl ether alcohol.
- esters and the corresponding amides can be made from esters with short chain alcohols, especially methyl or ethyl esters, by trans-esterification or amidation with the corresponding alcohol (YOH) or amine (YNH2) (where Y is as defined above).
- the esterification of the free acid can be carried out in a conventional manner for example using an acid catalyst which may be sulphuric, toluene sulphonic or a phosphoric acid.
- Phosphoric acids can be particularly useful as, after neutralisation, they may be a useful component of detergent compositions which include the surfactants of this invention.
- the compounds of the invention may be made by other methods.
- the anhydride may be reacted with a lower alcohol and the resulting half ester esterified with a polyalkylene glycol or polyalkylene glycol alkyl ether or condensed with an alkylene oxide and if desired end capped with a further lower alcohol.
- the poly ⁇ alkylene glycol chain length can be controlled by using a polyalkylene glycol or polyalkylene glycol alkyl ether of a narrow range of molecular weight, whereas the latter process gives a wide distribution of chain lengths.
- Alkenyl succinic anhydrides may be produced by reacting maleic anhydride preferably with an excess of an olefin having 6 to 22, particularly 14 to 22, carbon atoms for example a 50 to 200Z excess at a temperature in the range 150 to 400°C and preferably 180 to 250°C and removing excess olefin for example by distillation which is suitably carried out under vacuum. No catalyst is necessary, but is is preferred than an antioxidant be present.
- These anhydrides are well known commercial materials. In alkenyl succinic anhydrides prepared as described above the double bond normally lies in the 2-position in the alkenyl substituent.
- the unsaturated products can be hydrogenated or, and preferably, the intermediate alkenyl succinic anhydride can be hydrogenated to give an alkyl succinic anhydride.
- the hydrogenation is carried out over a hydrogenation catalyst such as Raney nickel or a Pd/C catalyst. Temperatures of from 15 to 100°C and pressures of 0 - 200 bar absolute may be used and, if desired a solvent may be present.
- the hydrogenation reaction on an alkenyl succinic anhydride may be carried out at 20°C using 5Z w/w of Pd/C catalyst over a period of for example 6 to 24 hours.
- the R, R 1 alkyl or alkenyl group of the compounds of the invention has a straight chain. Where the chain is not straight it is desirable that it has at most a total of two and preferably only one branch(es) on average. Preferably the whole molecule comprises at most three branches in total in all alkyl and alkenyl groups present.
- the products are readily made with low odour and, since polyalkylene glycols and polyalkylene glycol alkyl ether or their amine derivatives are readily transportable can be made at locations distant from alkylene oxide plants if they are used as reactants.
- Compounds according to the invention have emulsification properties and wetting and dispersion capabilities. These include use in oil in water emulsions for metal working fluids, based on semi-soluble oil and synthetics and for crude oil transportation and fuel systems, emollients for personal (skin) care; domestic detergent composition for example laundry liquids; the dispersion or organic and inorganic powders in paints and coatings (e.g. filler and pigments) and agrochemical formulations (e.g. pesticides); wetters in so-called industrial and institutional cleaning products (e.g. traffic film removers, bottle washes).
- industrial and institutional cleaning products e.g. traffic film removers, bottle washes.
- the surfactants of this invention include wool scouring and as inverting agents in the manufacture of acrylamide or similar products. These applications are described in more detail below.
- the woollen fleece includes, in addition to the wool fibre, a variety of materials including wool wax. Wool wax is a complex mixture of fatty materials secreted onto the wool by the skin of the sheep. Wool wax is removed from the wool, prior to use of the wool in textiles, by washing the wool with an aqueous mix including surfactants typically at moderately elevated temperatures e.g. 40 to 80°C, particularly 50 to 70°C. This process is called wool scouring.
- the surfactants of this invention are very effective wool scouring surfactants, in particular retaining their activity well after multiple scouring cycles, even when used in scouring wool with very fine fibres e.g. merino wool, which is difficult to scour because the proportion of wool fat is relatively high and the fibres have a high surface area to be treated.
- very fine fibres e.g. merino wool
- R 2 is a C**_ to CQ alkyl group, especially a methyl group are especially effective.
- the surfactant in this application is typically used at a concentration of from 0.1 to 5, particularly from 0.2 to 1.5, g.1-1.
- the invention accordingly includes a method of treating wool to remove wool wax which method comprises washing the wool, containing wool wax, with an aqueous mix including an effective amount of a compound of the formulae (I) or (II) above, in particular a compound of the formula (la) above, especially where m is 2, n is from 3 to 10 and where R 2 is a Ci to CQ alkyl group, particularly a methyl group.
- the invention also includes the use of such compounds of the invention as wool scouring surfactants.
- polymers such as polyacrylamide
- an emulsion polymerisation route in which the polymer is accumulated in an aqueous phase (in which it is soluble).
- aqueous phase in which it is soluble
- polyacrylamides can give aqueous solutions having high viscosities even at low concentrations; this is the basis of their use as thickeners and viscosity enhancers in aqueous systems. If the aqueous phase during polymerisation were the continuous phase, it would rapidly become very viscous, leading to difficulties in agitation and recovery of the product. To avoid this problem, the aqueous phase is normally the dispersed phase in an oil continuous phase i.e.
- a compound within the invention for this end use will depend on the specific operating conditions, we have found that compounds of the formula (la) above, particularly where m is 2, n is from 8 to 25, particularly 10 to 15, and where R 2 is H or a Ci to C5 alkyl group, particularly a methyl, ethyl, propyl or butyl group, are especially effective.
- the amount of surface active agent used to invert such emulsions will depend on the emulsion, in particular the proportion of disperse aqueous phase and the polymer concentration in the aqueous phase. Generally amounts in the range 1 to 5Z of the water in oil emulsion are typical.
- the invention accordingly includes a method of inverting a water in oil emulsion containing polyacrylamide in the aqueous phase which comprises including in the water in oil emulsion a compound of the formulae (I) or (II) above, in particular a compound of the formula (ia) above, especially m is 2, n is from 8 to 25, particularly 10 to 15, and where R 2 is H or a Ci to Cs alkyl group, particularly a methyl, ethyl, propyl or butyl group, and subsequently diluting the water in oil emulsion into water.
- the invention also includes the use of compounds of the invention as polyacrylamide water in oil emulsion inverting agents.
- Draves wetting was assessed using the skein test (ASTM D 2281 - 68); results are in seconds (s) [or minutes (m) - for slow wetters].
- 's' indicates that the substituent is an alkyl group; for R 2 H » hydrogen and a number the length of an alkyl group, for Y H indicates Y • » H + and a number the alkyl chain length.
- n may be rounded values; for compounds of the formula (II) the value for 'n* in this table is n+p in formula (II) as given above (with p » m) .
- Semi aqueous cleaning involves the cleaning of, e.g. metal, components with a solvent followed by a water rinse stage. Frequently solvents derived from terpenes are used in this application.
- Surface active agents can be added to expedite the removal of the solvent from the components being cleaned during the water rinse stage.
- Such surface active agents, or rinse aids as they are known must fulfil two criteria. Firstly they must effect good solvent removal and be soluble in the cleaning solvent. Secondly they must not stabilise mixtures of the solvent and water thus preventing effective separation of the mixture with adverse implications on waste disposal.
- Materials A and B below have the desired surface active properties to be effective rinse aids in semi aqueous cleaning formulations. They are also soluble in terpene solvents. Surprisingly tests have demonstrated that they exhibit rapid and more effective solvent and water separation as compared to other surfactants commonly used in this application.
- Complete separation means oil layer of 10Z and a water layer of 90Z of 0 the total volume.
- the following mixture was polymerised by heating to about 40°C using as the primary emulsifier a commercially available polymeric surfactant sold under the trade name "HYPERMER” 2296.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019940704735A KR950702215A (en) | 1992-06-26 | 1993-06-25 | SURFACTANTS DERIVED FROM POLYLXYALKYLENES AND SUBSTITUTED SUCCINIC ANHYDRIDES Derived from Polyoxyalkylenes and Substituted Succinic Anhydrides |
JP6502165A JPH07508546A (en) | 1992-06-26 | 1993-06-25 | Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides |
SK1596-94A SK159694A3 (en) | 1992-06-26 | 1993-06-25 | Surfactans derived from polyoxyalkylenes and anhydrides of substituted succinic acids and their using |
AU43505/93A AU679918B2 (en) | 1992-06-26 | 1993-06-25 | Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides |
EP93913432A EP0647248A1 (en) | 1992-06-26 | 1993-06-25 | Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides |
CA002139003A CA2139003A1 (en) | 1992-06-26 | 1993-06-25 | Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides |
FI946075A FI946075A0 (en) | 1992-06-26 | 1994-12-23 | Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB929213571A GB9213571D0 (en) | 1992-06-26 | 1992-06-26 | Surfactants |
GB9213571.4 | 1992-06-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994000508A1 true WO1994000508A1 (en) | 1994-01-06 |
Family
ID=10717766
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1993/001335 WO1994000508A1 (en) | 1992-06-26 | 1993-06-25 | Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides |
Country Status (15)
Country | Link |
---|---|
EP (1) | EP0647248A1 (en) |
JP (1) | JPH07508546A (en) |
KR (1) | KR950702215A (en) |
AU (1) | AU679918B2 (en) |
CA (1) | CA2139003A1 (en) |
CZ (1) | CZ328094A3 (en) |
FI (1) | FI946075A0 (en) |
GB (2) | GB9213571D0 (en) |
HU (1) | HUT68780A (en) |
NZ (1) | NZ253297A (en) |
RU (1) | RU2118641C1 (en) |
SK (1) | SK159694A3 (en) |
TW (1) | TW256854B (en) |
WO (1) | WO1994000508A1 (en) |
ZA (1) | ZA934479B (en) |
Cited By (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995006096A1 (en) * | 1993-08-23 | 1995-03-02 | Imperial Chemical Industries Plc | Surfactants |
WO1995022897A1 (en) * | 1994-02-24 | 1995-08-31 | Imperial Chemical Industries Plc | Emulsifier compositions |
WO1996016930A1 (en) * | 1994-12-02 | 1996-06-06 | Imperial Chemical Industries Plc | Succinic acid derivatives and their use as surfactants |
EP0747342A1 (en) * | 1995-06-09 | 1996-12-11 | Mitsui Toatsu Chemicals, Incorporated | Unsaturated hemiesters of alkyl succinic acid, polymers therefrom and use of said polymers |
WO1997041178A1 (en) * | 1996-05-02 | 1997-11-06 | Ici Americas Inc. | Aqueous dispersions containing substituted succinic anhydride derivatives |
EP0809623A1 (en) * | 1995-02-15 | 1997-12-03 | Basf Aktiengesellschaft | Alk(en)yl dicarboxylic acid bisesters, their use and method for preparing them |
WO1998037957A1 (en) * | 1997-02-27 | 1998-09-03 | Imperial Chemical Industries Plc | Surfactants |
US5807923A (en) * | 1993-08-23 | 1998-09-15 | Imperial Chemical Industries Plc | Process of emulsion polymerization |
EP0909593A2 (en) * | 1997-10-14 | 1999-04-21 | The Lubrizol Corporation | Surfactant-assisted soil remediation |
WO1999049963A1 (en) * | 1998-03-28 | 1999-10-07 | Avecia Limited | Dispersants |
US5993793A (en) * | 1996-06-21 | 1999-11-30 | L'oreal | Use of succinic anhydride derivatives in skin cleansing compositions |
WO2001026791A2 (en) * | 1999-10-11 | 2001-04-19 | Imperial Chemical Industries Plc | Polymeric surfactants |
EP1120102A2 (en) | 2000-01-21 | 2001-08-01 | L'oreal | Nanoemulsion containing amphiphilc lipids and a nonionic polymer and its use in cosmetics |
WO2002059159A1 (en) * | 2001-01-24 | 2002-08-01 | Imperial Chemical Industries Plc | Anionic surfactants |
US6780209B1 (en) | 2000-01-24 | 2004-08-24 | The Lubrizol Corporation | Partially dehydrated reaction product process for making same, and emulsion containing same |
US6998426B2 (en) | 2000-07-13 | 2006-02-14 | L'oreal | Nanoemulsion containing nonionic polymers, and its uses |
WO2007131860A1 (en) * | 2006-05-12 | 2007-11-22 | Unilever N.V. | Aqueous liquid cleaning compositions and their use |
EP2343036A1 (en) | 2009-12-23 | 2011-07-13 | L'Oréal | Cosmetic composition in the form of a nanoemulsion containing a volatile linear alkane |
WO2012029038A1 (en) | 2010-09-01 | 2012-03-08 | Basf Se | Amphiphile for solubilization of water-soluble active ingredients |
US8338356B2 (en) | 2008-12-25 | 2012-12-25 | Dow Global Technologies Llc | Surfactant compositions with wide pH stability |
WO2014080190A1 (en) | 2012-11-20 | 2014-05-30 | Croda International Plc | Penetrants for agrochemical formulations |
WO2014105877A1 (en) | 2012-12-27 | 2014-07-03 | L'oreal | Low viscosity meta-stable photoprotection composition |
WO2014184660A2 (en) | 2013-05-17 | 2014-11-20 | L'oreal | Emulsion stabilization |
WO2014184658A2 (en) | 2013-05-17 | 2014-11-20 | L'oreal | Stable bubbles via particle absorption by electrostatic interaction |
WO2015023434A1 (en) | 2013-08-14 | 2015-02-19 | Croda, Inc. | Adjuvancy combination |
WO2015023426A1 (en) | 2013-08-14 | 2015-02-19 | Croda, Inc. | Spray drift reduction |
US9168218B2 (en) | 2011-01-25 | 2015-10-27 | L'oreal S.A. | Use of photoluminescent polymers in cosmetic products |
US9452406B2 (en) | 2013-05-17 | 2016-09-27 | L'oreal | Bubble encapsulation via silicilic acid complexation |
EP3075436A1 (en) * | 2015-04-02 | 2016-10-05 | Afton Chemical Limited | Diesel exhaust fluid solutions and methods of using the same |
DE102015015911A1 (en) | 2015-12-09 | 2017-06-14 | Nanopartica Gmbh | Highly efficient nanotransport system by covalently bonded alkenyl succinic anhydride derivatives on dendritic polymers |
WO2018005340A1 (en) | 2016-07-01 | 2018-01-04 | Croda, Inc. | Spray drift reduction |
US10028895B2 (en) | 2013-05-17 | 2018-07-24 | L'oreal | Emulsion stabilization via silicilic acid complexation |
WO2018231567A1 (en) | 2017-06-13 | 2018-12-20 | Croda, Inc. | Agrochemical electrolyte compositions |
US10196318B2 (en) | 2014-02-28 | 2019-02-05 | Croda International Plc | Micronutrient compositions |
WO2019185851A1 (en) | 2018-03-28 | 2019-10-03 | Croda International Plc | Agrochemical polymer dispersants |
US11046813B2 (en) | 2013-10-18 | 2021-06-29 | Croda, Inc. | Alkoxylated polysorbate ester adjuvants |
US11044906B2 (en) | 2016-05-25 | 2021-06-29 | Croda International Plc | Polymeric coating compositions |
WO2021202951A1 (en) | 2020-04-03 | 2021-10-07 | Croda International Plc | Agrochemical adjuvants |
WO2022040038A2 (en) | 2020-08-17 | 2022-02-24 | Croda International Plc | Agrochemical adjuvants |
WO2022074064A1 (en) | 2020-10-07 | 2022-04-14 | Croda International Plc | Suspension concentrate dispersants |
WO2022187209A1 (en) | 2021-03-02 | 2022-09-09 | Croda International Plc | Agrochemical adjuvants from stachybotrys chartarum |
WO2023083797A1 (en) | 2021-11-09 | 2023-05-19 | Croda International Plc | Suspension concentrate dispersants |
WO2023152569A1 (en) | 2022-02-14 | 2023-08-17 | Croda International Plc | Agrochemical adjuvants |
WO2023152566A1 (en) | 2022-02-14 | 2023-08-17 | Croda International Plc | Agrochemical adjuvants |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6841610B2 (en) * | 2016-07-15 | 2021-03-10 | 松本油脂製薬株式会社 | Cleaning agent composition and cleaning method |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0107199A2 (en) * | 1979-10-26 | 1984-05-02 | CHINOIN Gyogyszer és Vegyészeti Termékek Gyára RT. | Anionic surface active agents and the preparation thereof |
GB2131820A (en) * | 1982-12-13 | 1984-06-27 | Chevron Res | Nonionic emulsifier and hydrocarbyl substituted succinic anhydride compositions emulsified therewith |
WO1987000856A1 (en) * | 1985-07-29 | 1987-02-12 | The Lubrizol Corporation | Water-based functional fluid thickening combinations of surfactants and hydrocarbyl-substituted succinic acid and/or anhydride/amine terminated poly(oxyalkylene) reaction products |
EP0384605A1 (en) * | 1989-02-06 | 1990-08-29 | Texaco Development Corporation | Ori-inhibited motor fuel composition |
-
1992
- 1992-06-26 GB GB929213571A patent/GB9213571D0/en active Pending
-
1993
- 1993-06-22 ZA ZA934479A patent/ZA934479B/en unknown
- 1993-06-24 GB GB939313096A patent/GB9313096D0/en active Pending
- 1993-06-25 CZ CZ943280A patent/CZ328094A3/en unknown
- 1993-06-25 AU AU43505/93A patent/AU679918B2/en not_active Ceased
- 1993-06-25 JP JP6502165A patent/JPH07508546A/en active Pending
- 1993-06-25 WO PCT/GB1993/001335 patent/WO1994000508A1/en not_active Application Discontinuation
- 1993-06-25 NZ NZ253297A patent/NZ253297A/en unknown
- 1993-06-25 EP EP93913432A patent/EP0647248A1/en not_active Withdrawn
- 1993-06-25 RU RU94046395A patent/RU2118641C1/en active
- 1993-06-25 SK SK1596-94A patent/SK159694A3/en unknown
- 1993-06-25 CA CA002139003A patent/CA2139003A1/en not_active Abandoned
- 1993-06-25 HU HU9403701A patent/HUT68780A/en unknown
- 1993-06-25 KR KR1019940704735A patent/KR950702215A/en not_active IP Right Cessation
- 1993-06-26 TW TW082105101A patent/TW256854B/zh active
-
1994
- 1994-12-23 FI FI946075A patent/FI946075A0/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0107199A2 (en) * | 1979-10-26 | 1984-05-02 | CHINOIN Gyogyszer és Vegyészeti Termékek Gyára RT. | Anionic surface active agents and the preparation thereof |
GB2131820A (en) * | 1982-12-13 | 1984-06-27 | Chevron Res | Nonionic emulsifier and hydrocarbyl substituted succinic anhydride compositions emulsified therewith |
WO1987000856A1 (en) * | 1985-07-29 | 1987-02-12 | The Lubrizol Corporation | Water-based functional fluid thickening combinations of surfactants and hydrocarbyl-substituted succinic acid and/or anhydride/amine terminated poly(oxyalkylene) reaction products |
EP0384605A1 (en) * | 1989-02-06 | 1990-08-29 | Texaco Development Corporation | Ori-inhibited motor fuel composition |
Cited By (67)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995006096A1 (en) * | 1993-08-23 | 1995-03-02 | Imperial Chemical Industries Plc | Surfactants |
US5807923A (en) * | 1993-08-23 | 1998-09-15 | Imperial Chemical Industries Plc | Process of emulsion polymerization |
US5770550A (en) * | 1993-08-23 | 1998-06-23 | Imperial Chemical Industries Plc | Surfactants |
WO1995022897A1 (en) * | 1994-02-24 | 1995-08-31 | Imperial Chemical Industries Plc | Emulsifier compositions |
WO1995022896A1 (en) * | 1994-02-24 | 1995-08-31 | Imperial Chemical Industries Plc | Adjuvant compositions |
US5798331A (en) * | 1994-12-02 | 1998-08-25 | Imperial Chemical Industries Plc | Succinic acid derivatives and their use as surfactants |
WO1996016930A1 (en) * | 1994-12-02 | 1996-06-06 | Imperial Chemical Industries Plc | Succinic acid derivatives and their use as surfactants |
CN1072642C (en) * | 1994-12-02 | 2001-10-10 | 帝国化学工业公司 | Butanedioic acid derivative and their use as surfactants |
AU695780B2 (en) * | 1994-12-02 | 1998-08-20 | Imperial Chemical Industries Plc | Succinic acid derivatives and their use as surfactants |
US5872149A (en) * | 1995-02-15 | 1999-02-16 | Basf Aktiengesellschaft | Alk(en)yldicarboxylic acid bisesters, their use, and processes for their preparation |
EP0809623A1 (en) * | 1995-02-15 | 1997-12-03 | Basf Aktiengesellschaft | Alk(en)yl dicarboxylic acid bisesters, their use and method for preparing them |
EP0809623B1 (en) * | 1995-02-15 | 2000-01-19 | Basf Aktiengesellschaft | Alk(en)yl dicarboxylic acid bisesters, their use and method for preparing them |
US6057412A (en) * | 1995-06-09 | 2000-05-02 | Mitsui Chemicals, Inc. | Amphipathic compound having succinic acid skeleton |
US5872287A (en) * | 1995-06-09 | 1999-02-16 | Mitsui Chemicals, Inc. | Amphipathic compound having succinic acid skeleton |
EP0747342A1 (en) * | 1995-06-09 | 1996-12-11 | Mitsui Toatsu Chemicals, Incorporated | Unsaturated hemiesters of alkyl succinic acid, polymers therefrom and use of said polymers |
US6359093B1 (en) | 1995-06-09 | 2002-03-19 | Mitsui Chemicals, Inc. | Amphipathic compound having succinic acid skeleton |
WO1997041178A1 (en) * | 1996-05-02 | 1997-11-06 | Ici Americas Inc. | Aqueous dispersions containing substituted succinic anhydride derivatives |
US5993793A (en) * | 1996-06-21 | 1999-11-30 | L'oreal | Use of succinic anhydride derivatives in skin cleansing compositions |
WO1998037957A1 (en) * | 1997-02-27 | 1998-09-03 | Imperial Chemical Industries Plc | Surfactants |
CN1126589C (en) * | 1997-02-27 | 2003-11-05 | 帝国化学工业公司 | Surfactants |
EP0909593A2 (en) * | 1997-10-14 | 1999-04-21 | The Lubrizol Corporation | Surfactant-assisted soil remediation |
US6303795B1 (en) | 1997-10-14 | 2001-10-16 | The Lubrizol Corporation | Succinimide-based surfactant suitable for soil remediation |
EP0909593A3 (en) * | 1997-10-14 | 2001-03-14 | The Lubrizol Corporation | Surfactant-assisted soil remediation |
US6599947B2 (en) | 1998-03-28 | 2003-07-29 | Avecia Limited | Dispersants |
WO1999049963A1 (en) * | 1998-03-28 | 1999-10-07 | Avecia Limited | Dispersants |
WO2001026791A2 (en) * | 1999-10-11 | 2001-04-19 | Imperial Chemical Industries Plc | Polymeric surfactants |
WO2001026791A3 (en) * | 1999-10-11 | 2001-10-11 | Ici Plc | Polymeric surfactants |
EP1120102A2 (en) | 2000-01-21 | 2001-08-01 | L'oreal | Nanoemulsion containing amphiphilc lipids and a nonionic polymer and its use in cosmetics |
US8114389B2 (en) | 2000-01-21 | 2012-02-14 | L'oreal S.A. | Nanoemulsions comprising at least one amphiphilic lipid, at least one oil, and at least one nonionic polymer, and uses thereof |
US6780209B1 (en) | 2000-01-24 | 2004-08-24 | The Lubrizol Corporation | Partially dehydrated reaction product process for making same, and emulsion containing same |
US7044988B2 (en) | 2000-01-24 | 2006-05-16 | The Lubrizol Corporation | Partially dehydrated reaction product, process for making same, and emulsion containing same |
US6998426B2 (en) | 2000-07-13 | 2006-02-14 | L'oreal | Nanoemulsion containing nonionic polymers, and its uses |
WO2002059159A1 (en) * | 2001-01-24 | 2002-08-01 | Imperial Chemical Industries Plc | Anionic surfactants |
US6858573B1 (en) | 2001-01-24 | 2005-02-22 | Imperial Chemical Industries Plc | Anionic surfactants |
WO2007131860A1 (en) * | 2006-05-12 | 2007-11-22 | Unilever N.V. | Aqueous liquid cleaning compositions and their use |
US8338356B2 (en) | 2008-12-25 | 2012-12-25 | Dow Global Technologies Llc | Surfactant compositions with wide pH stability |
EP2343036A1 (en) | 2009-12-23 | 2011-07-13 | L'Oréal | Cosmetic composition in the form of a nanoemulsion containing a volatile linear alkane |
WO2012029038A1 (en) | 2010-09-01 | 2012-03-08 | Basf Se | Amphiphile for solubilization of water-soluble active ingredients |
EP2611847A4 (en) * | 2010-09-01 | 2016-09-07 | Basf Se | Amphiphile for solubilization of water-soluble active ingredients |
US9168218B2 (en) | 2011-01-25 | 2015-10-27 | L'oreal S.A. | Use of photoluminescent polymers in cosmetic products |
WO2014080190A1 (en) | 2012-11-20 | 2014-05-30 | Croda International Plc | Penetrants for agrochemical formulations |
US9681658B2 (en) | 2012-11-20 | 2017-06-20 | Croda International Plc | Penetrants for agrochemical formulations |
WO2014105877A1 (en) | 2012-12-27 | 2014-07-03 | L'oreal | Low viscosity meta-stable photoprotection composition |
US9452406B2 (en) | 2013-05-17 | 2016-09-27 | L'oreal | Bubble encapsulation via silicilic acid complexation |
US9433578B2 (en) | 2013-05-17 | 2016-09-06 | L'oreal | Stable bubbles via particle absorption by electrostatic interaction |
US10028895B2 (en) | 2013-05-17 | 2018-07-24 | L'oreal | Emulsion stabilization via silicilic acid complexation |
WO2014184658A2 (en) | 2013-05-17 | 2014-11-20 | L'oreal | Stable bubbles via particle absorption by electrostatic interaction |
WO2014184660A2 (en) | 2013-05-17 | 2014-11-20 | L'oreal | Emulsion stabilization |
WO2015023426A1 (en) | 2013-08-14 | 2015-02-19 | Croda, Inc. | Spray drift reduction |
WO2015023434A1 (en) | 2013-08-14 | 2015-02-19 | Croda, Inc. | Adjuvancy combination |
US10888091B2 (en) | 2013-08-14 | 2021-01-12 | Croda, Inc. | Adjuvancy combination |
US11046813B2 (en) | 2013-10-18 | 2021-06-29 | Croda, Inc. | Alkoxylated polysorbate ester adjuvants |
US10822286B2 (en) | 2014-02-28 | 2020-11-03 | Croda International Plc | Micronutrient compositions |
US10196318B2 (en) | 2014-02-28 | 2019-02-05 | Croda International Plc | Micronutrient compositions |
EP3075436A1 (en) * | 2015-04-02 | 2016-10-05 | Afton Chemical Limited | Diesel exhaust fluid solutions and methods of using the same |
DE102015015911A1 (en) | 2015-12-09 | 2017-06-14 | Nanopartica Gmbh | Highly efficient nanotransport system by covalently bonded alkenyl succinic anhydride derivatives on dendritic polymers |
US11044906B2 (en) | 2016-05-25 | 2021-06-29 | Croda International Plc | Polymeric coating compositions |
WO2018005340A1 (en) | 2016-07-01 | 2018-01-04 | Croda, Inc. | Spray drift reduction |
WO2018231567A1 (en) | 2017-06-13 | 2018-12-20 | Croda, Inc. | Agrochemical electrolyte compositions |
WO2019185851A1 (en) | 2018-03-28 | 2019-10-03 | Croda International Plc | Agrochemical polymer dispersants |
WO2021202951A1 (en) | 2020-04-03 | 2021-10-07 | Croda International Plc | Agrochemical adjuvants |
WO2022040038A2 (en) | 2020-08-17 | 2022-02-24 | Croda International Plc | Agrochemical adjuvants |
WO2022074064A1 (en) | 2020-10-07 | 2022-04-14 | Croda International Plc | Suspension concentrate dispersants |
WO2022187209A1 (en) | 2021-03-02 | 2022-09-09 | Croda International Plc | Agrochemical adjuvants from stachybotrys chartarum |
WO2023083797A1 (en) | 2021-11-09 | 2023-05-19 | Croda International Plc | Suspension concentrate dispersants |
WO2023152569A1 (en) | 2022-02-14 | 2023-08-17 | Croda International Plc | Agrochemical adjuvants |
WO2023152566A1 (en) | 2022-02-14 | 2023-08-17 | Croda International Plc | Agrochemical adjuvants |
Also Published As
Publication number | Publication date |
---|---|
GB9313096D0 (en) | 1993-08-11 |
JPH07508546A (en) | 1995-09-21 |
FI946075A (en) | 1994-12-23 |
FI946075A0 (en) | 1994-12-23 |
GB9213571D0 (en) | 1992-08-12 |
ZA934479B (en) | 1995-03-22 |
NZ253297A (en) | 1997-02-24 |
AU4350593A (en) | 1994-01-24 |
CZ328094A3 (en) | 1995-06-14 |
TW256854B (en) | 1995-09-11 |
HUT68780A (en) | 1995-07-28 |
RU2118641C1 (en) | 1998-09-10 |
KR950702215A (en) | 1995-06-19 |
RU94046395A (en) | 1996-11-20 |
EP0647248A1 (en) | 1995-04-12 |
AU679918B2 (en) | 1997-07-17 |
CA2139003A1 (en) | 1994-01-06 |
SK159694A3 (en) | 1995-06-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0647248A1 (en) | Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides | |
US4340382A (en) | Method for treating and processing textile materials | |
JPH08103646A (en) | Anionic surface active agent and detergent composition containing same | |
WO1998023365A1 (en) | Novel nonionic gemini surfactants | |
EP0874802A1 (en) | Fatty acid derivatives and the use thereof as surface active agents in washing and cleaning agents | |
JPH08103645A (en) | Amphoteric surfactant and detergent composition containing same | |
JP4112500B2 (en) | C10-alkanol alkoxylates and uses thereof | |
GB1601652A (en) | Liquid detergents comprising nonionic surfactants | |
CA1038766A (en) | Amphoteric surface active agents | |
US4592875A (en) | Alkoxylated ether sulfate anionic surfactants from plasticizer alcohol mixtures | |
CA2310646A1 (en) | An ortho ester-based surfactant, its preparation and use | |
US5811384A (en) | Nonionic gemini surfactants | |
AU739995B2 (en) | Surfactants | |
CA1176648A (en) | Carbonate and carboxylic acid ester group-containing non-ionic surface-active agents | |
WO2017073741A1 (en) | Liquid detergent | |
JP3525820B2 (en) | Nonionic surfactant | |
JP2003336092A (en) | Concentrated liquid detergent composition | |
EP0948393A1 (en) | Detergent compositions containing low concentration levels of gemini surfactants | |
WO1998037062A1 (en) | Novel nonylphenol nonionic gemini surfactants | |
US20020147366A1 (en) | Alkoxylated tertiary and quaternary amine surfactants | |
JPS6114295A (en) | Alkoxylated ether sulfate anionic surfactant | |
JP2005187415A (en) | Fatty acid polyoxyalkylenealkyl ether and method for producing the same | |
KR900004552B1 (en) | A process for the preparation of a schifb base surfactants | |
CN115697952A (en) | Compound, precursor compound thereof, surfactant composition, and cleaning agent composition | |
JP4454097B2 (en) | Low foaming detergent composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU BG CA CZ FI HU JP KR NO NZ PL RO RU SK UA US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1993913432 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 253297 Country of ref document: NZ |
|
WWE | Wipo information: entry into national phase |
Ref document number: 159694 Country of ref document: SK Ref document number: 2139003 Country of ref document: CA Ref document number: PV1994-3280 Country of ref document: CZ |
|
WWE | Wipo information: entry into national phase |
Ref document number: 946075 Country of ref document: FI |
|
WWP | Wipo information: published in national office |
Ref document number: 1993913432 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: PV1994-3280 Country of ref document: CZ |
|
WWR | Wipo information: refused in national office |
Ref document number: PV1994-3280 Country of ref document: CZ |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1993913432 Country of ref document: EP |