GB1591293A - Method of improving fluorinated surfactants - Google Patents
Method of improving fluorinated surfactants Download PDFInfo
- Publication number
- GB1591293A GB1591293A GB22282/79A GB2228279A GB1591293A GB 1591293 A GB1591293 A GB 1591293A GB 22282/79 A GB22282/79 A GB 22282/79A GB 2228279 A GB2228279 A GB 2228279A GB 1591293 A GB1591293 A GB 1591293A
- Authority
- GB
- United Kingdom
- Prior art keywords
- surfactant
- salt
- magnesium
- anionic
- fluorinated
- 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.)
- Expired
Links
- 239000004094 surface-active agent Substances 0.000 title claims description 84
- 238000000034 method Methods 0.000 title claims description 16
- 125000000129 anionic group Chemical group 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 38
- 159000000003 magnesium salts Chemical class 0.000 claims description 21
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 125000002091 cationic group Chemical group 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- -1 alkali metal salt Chemical class 0.000 claims description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 10
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229920001774 Perfluoroether Polymers 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
- 239000010452 phosphate Substances 0.000 claims 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 2
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- 101100456896 Drosophila melanogaster metl gene Proteins 0.000 claims 1
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
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- 239000001301 oxygen Substances 0.000 claims 1
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- 229930195733 hydrocarbon Natural products 0.000 description 7
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- 150000001298 alcohols Chemical class 0.000 description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 2
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- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
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- 150000003460 sulfonic acids Chemical class 0.000 description 2
- BFSPAPKTIGPYOV-BQYQJAHWSA-N (e)-1-[4-(4-hydroxyphenyl)piperazin-1-yl]-3-thiophen-2-ylprop-2-en-1-one Chemical compound C1=CC(O)=CC=C1N1CCN(C(=O)\C=C\C=2SC=CC=2)CC1 BFSPAPKTIGPYOV-BQYQJAHWSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 101100294105 Caenorhabditis elegans nhr-35 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- 108010010803 Gelatin Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 241001494479 Pecora Species 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
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- 239000002421 finishing Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 description 1
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- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
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- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
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- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
- G03C5/3053—Tensio-active agents or sequestering agents, e.g. water-softening or wetting 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/69—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine
- A61K8/70—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine containing perfluoro groups, e.g. perfluoroethers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61Q19/00—Preparations for care of the skin
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/0035—Aqueous solutions
- A62D1/0042—"Wet" water, i.e. containing surfactant
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0071—Foams
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- A—HUMAN NECESSITIES
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- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
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- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
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Description
PATENT SPECIFICATION () 1591293
CM ( 21) Application No 22282/79 ( 22) Filed 28 Dec 1977 f 5 ( 62) Divided out of No1 591 292 ( 19)( ( 31) Convention Application No's 756 032 and 756 031 USE ( 32) Filed 30 Dec 1976 in ht: ( 33) United States of America (US) ( 44) Complete Specification published 17 June 1981 ( 51) INT CL 3 Cll D 10/02 (Cll D 10/02, 1/02, 1/04, 1/12, 1/34, 1/38, 1/62, 1/66, 1/88, 3/04) ( 52) Index at acceptance C 5 D 6 A 6 6 B 12 A 6 B 12 B 1 6 B 12 C 6 B 12 FX 6 B 12 G 6 6 B 12 H 6 B 12 K 2 6 B 12 P 6 815 6 B 1 6 B 2 6 C 8 ( 54) METHOD OF IMPROVING FLUORINATED SURFACTANTS ( 71) We, CIBA-GEIGY AG, a Swiss body corporate, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-
Numerous surfactant applications depend on the attainment of low surface 5 tensions Whereas conventional hydrocarbon surfactants can attain surface tensions of as low as 23 dynes/cm, fluorinated surfactants are unique in that they can attain surface tensions of 15-20 dynes/cm, and at best of 14 5 dynes/cm Such extremely low surface tensions are, however, only reached at high concentrations of fluorinated surfactants and only with highly specific structures Since fluorinated 10 surfactants are exceedingly expensive, it is imperative that the lowest surface tension is attained with the minimum quantity of surfactants.
The problem of attaining the lowest possible surface tension with fluorinated surfactants has been the subject of innumerable patents and publications, which detail specific and idealized structures having such properties is In all cases the preferred candidate surfactants have distinctive and highly specific structures, which if varied even slightly often drastically alter the attainable surface tensions A fundamental reason that the attainment of a minimal surface tension at the lowest practicable use level is not easily answered is that the surface tension decreases as the fluorinated tail increases, while the solubility generally 20 decreases so markedly when even one -CF 2 group is added that precipitation of the sparingly soluble fluorosurfactant frequently occurs.
It has long been known that the surface tension of hydrocarbon surfactants, which at best is 26-27 dynes/cm, can be depressed to 23 dynes/cm with sparingly soluble alcohols In fact, the adventitious nature of this effect is so marked that 25 surface tension curves of conventional commercial surfactants frequently have minima unless the surfactant is scrupulously purified.
Bernett and Zisman, J Phys Chem, 65, 448 ( 1961), teach that synergistic mixtures of conventional hydrocarbon surfactants and fluorinated 1,1 dihydro alcohols can be prepared which attain low surface tensions with smaller 30 concentrations of the fluorinated agent The resultant solutions are, however, unstable and the fluorinated alcohols are, moreover, volatile and acidic With the ammonium salt of a perfluorononaoic acid, the fluorinated 1,1dihydroalcohols are not sufficiently soluble and eventually form gelatinous precipitates.
In a further effort to prepare better surfactants the prior art suggested 35 preparing magnesium salts of anionic perfluorinated surfactants (Shinoda et al, J.
Phys Chem, 76, 909 ( 1972)) and magnesium salts of hydrocarbon anionic surfactants (Reichenberg, Trans Faraday Soc, 43, 467 ( 1947)) It has been found, however, that when a magnesium salt is added to an aqueous solution of a fluorinated surfactant, preferably an anionic fluorinated surfactant, a further 40 substantial lowering of the surface tension of the solution results The aqueous solutions may contain further ingredients such as fluorinated synergists.
The present invention is directed to a method of improving the surface tension properties of solutions of cationic, anionic, non-anionic, amphoteric or mixed function fluorinated surfactants characterised in that to said surfactant solutions a 45 magnesium salt is added For example the surface tension properties of anionic fluorinated surfactant solutions can be improved by adding to said solutions a magnesium salt.
This invention is also directed to a method of lowering surface tension of an aqueous solution of an alkali metal salt of an anionic fluorinated surfactant by 5 adding thereto from 0 1 to 5 equivalents per equivalent of said anionic surfactant of a magnesium salt consisting of magnesium sulfate, magnesium nitrate, magnesium chloride and magnesium acetate.
Although all above listed magnesium salts are very effective in lowering the surface tension, magnesium sulfate is preferred from an economic and corrosion 10 standpoint Also from the economic (cost/performance) standpoints it is preferable that the magnesium salt is used in the amount of I to 4 equivalents per equivalent of the anionic surfactant, and most preferably in the amount of 1 5 to 2 5 equivalents.
Furthermore, the magnesium salt lowers the surface tension most effective if the surface solution is made using distilled or deionised water or low hardness water, 15 that is, water containing less than 5 mg/1 of minerals, in other words, having less than 5 ppm (parts per million) of minerals.
The method of this invention is effective especially with fluorinated anionic surfactants, regardless of the chemical structure Preferred anionic fluorinated surfactants are carboxylic acids and salts thereof, sulfonic acids and salts thereof, 20 phosphonates, phosphates, related phosphoro derivatives and salts thereof.
Preferred surfactants have the formula: (R%)n Am Q wherein R, is a straight or branched chain perfluoroalkyl of 1 to 18 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, N is an integer of I or 2, m is 1 or 2 and Q is a water solubilising group which is anionic, cationic, non-ionic or 25 amphoteric moiety, or a combination of such moieties, A is a multivalent linking group, preferably a divalent group such as aikylene of I to 12, and preferably of 1 to 4 carbon atoms; arylene, alkyl substituted phenylene or the group C 6 H 4 YC 6 H 4 where Y is alkylene of 1 to 4 and preferably methylene, oxygen or sulfur, sulfonamidoalkylene or carbonamidoalkylene 30 Typical anionic groups of Q are carboxylic, ammonium or metal carboxylate where the metal is an alkali or alkali earth metal, especially sodium, potassium, calcium or magnesium, sulfinic or sulfonic acid group or ammonium or a metal salt thereof or phosphonic (OP(OH)2) or phosphoric (OP(OH 3) acid group or ammonium or metal salt thereof Typical cationic groups of Q are -NH 2, NHR 35 where R is lower alkyl (of I to 4 carbons), -NRX where R 3 is hydrogen or lower alkyl and X is an anion such as a halide, especially chloride, sulfate phosphate or hydroxyl Typical non-ionic groups of Q are amine oxides and groups derived from polyethylene oxide and mixed polyethylene oxide polypropylene oxide polyols.
Typical amphoteric and mixed groups are respectively 40 -N(CH 3)2 C 2 H 4 C 02 and -N(CH 3)C 2 H 4 CO 2 H) O.
The mixed group surfactants are those fluorinated surfactants which within the same molecule contain anionic and cationic moieties or anionic and nonionic moieties or cationic and non-ionic moieties or cationic and amphoteric moieties or anionic and amphoteric moieties or non-ionic and amphoteric moieties The above 45 mentioned classes of fluorinated surfactants are also exemplified in German Offenlegungsschrift No 2,656,677.
The R, group can be, as stated above, broadly a perfluoroalkyl of 1 to 18 carbons, but preferably it is a perfluoroaliphatic of 5 to 12 carbon atoms.
It should be noted that in some instances more than one R, group may be 50 bonded through multivalent linking groups A to a single Q group and in other instances, a single R, group may be linked through a multivalent linking group A to more than one polar solubilizing group.
The present invention also provides an aqueous surfactant composition having improved surface properties which contains a mixture of a cationic, anionic, non 55 ionic amphoteric or mixed function fluorinated surfactant and a magnesium salt.
Of special interest are those compositions which contain a mixture of an anionic fluorinated surfactant and a magnesium salt.
Preferred are those compositions which contain an alkali metal salt of the anionic fluorinated surfactant and 0 1 to 5 equivalents per equivalent of the 60 surfactant of a magnesium salt which is magnesium sulfate, magnesium nitrate, 1,591,293 magnesium chloride or magnesium acetate In these compositions magnesium sulfate is the most suitable species.
The resultant fluorinated surfactant/magnesium salt composition of this invention can be used advantageously in place of conventional fluorinated surfactants for all purposes for which said conventional fluorinated surfactants are 5 recommended Naturally, various surfactant mixtures will be preferable for special considerations For example, while cationic or anionic surfactant derived compositions may exhibit special substantivity, amphoteric or non-ionic fluorosurfactants may be more preferable for compatibility with the overall formulation Thermal or hydrolytic stability considerations may lead to the choice 10 of particularly stable functionalities for both synergist and surfactant, e g acid plating baths; non-ionic surfactant derived compositions may have special utility in non-aqueous or low foaming formulations; cationic surfactant derived compositions may be particularly syncergistic with disinfectants These examples are merely exemplary of the compositions, and preferred compositions should be 15 chosen with due regard to the actual application These compositions, just as concentional fluorochemical surfactants, are useful for improving or imparting properties such as wetting, penetration, spreading, levelling, foam stability, flow properties, emulsification, dispersion, and oil and water repellency Based on these unique properties are numerous applications, some of which follow Although 20 applications are suggested for a particular use area, the general applicability of each concept is to be inferred for other applications.
Plastics and Rubber Industry Emulsifying agent for polymerization, particularly fluoromonomers As a latex stabilizer 25 To aid in the preparation of agglomerates of powdered fluorocarbon polymers In synergistic mixtures with hydrocarbon surfactants to wet low energy surfaces including natural and synthetic rubbers, resins, plastics As an adjuvant for foam applications and as foaming agents to aid in lead detection As a foam additive to control spreading, crawling, edge buildup 30 As a mold release agent for silicones In refractory processes As an antimist film former Additive for elimination of trapped air in plastic laminates Wetting agent for resin molds for definition, strength 35 Hot melt additive for oil and grease repellency Resin additive for improved wetting of and bonding with fillers Flow modifier for extruding hot melts: spreading, uniformity, anticratering Adjuvant for resin etchant Mold release agent, demolding agent 40 Retarder for plasticizer migration or evaporation Internal antistatic agent for polyolefins Antiblocking agent for polyolefins Petroleum Industry I 1,591,293 4 1,591,293 4 Wetting assistant for oil well treatments, drilling muds As a film evaporation inhibitor for gasoline, jet fuel, solvents, hydrocarbons Lubricants, cutting oil improver, to improve penetration times In extreme pressure lubricants Oil spill collecting agent 5 Additive to improve tertiary oil well recovery Textile and Leather Industries Soil release and soil proofing agent Oil/water repellent textile and leather treatment Wetting agent to improve coverage and penetration of pores of substrates 10 Antifoaming agent in textile treatment baths Wetting agent for finish-on-yarn uniformity Penetrating agent for finishes on tow, heavy denier fibers Emulsifying agent/lubricant for fiber finishes Cleaner/metal treating agent for polymerization equipment 15 Flow modifier for spinning of hot melts, solutions Additives for fabric finishes for spreading, uniformity Wetting agent for dyeing Penetration aid for bleaches Wetting agent for binder in nonwoven fabrics 20 Paint, Pigment and Finishing Industries Levelling, anticratering adjuvant for finishes and paints Adjuvant for control of soiling Agent to control differential evaporation of solvents Leveling agent for floor waxes 25 Adjuvant for waxes to improve oil and water repellency Adhesion improver for oily or greasy surfaces To combat pigment flotation problems Improver for automotive finishes, based on water-based coatings in which the pigments are rendered nonreactive 30 Pigment grinding aid to promote wetting, dispersion, color development Foam generator substance for the application of dyes, inks Electrolytic conversion coatings 1,591,293 5 Mining and Metal Working Industries In cleaning agents for property improvement Additive for solvent cleaning Additive for metal pickling baths to increase bath life and acid runoff Additive for chrome electroplating: surface tension reduction, foaming 5 Additive for soldering flux, especially for electronic circuitry Protective agent for coatings (tarnish resistance, grease repellency) Corrosion inhibitor Additive for etchant solution for improved definition To form antimist films and anticondensation surfaces 10 Plastic preplate and silicon etchant technology In soldering flux for microelectronics to reduce foaming In chemical roughing agent solutions, prior to galvanization As a colloidal dispersion aid for magnetic solids Protective coatings for aluminium and as an antiblocking agent 15 Wetting agent for leaching copper ores and as a froth flotation agent To promote ore wetting and quicker breaking of the protecting oxide layer Pharmaceutical Industry Improve the properties and penetration of antimicrobial agents Improve the properties of biochemicals, biocides, algicides, bacteriocides and 20 bacteriostats Improve the strength, homogeneity, and reduce the permeability of encapsulated materials Emulsify fluorochemical blood substitutes Agriculture and Forestry 25 Wetting agent for herbicides, fungicides, weed killers, hormone growth regulators, parasiticides, insecticides, germicides, bactericides, nematocides, microbiocides, defoliants and fertilizers As an ingredient in chemosterilents, insect repellents and toxicants For wettable powder pesticides and chemical powders 30 Corrosion inhibitor for chemical applicators Wetting agent for foliage Wetting additive for live stock dips, or to wet sheep skins during desalination Wetting adjuvant for manufacture of plywood veneer Penetrant for preservative impregnation 35 6 I,J 1 I, -'7 U Pulping aid For cleaning tubes in paper making, dyeing Grease/oil repellents for paper Fire Fighting Wetting agent for fighting forest fires 5 Ingredient of AFFF, aqueous film forming extinguishing agents (foams) Component of fluoroprotein foams Additives to dry chemical extinguishing agents Agent in aerosol-type extinguishers Wetting agent for sprinkler water 10 Automotive, Building Maintenance and Cleaning Wetting agent for cleaning compositions Additive for alkaline cleaners Glass cleaner Wetting agent for automobile waxes 15 Adjuvant to improve oil/water repellency of wax Lubricant/corrosion inhibitor for antifreeze Rinse-aid for car washes In dry cleaning compositions and solvent cleaners, for water displacement and foaming May improve soil suspension and decrease redeposition 20 Foaming agents for pipe cleaning Anti-mist film foamer for glass and plastics In foams for dust suppression Cleaner for building exteriors For acidic concrete cleaners 25 Air entrainment additive for low density concrete Bubble foamer for air tracing, in ventilating systems Household, Cosmetic and Personal Products Rinse-aid for dishwashing Liquid polishing compositions 30 Floor polish levelling agent Additive for alkaline oven cleaners Synergistic improver for disinfectants 1 r 41 10,r Ar Carpet cleaners Synergistic wetting agent in detergent formulations Additive for protective coatings on metals (tarnish resistance, grease resistance) Gloss and antistatic improver Hair shampoo ingredient 5 Shaving foam ingredient Oil and water repellent cosmetic powders ingredient Ingredient of lotions or creams for skin or hair Ingredient of skin protection creams Photography and Graphic Arts 10 Printing ink additive for ink flow and levelling, both aqueous and solvent based Wetting agent for writing inks To combat pigment flooding and flotation in printing inks To form ink repellent surfaces for waterless lithoplates, or electrographic coatings i 5 Prevent reticulation of gelatin layers and improve uniformity 15 Assist in film drying Improve film coatings and reduce "contraction flecks" Wetting, levelling, anti-cratering assist agent Surfactant for developer solutions Photoemulsion stabilizer 20 Prevent photo-lubricant agglomeration Coating aid in the preparation of multiple layer film elements Antistatic wetting agent for film coatings Antifogging agent for films Bonding agent for fillers and fluoropolymer films 25 In coatings for nematic liquid crystal cells Illustrative examples of RT-anionics which can be used in the compositions of this invention are the below shown acids and their alkali metal salts Preferred anionic groups are carboxylate and sulfonate The anionic surfactant should generally contain 30-65 % of carbon bound fluorine in order to attain suitable 30 solubility properties The anionic surfactant may be present as free acid, an alkali metal salt thereof, ammonium, or substituted ammonium The followng patent numbers appearing in parenthesis are patents which more fully disclose the represented class of compounds.
I 1,591,293 8 1,591,2938 Carboxylic Acids and Salts thereof Rf(C 1-2)1-2 C O OH Rf O(C F 2) 220 C 00 HRt O(C F 2)2-2 (CH 2)2-1 C 00 H RO(CH,),-,,C 00 H Rf SO 2 N(C 2 H)CH 2 COOH R 1,O(CFO),CF 2 COOH CF 2 COOH RO lCF(CF 3,)CF 2 OICF(CF:)CON(CH,) CHCOOH (C 2 F 5)2 (CF 3)CCH 2 COOH C 10 F 1,OCH 4 CON(CH 3)CH 2 C 00 H Rf(CH,),-,SCH(COOH)CH 2 COOH Rf(CHA-,1 S(CH 2)1-1,C 00 H Sulfonic Acids and Salts Thereof RSO 3 HRf C 6 H 4 l SOH Rf(CH 2),20503 H RSO 2 NI-CHQC 6 H 45 O 3 H RSO 2 N(C 1-3)(C,1-10),20503 H RCH Cl-2 OCH 2 CHCH 25 O 3 H R Cff Ci HSOH C 121 F 230 CH 503 H (C 2 F 5)3 C O (CHI 5353 H C F 3 (CYF),C O (CHI 5353 H (C 2 F,5)2 (CF 3)CCH=C(CF 3)SOH Rf OCF(CF,)CF 2 OCF(CF 3)CONHCHSOH RCH)-0-(CH H,0 X-;SO 3 H (Scholberg et al, J Phys Chem 57, 923-5 ( 1953) (German 1,916,669) (German 2,132,164) (German 2,132,164) (U.S 3,409,647) (U.S 3,258,423) (French 1,531,902 (French 1,537,922) (U.S 3,798,265) (British 1,176,493) (British 1,270,662) (U.S 3,706,787) German 2,239,709; U.S 3,172,910 (U.S 3,475,333) (German 2,134,973) (German 2,309,365) (German 2,315,326) (South African 693,583) (Canadian 842,252) (German 2,230,366) (German 2,240,263) (British 1,153,854) (British 1,153,854) (British 1,206,596) (U.S 3,798,265) (German 2,310,426) 1,591,293 Phosphonates, Phosphates, Related Phosphoro Derivatives, and Salts Thereof Rf PO(OH)2 (R,)2 PO(OH) Rf SO 2 N(Et)C 2 HOPO(OH)2 Rf CH 2 OPO(OH)2 C 8 F 15 OC 6 H 4 CH 2 PO(OH)2 Rf OCH 4 CH 2 PO(OH)2 Others (and Salts Thereof) Rf SO 2 N(CH 3)C 2 H 4 OSO 3 H Rf C 6 H 40 H Rf(CH 2),_ 2 520523 Na Rf(CH 2),_ 20 SO 02 N(CH 3)CH 2 CH 25203 Na Rf SO 2 H (German 2,110,767) (German 2,125,836) (German 2,158,661) (German 2,215,387) (German 2,230,366) (German 1,621,107) (U.S 3,475,333) (German 2,115,139) (German 2,115,139) (U.S 3,562,156) Illustrative examples of Rf-cationics and Rf-amphoterics which can be used in the compositions of this invention are described in Table lc and lb, but also include compounds more fully disclosed in the following patents.
United States 2,727,923, 2,759,019, 2,764,602, 2,764,603, 3,147,065, 3,510,494, 3,630,951, 3,681,413, 3,681,441, 3,759,981, 3,839,425, 3,933,819, 3,941,705, 3,957,657 3,207,730, 3,257,407, 3,766,274, 3,828,085, German 1,925,555, 2,215,387, 3,325,855, 2,013,104, 2,119,302, 2,120,868, 2,127,232, 2,219,642, 2,224,653, 2,230,366, 2,236,729, 2,337,638, 2,357,916, 2,438,868, 2,523,402 2,132,164, 2,165,057, 2,239,709, 2,315,326, British 1,270,662, 1,288,678, 1,289,436 French 2,035,589, 2,128,028 Belgium 788,335, 801,585 Illustrative examples of Rf-nonionics which can be used in the compositions of this invention are described in Table ld, but also include compounds more fully disclosed in the following patents.
United States 2,723,999, 3,621,059, 3,721,700, 3,883,596, 3,952,075, 1,925,555, 1,966, 708, 2,160,852, 2,215,386 German 2,215,388, 2,230,366, 2,244,028, 2,250,718, 2,325,855 2,334,346, 2,337, 638, 2,501,239 British 1,130,822, 1,148,486, 1,155,607, 1,176,492 Netherlands Japanese 40 (early publication) 75-157,275 Belgium 817,369 7,009,980 The following Examples further illustrate the present invention.
Experimental Part Tables Ila through Id list R,-anionic, amphoteric, cationic, and nonionic surfactants and Table 2 lists Rf-synergists which are used in the examples following the tables.
The commercially available surfactants used in the examples are:
F-1 I, which is an alkali metal salt of a perfluoroalkyisulfonic acid F-2, which is a perfluoroalkanesulfonamido alkylenemonocarboxylic acid salt as disclosed in U S 2,809,990 F-3, which is a cationic quaternairy ammonium salt derived from a perfluoroalkanesulfonamidoalkylenedialkylamine as disclosed in U S 2,759, 019, namely C 8 F,7 SO 2 NHC 3 H^N(CH 3)31F-4, which is a nonionic perfluoroalkanesulfonamido polyalkylene oxide derivative F-5 and F-6, anionics derived from linear perfluoroalkyl telomers F-7, an amphoteric carboxylate derived from linear perfiuoroalkyl telomers F-8, a cationic quaternary ammonium salt derived from linear perfluoroalkyl telomers F-9, a nonionic derived from linear perfluoroalkyl telomers F-10 und F 1, anionics derived from branched tetrafluoroethylene oligomrers as disclosed in G B 1,148,486 F-12, a cationic derived from branched tetrafluoroethylene oligomers as disclosed in D T 2,224,653 F-13, a nonionic derived from branched tetrafluoroethylene oligomers as disclosed in British Specifications 1,130,822, 1,176,492 and 1,155,607
Table I a
Fiuorinated Anionic Surfactants used in Examples I t O 29 R,-Surfactant Name Formula 2-Methyl-2-( 3-l i,1,2,2-tetrahydroperfluoroalkylthio propionamide) I -propanesulfonic acid, sodium salt' as above as above as above as above as above as above as above, 45 ",o as above, 45 % as above, 100 "/' 1, i,2,2-Tetrahydroperfluoroalkylsulfonate, potassium salt Perfitibrdaikiiioic acid, jotdssiu m sait R,CH 2 CH 2 SCH 2 CH 2 CONHC(CH 3)2 CH 25 O 3 Na wherein: %C 6 F 13 <%C 8 F 17o C 10 F 21 39 41 13 44 42 10 52 35 8 36 4 32 42 21 27 44 23 48 26 Rf CH 2 CH 25 O 3 K wherein:
R,COOK 32 20 62 6 Al A 2 A 3 A 4 A 5 A 6 A 7 A 8 A 9 A 10 Al 12 A 122 i,5 i; 293 Table Ia (Continuation) Rf-Surfactant Name Formrn U I a A 13 A 8, magnesium salt C 6 F 13 A 14 F-I 1 A 15 F-2 A 16 F-5 A 17 F 6 A 18 F-9 A 19 F-10 A 20 C 8 F 17502 N(C 2 H 5)i CH 2 CO 2 K A 2 I Cj F 50,1 K A 22 CJ 1 SONHCHC 6 H 4,SO Na Rf is amixture consisting p'rincipal of GCF 13 8 N C 1 F 2 in the approkimate ratio 2:2:1 or as stated 35 % solution in 17 5 %' hexylene glycol 47 5 ?% water or as otherwise stated.
2 Approxirnate hbmolog distribution Table lb
Fluorinated Amnphoteric Surfadctants used in Examples I to 29 JR,-Surfactant Name or Formula Formula A 23 a N-l 3-(di 'ethylaminio)propyll-2 and 3 1 'C 13 C F 1 1 C 12, ( 1, 1,2,2-tetrahydrooerfluoroalkylthio) succinamnic acid, 60 %? 4 solids 32 36 22 A 23 b,,39 41 13 A 23 c, 44 42 10 A 24 C,6 F,,350 N(C HC 02)CH 6,N(CH,), A 25 C 6 F,,CH 2 CHSCH 2 CHN(CH 3),CHCO, 00 A 26 C 8 F 17 C 2 H 4 CONH(CH 2),N(C H 3)2 CH 2 CH 2 C 02 0 D O A 27 C 6 F,3502 N(CH 503)CHN(CH 31)2 (CE 2 H 4 OH) 00 A 28 C 8,F 17 CH 2 CH(C 02)N(CH,), o D O A 29 C 6 FI 3 SO 2 N(CH 2 CH 2 CO 2)C 3,H 6 N(CH 3)2 CH 2 CH 20 H A 30 F 14 (Du Pont) A 31 I C 7 F,5 CONHCH 6 N(CH 3)2 CH-2 CH 2 C 02 1 1 1,591,293 1 1 Table I c
Fluorinated Cationic Surfactants used in Examples I to 29 R,-Surfactant A 32 Name or formula CFSO 2 N HC O H 6 N(CH)C Cj,1 SO 2 NI-CH,6 N(CH,) 3 Cl e A 33 C 8 F 1,SO 2 NHC 3 H 6 N(CH 3)C 2 Hs OSO 2 OC 2 Hs o e A 34 C 8 F,,17 SO 2 NHC 3 H 6 N(CH 3)31 A 35 C Fis CONHC 3 H 6 N(CH 3)3 Cl ) A 36 C 8 F 1 SO 2 NHC 3 H 6 N(CH 3)2 CH 2 C 6 Hs CI 0) A 37 C 8 F,,SO 2 N(CH 3)C 3 H 6 N(CH 3)31 l CF 1 17 SO 2 NHC 3 H 6 ?(C 2 H 5 s)c O ( 5020 C 2 H 5 03 e A 39 C 6 F,13 CH 2 C-1 H 2 SCH 2 CH 2 N(CH 3)31 l A 40 F-3 F-8 A 42 F 15 (JCJ) Table Id
Fluorinated Non-ionic Surfactants used in Examples R,-Surfactant Name or Formula A 43 F-4 A 44 F-9 A 45 F-13 Examples I to 15.
Fluorinated surfactants of the diverse types as shown in Table 2 were compared at the same dilution with added magnesium sulfate The anionic Rfsurfactants show the best improvement in surface tension.
The test solutions exhibit varying degrees of clarity and, significantly, many of the solutions are clear It has been found that the addition of small quantities of conventional hydrocarbon surfactants to the cloudy compositions will frequently improve their compatibility.
A 38 A 41 Rf(CH 2)1; 2, 1.591 293 1,591,293 I able 2 R,-Surfactant Variable Solvent Magnesium Sulfate Heptahydrate Example Surface Number Rf-Surfactant Mg SO 4 7 H 202 Tension 1 Clarity' 3 none F-I , anionic I F-2 + 26.0 21.5 20.4 , anionic F-3 F-3 18.3 b c 18.5 , cationic F-9 F-9 , anionic 18.1 26.0 21.4 22.7 a c 23.5 + + + F-13 F-13 non-ionic + 6 5 dilution in distilled water; corresponds R,-synergist to 0 1 % R,-surfactant and 0 02 2 Ingredient present (+), absent (-) 3 Clarity: = clear; a = opalescent; b = slight precipitate; c = precipitate 41 ngredients corrected for dilution as necessary; 100/ actives Filtered solution for measurement of surface tension.
1 67 %,4 % 0 6 ",, l 1,591,293 Table 2 (Continuation) Example Surface Number R,-Surfaciant Mg SO, 7 H 2,02 Tension' Clarity 1 ' 3 F-15 anionic F-6 anionic F-6 non-ionic F-8 amphoteric + + + + 28.5 27.4 18.3 17.9 19.3 18.8 17.8 17.3 20.8 20.9 19.9 20.0 19.7 19.6 a c Table 2 (Continuation) Rf-Surfactant A 12 anionic Al anionic A 8 , anionic Mg SO 4 7 H 202 + + + dilutioh lf-synergist in distilled water; corresponds to 0 1 % Rr-surfactant and 0 02 % 2 Ihgredieht present (±), absent (-) 3 Clarity:-= clear; a = opaliesceht; b = slight precipitate; C = precipitate Examipie i 6 This Example shows the effect of Mg SO 4 7 H 20 on a particular R,Sirfactant.
Solids Compositioni Rf-S Urfactant A 3 Mg SO 4 7 H 2 O parts parts Surface Tension (dynes/cm) % Solids 2,3 I s 01 28 2 26 6 48 1 30 19 7 20 1 43 9 The compositions contain approximately 2 % solids in 25/75 butyl carbitol/water 2 Based on Rf-Surfactant A 3 Clarity: clear Examples 17-29.
The following tables summarize the results of measurement on example systems of individual anionic fluorochemical suffactants (Table 3) Table 4 demonstrates the effect of varying amounts of magnesium.
In preparation for the testing reported in Table 8 solutions of the named surfactants were prepared at 0 1 % in distilled water and their surface tensions were measured using the Cenco-Du-Nuoy ring tensionmeter after 5 minutes Example
Number Surface Tension' 24.9 Clarity'T 3 18.8 28.9 2 i.4 29.6 i 9.7 001 1.591 293 IS equilibration To a fresh aliquot of that solution a stoichiometric amount of magnesium sulfate was added and the surface tension of each solution was again measured Table 8 shows the depression of the surface tension achieved by using the magnesium salt.
Table 3
Surface Tension (dynes/cm) Example
Number R,-Surfactant As Is With Magnesium Added Change 17 F-1 26 0 21 5 -5 5 18 F-2 20 4 18 3 -2 1 19 F-10 26 0 21 4 -5 6 F-5 18 3 17 9 -0 4 21 F-6 19 3 18 8 -0 5 22 A-12 24 9 18 8 -6 1 23 A-I 28 9 21 4 -7 5 24 A-8 29 6 19 7 -9 9 A-3 28 2 19 7 -8 5 Table 4 shows the relationship between the relative amounts of magnesium salt and surfactant employed and the surface tension depression achieved.
Table 4
Surface Tension Depression (dynes/cm) Example
Number Magnesium Level Surfactant (A 3) 26 None -027 0 2 Equivalents 8 1 28 I Equivalent 9 5 29 5 Equivalents 10 4In our Application No 53942/77 (Serial No 1,591,292) we describe and claim a method of improving the surface tension properties of solutions of cationic, anionic, non-ionic, amphoteric or mixed function fluorinated surfactants characterised in that to the said surfactant solution at least one flourinated synergist of the formula:
(Rf)n Tm Z wherein Rf is a straight or branched chain perfluoroalkyl of I to 18 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, n is an integer of I or 2, T is a divalent group -R 3 or a group-R 3 SCH 2 CHR, where R 3 is straight i,591,293 - À 7 or branched chain alkylene or haloalkylene of 1 to 12 carbons, arylene of 6 to 12 carbons, alkylenethioalkylene or alkyleneiminoalkylene of 2 to 12 carbons where in said imino group the nitrogen atom is secondary or tertiary and R, is hydrogen or alkyl of I to 12 carbons, Z is a neutral or a polar group selected from -CONRR 2, -CN, -CONR, -COR 2, -SO 2 NR, -R 3 (O 2 CR) and -CO 2 R, where R, and R 2 are independently hydrogen, alkyl of I to 12 carbons or alkyl substituted with one or more -OH, -COCH 3, -SH, -CONH(CH 3), and R 3 is as defined above, m is an integer from 0 to 2, the fluorinated synergist has solubility in water at 25 C below 001 % by weight, and component ( 2) a magnesium salt is added, as well 10 as surfactant compositions comprising these ingredients No claim is made herein to this method diid these conmpbsitions Subject to this disclaimer:
Claims (21)
1 A method of improving the surface tension properties of a solution of a cationic, andionic' nonionic, amphoteric or 'mixed function fluorinated surfactant 15 which comprises preparing the 'said surfactant solution with a magnesium salt' m
2 ' A m'ih 6 d, according to claim I' wherein' the fluorina ed suirfactant is of the formula:
(Rf)n Am Q wherein 20 R is a straight or branched chain per fluoroalkyl, of 1 to 18 carbon atoms or said perfluorobalkyl substituted by perfluoroalkoxy 'of 2 to 6 carbon atoms, Q is a water soltibilizing group which is an anionic, cationic, nionionic or amphoteric moiety or a coibi'nation of such moieties, A is a mó,ltiva Lent linking group, 25 n is I O or:2 and mi isf 0,' I or 2 ' 3; 'A method' a'cc O ridihg to,'c aim 2 wlerein A is alkylene of I to 1,2 carb 9 n atoms; aryiene, 'alkyl' siubstituted phenylene or the group C 8 H 4 Yr CH 4 where Y is
3 a 11 ytene of l;to 4, oxygen or sulfur, sulfonamidoalkylene'or carbonamidoalkylene.
"
4 A ethod according to claim 3 wherein A is alkylene of'1 to 4 carbon 30 atoms or C 6 H 4 ' 6 H 4 whfiere Y is methylene.
A nietliodi ac cording to claim 2, wherein A is phenylene.
6 A r/net$hod according to any one of claims 1, to 5 wherein the fluorinated group in' the surfactant is perfluoroalkyl of 5 to 12 carbon atoms.
'
7 A method according to any one of claims I to 6 which comprises adding a 35 solution of a magnesiumn salt to anionic fluorinated surfactant '
8 A metl Cod'a'ccordingd to any 'one of claims I, to 7 which comprises adding 0 1.
to 5 equivalets er equiaent of the surfactanit of magnesium sulfate, magnesium nitrate, magnesium chloride or magnesium acetate to an alkali metal salt of an anionic fluorinated surfactant 40
9 A method according to claim 8, which comprises adding magnesium sulfate.
A nethod according to claim 8 or 9, wherein the anionic fluorinated surfactant is a carboxylic acid or salt thereof, a sulfonic acid or salt thereof, a phosphonate, phosphate, or a phosphoro derivative or salt thereof.
11 A surfactant composition having improved surface tension properties 45 which contains a mixture of a cationic, anionic, non-ionic, amphoteric or mixed function fluorinated surfactant and a magnesium salt.
12 A surfactant composition according to claim 11 in which the fluorinated surfactant is of the formula (Rf)n Am Q 50 wherein R, N and m, and Q are as defined in claim 2 and A is as defined in any one of claims 2 to 4.
13 A surfactant composition according to claim 11 or 12, characterised in that the fluorinated groups in the surfactants are perfluoroalkyl of 5 to 12 carbon atoms 55
14 A surfactant composition according to any one of claims 11 to 12 which contains an anionic fluorinated surfactant and a magnesium salt.
An aqueous surfactant composition according to claim 14, which contains an alkali metal salt of the anionic fluorinated surfactant and 0 1 to 5 equivalents per equivalent of the surfactant of a magnesium salt which is magnesium sulfate, 60 1.7 1.591 293 18 1,591,293 18 magnesium nitrate, magnesium chloride and magnesium acetate.
16 A surfactant composition according to claim 15 which contains magnesium sulfate.
17 A surfactant composition according to any one of claims 12 to 16, in which the anionic fluorinated surfactant is a carboxylic acid or a salt thereof, a sulfonic 5 acid or a salt thereof, a phosphonate, a phosphate or a related phosphoro derivative or a salt thereof.
18 A method according to claim I substantially as described in any one of Examples I to 16.
19 A method according to claim I substantially as described in any one of 10 Examples 17 to 29.
A surfactant composition according to claim 11 substantially as described in any one of Examples I to 16.
21 A surfactant composition according to claim 11 substantially as described in any one of Examples 17 to 29 15 22 A solution of a fluorinated surfactant whenever prepared by a method as claimed in any one of claims I to 10, 18 and 19.
J A KEMP & CO, Chartered Patent Agents, 14 South Square, Gray's Inn, London, WCIR 5 EU.
Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1981.
Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.
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US75603276A | 1976-12-30 | 1976-12-30 | |
US05/756,031 US4089804A (en) | 1976-12-30 | 1976-12-30 | Method of improving fluorinated surfactants |
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GB1591293A true GB1591293A (en) | 1981-06-17 |
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GB22282/79A Expired GB1591293A (en) | 1976-12-30 | 1977-12-28 | Method of improving fluorinated surfactants |
GB53942/77A Expired GB1591292A (en) | 1976-12-30 | 1977-12-28 | Method of improving fluorinated surfactants |
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GB53942/77A Expired GB1591292A (en) | 1976-12-30 | 1977-12-28 | Method of improving fluorinated surfactants |
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AU (1) | AU517771B2 (en) |
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BR (1) | BR7708741A (en) |
CA (1) | CA1102652A (en) |
CH (1) | CH634873A5 (en) |
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FR (1) | FR2376208A1 (en) |
GB (2) | GB1591293A (en) |
MX (1) | MX148221A (en) |
NL (1) | NL7714204A (en) |
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WO2006132568A2 (en) * | 2005-06-09 | 2006-12-14 | Andrey Leonidovich Dushkin | Fire-extinguishing composition |
WO2024088385A1 (en) * | 2022-10-27 | 2024-05-02 | 中国石油化工股份有限公司 | Water-lock releasing chemical agent for oil and gas reservoirs, preparation method therefor and use thereof |
Families Citing this family (9)
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DE2963744D1 (en) * | 1978-10-20 | 1982-11-04 | Ciba Geigy Ag | Perfluoroalkylalkylenemercapto group containing non-ionic surfactants, process for their manufacture and their use |
JPS5929194A (en) * | 1982-08-09 | 1984-02-16 | Fuji Photo Film Co Ltd | Heat-sensitive recording paper |
FR2620445B1 (en) * | 1987-09-16 | 1990-07-20 | Centre Nat Rech Scient | NOVEL FLUORINATED DERIVATIVES OF AMINO ACIDS, IN PARTICULAR FOR USE AS SURFACTANTS OR COTENSIOACTIVES AND BIOMEDICAL PREPARATIONS COMPRISING SUCH DERIVATIVES |
FR2637599B1 (en) * | 1988-10-10 | 1991-01-11 | Szonyi Istvan | NOVEL AMIDOFLUORINATED COMPOUNDS, THEIR PRODUCTION AND THEIR USE |
US20030148232A1 (en) * | 2001-09-21 | 2003-08-07 | Orem Michael W. | Fluorinated surfactants in overcoat compositions and elements containing same |
EP1296182A1 (en) | 2001-09-21 | 2003-03-26 | Eastman Kodak Company | Fluorinated surfactants in overcoat compositions and elements containing same |
GB0223835D0 (en) | 2002-10-12 | 2002-11-20 | Eastman Kodak Co | Method of making a material |
DE102008018180A1 (en) * | 2008-04-02 | 2009-10-15 | Hansgrohe Ag | Method for quantitative detection of perfluorinated surfactant e.g. perfluorinated alkylsulfonate contained in sewage sludge, involves determining interaction product formed by mixing perfluorinated surfactants and chromophore |
CN113433276B (en) * | 2021-06-07 | 2022-03-25 | 中南大学 | Quantum chemistry high-throughput screening method of chalcopyrite inhibitor |
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US3194840A (en) * | 1961-12-18 | 1965-07-13 | Procter & Gamble | N, n-diloweralkyl, 1, 1-dihydrogen perfluoroalkyl amine oxides |
US3509061A (en) * | 1966-10-18 | 1970-04-28 | Us Navy | Method and compositions for displacing organic liquids from solid surfaces |
NL172234C (en) * | 1971-06-02 | 1983-08-01 | Hoechst Ag | METHOD FOR PREPARING PERFLUORATED CARBONIC ACID AMIDEAMINE COMPOUNDS. |
GB1337467A (en) * | 1971-10-13 | 1973-11-14 | Dow Corning Ltd | Wetting compositions and treatment of surfaces therewith |
DE2339987A1 (en) * | 1972-08-15 | 1974-03-14 | Ici Ltd | MELTING AGENTS AND METHODS FOR MELTING TEXTILES |
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1977
- 1977-12-15 CH CH1545277A patent/CH634873A5/en not_active IP Right Cessation
- 1977-12-21 NL NL7714204A patent/NL7714204A/en not_active Application Discontinuation
- 1977-12-23 AU AU31994/77A patent/AU517771B2/en not_active Expired
- 1977-12-24 DE DE2758013A patent/DE2758013C3/en not_active Expired
- 1977-12-24 DE DE2759790A patent/DE2759790C2/en not_active Expired
- 1977-12-28 CA CA293,998A patent/CA1102652A/en not_active Expired
- 1977-12-28 GB GB22282/79A patent/GB1591293A/en not_active Expired
- 1977-12-28 GB GB53942/77A patent/GB1591292A/en not_active Expired
- 1977-12-28 FR FR7739523A patent/FR2376208A1/en active Granted
- 1977-12-29 BE BE183957A patent/BE862459A/en not_active IP Right Cessation
- 1977-12-29 JP JP15863877A patent/JPS5385787A/en active Granted
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2006132568A2 (en) * | 2005-06-09 | 2006-12-14 | Andrey Leonidovich Dushkin | Fire-extinguishing composition |
WO2006132568A3 (en) * | 2005-06-09 | 2007-03-15 | Andrey Leonidovich Dushkin | Fire-extinguishing composition |
WO2024088385A1 (en) * | 2022-10-27 | 2024-05-02 | 中国石油化工股份有限公司 | Water-lock releasing chemical agent for oil and gas reservoirs, preparation method therefor and use thereof |
Also Published As
Publication number | Publication date |
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DE2759790C2 (en) | 1982-09-23 |
DE2758013C3 (en) | 1981-11-05 |
GB1591292A (en) | 1981-06-17 |
CA1102652A (en) | 1981-06-09 |
BE862459A (en) | 1978-06-29 |
CH634873A5 (en) | 1983-02-28 |
BR7708741A (en) | 1978-08-01 |
NL7714204A (en) | 1978-07-04 |
FR2376208A1 (en) | 1978-07-28 |
MX148221A (en) | 1983-03-28 |
JPS5385787A (en) | 1978-07-28 |
FR2376208B1 (en) | 1980-10-10 |
JPS6254533B2 (en) | 1987-11-16 |
AU517771B2 (en) | 1981-08-27 |
DE2758013B2 (en) | 1981-01-29 |
AU3199477A (en) | 1979-06-28 |
DE2758013A1 (en) | 1978-07-06 |
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Effective date: 19941228 |