US3304330A - Tertiary phosphine oxide compounds - Google Patents

Tertiary phosphine oxide compounds Download PDF

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US3304330A
US3304330A US173834A US17383462A US3304330A US 3304330 A US3304330 A US 3304330A US 173834 A US173834 A US 173834A US 17383462 A US17383462 A US 17383462A US 3304330 A US3304330 A US 3304330A
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oxide
sodium
alkyl
detergent
water
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Iii John Thomas Yoke
Robert G Laughlin
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/52—Halophosphines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • 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
    • C09K23/14—Derivatives of phosphoric acid
    • 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
    • C11D1/79—Phosphine oxides
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • This invention relates to novel tertiary phosphine oxide detergents and detergent compositions containing them.
  • Thermal stability is a highly desirable property which is lacking in many detergents. Such stability is particularly desirable when detergents are subjected to heat during use or processing, as for example, in spray drying granular detergent compositions.
  • a degree of bacteriostatic activity is also desirable in organic detergent compounds.
  • Another advantageous property for an organic detergent is a low degree of hydroscopicity which results in improved crystallinity.
  • detergents which are hygroscopic are used in bar or granular form, desirable physical properties are impaired. Bars become soft and slimy and granules tend to cake and lose their free flowing and quick dissolving characteristics.
  • a high degree of detergency in cool or cold water is also highly desirable. Many fabrics such as those containing crease resistant additives should be washed in cool water to retain their crease resistant properties. Wool garments should be washed in cool water to avoid shrinkage. In some locations warm or hot water is not available.
  • the phosphine oxides of this invention are probably resonance hybrids, the major canonical forms of which are:
  • R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R and R are each alkyl or monohydroxyalkyl groups containing from 1 to 3'carbon atoms.
  • the class of compounds described above will hereinafter be referred to more simply as RR'RP O.
  • Tertiary phosphine oxides as a broad class of compounds are known. It was sunprising to find, however, that the particular trialkyl phosphine oxides described above have highly desirable properties for use as organi detergents.
  • R, R and R" must be as de-- scribed above. If R is longer in chain length than 18 carbon atoms or shorter in chain length than 10 carbon atoms, desire-d detergency characteristics are not obtained. Likewise, if R and R" contain more than 3 carbon atoms, desired detergency characteristics and bacterio static activity are not obtained.
  • the most preferred tertiary phosphine oxides are the C -C alkyldimethylphosphine oxides; particularly desirable are C -C alkyldimethylphosphone oxides which have good sudsing characteristics.
  • the C C .a1kyldimethylphosphine oxides show 'bacteriostatic activity against Gram positive organisms. (Some tests indicate activity also against Gram negative organisms.) These phosphine oxides also exhibit the desired high degree,
  • the C -C alkyl diethyl phosphine oxides have about as good detergency characteristics as the dimethyl compounds.
  • the alkenyldimethylphosphine oxides'do not have as desirable non-hygroscopicity characteristics as the corresponding alkyl and hydroxyalkyl-dimethylphosphineoxides.
  • the alkenyl compounds, as well as the alkyl and hydroxyalkyl compounds, have a degree of thermal stability, however.
  • tertiary phosphine oxides of this invention can be prepared by methods similar to the methods for preparing the tertiary phosphine oxides which are known in the art. Such methods are discussed in an article by K. Darrell Berlin and George B. Butler, Chemical Reviews, volume 60, pp. 243-259, June 1960. In general, tertiary phosphine oxides of this invention can be prepared by oxidizing the corresponding tertiary phosphine, for example, with hydrogen peroxide.
  • R can be derived from naturally occurring fats and oils or from synthetic sources. Mixtures of phosphine oxides are very suitable wherein the R groups vary. in chain length in the C to C range, as for example, the alkyl groups 3 from coconut fatty alcohol (or distilled coconut fatty alcohol).
  • detergent compositions are useful per se as detergent and surface active agents. Desirably they are used with other materials to form detergent compositions, as for example, liquid, bar, flake, granular or tabletted granular compositions.
  • Such detergent compositions can contain the tertiary phosphine oxides of this invention and a material is selected from the class consisting of anionic organic detergents, nonionic organic detergents, watersoluble inorganic alkaline builder salts, water-soluble organic alkaline sequestrant builder salts and mixtures thereof wherein the ratio of phosphine oxide to this class of material is in the range of about 4:1 to about 1:20. (Parts, ratios and percentages herein are by weight.)
  • Granular or flake detergent compositions preferably contain about 5% to about 50% (desirably to 30%) of the phosphine oxides of this invention and liquid formulations contain about 4% to about 20% of such phosphine oxides.
  • Granular or flake detergent compositions preferably contain at least an equal amount of an alkaline builder salt.
  • Liquid formulations preferably contain from about 8% to about 40% of a water soluble alkaline builder salt, the balance of the composition being a solvent such as water, and/or other liquid vehicles as hereinafter more fully described.
  • bar formulations When used with anionic detergents, such as a soap base, and, if desired, inert fillers, bar formulations contain about 5% to about 50% of phosphine oxide. Bar formulations can contain about 40% to about 80% of the phosphine oxides of this invention as the only detergent component, if desired, and the balance inert fillers or builders.
  • Water-soluble inorganic alkaline builder salts used alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium monoand di-ortho phosphate and potassium bicarbonate. Such inorganic builder salts enhance the detergency of the subject phosphine oxides.
  • organic alkaline sequestrant builder salts used alone or in admixture are alkali metal, ammonium or substituted amomnium, aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(Z-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium, potassium and triethanolammonium N-(Z-hydroxyethyl)--nitrilo diacetates.
  • alkali metal salts of phytic acid e.g., sodium phytate are also suitable as organic alkah'ne seqnestrant builder salts (see US. Patent 2,739,942).
  • Anionic organic detergents which can be used in the compositions of this invention alone or in admixture include both the soap and non-soap detergents.
  • suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • anionic organic non-soap detergents are: alkyl glyceryl ether sulfonates; alkyl sulfates; alkyl monoglyceride sulfates or sulfonates; alkyl polyethenoxy ether sulfates; acyl sarcosinates; acyl esters of isethionates; acyl N-rnethyl taurides; alkyl benzene sulfonates; alkyl phenol polyethenoxy sulfonates.
  • the alkyl and acyl groups respectively, contain 10 to 20 carbon atoms.
  • water-soluble salts the sodium, potassium, ammonium and alkylolammonium salts, for examples.
  • Specific examples are: sodium lauryl sulfate; potassium N-methyl 4 lauroyl tauride; triethanolamine dodecyl benzene sulfonate.
  • nonionic organic detergents which can be used in the compositions of this invention alone or in admixture are: polyethylene oxide condensates of alkyl phenols wherein the alkyl group contains from 6 to 12 carbon atoms (e.g., t-octylphenol) and the ethylene oxide is present in a molar ratio of ethylene oxide to alkyl phenol in the range of 10:1 to 25:1; condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and.
  • ethylene diamine wherein the molecular weight of the condensation products ranges from 5000 to 11,000; the condensation prod ucts of from about 5 to 30 moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing from 8 to 18 carbon atoms (e.g., lauryl alcohol); C -C alkyl di-(C C alkyl) amine oxides (e.g.,
  • phosphine oxides of this invention particularly the C -C alkyldimethylphosphine oxides
  • the water soluble inorganic alkaline builder salts or organic alkaline sequestrant builder salts as described above, heavy-duty laundering compositions are obtained which have outstanding effectiveness in both cool water and hot water detergency.
  • the ratio of phosphine oxide to builder in such compositions is in the range of 1:1 to 1:10. It is quite surprising that the phosphine oxides of this invention, when employed in heavy-duty laundering compositions have outstanding cool water detergency effectiveness.
  • phosphine oxides are much more effective in this respect than soap, such as coconut oil soap, and are also much more effective than commonly used laundering active detergents such as alkylbenzenesulfonate (the alkyl being derived from tetrapropylene) and C -C alkyl sulfates.
  • the detergent compositions of this invention can contain any of the usual adjuvants, diluents and additives, for example, ampholytic, cationic or zwittcrionic detergents, perfumes, anti-tarnishing agents, anti-redeposition agents, bacteriostatic agents, dyes, fluorescers, suds builders, suds depressors, and the like without detracting from the advantageous properties of the composition.
  • adjuvants for example, ampholytic, cationic or zwittcrionic detergents, perfumes, anti-tarnishing agents, anti-redeposition agents, bacteriostatic agents, dyes, fluorescers, suds builders, suds depressors, and the like without detracting from the advantageous properties of the composition.
  • the desired alkyl radicals in RR'RP O can be obtained by selecting the appropriate reaction products.
  • a methylpropyldodecylphosphine. .oxide is desired, one mole each of methyl magnesium iodide and propyl magnesium iodide are used in Equation ,4 above; however, in such a reaction, a gross mixture of phosphine oxides including this compound would result.
  • Watersolubility of dimethyldodecylphosphine oxide at 27 0. was 50 to 55%.
  • the thermal stability of this compound is excellent, having been recovered substantially unchanged after being heated at 175 C. for two hours in a nitrogen atmosphere.
  • This compound is very resistant to hydrolysis, breaking down only with vigorous treatment such as fusion with caustic or high temperature acidification.
  • the low degree of hygrosc-opicity was shown when dimethyldodecylphosphine oxide, a crystalline solid, was allowed to standin room -air for several days without losing its crystalline form. Many other crystalline organic detergents form syrups when subjected to the same test. Further quantitative tests have shown that the water pickup by this compound at 70 F. and 80% relative humidity is very low (0.2% of sample weight).
  • the bacteriostatic efficacy of dimethyldodecylphosphine oxide was determined. In an aqueous matrix, it required a concentration of only 17.5 to 19 p.p.m. of this compound to arrive at the bacteriostatic breakpoint of M. aureus (gram positive). Bacteriostatic breakpoint is that concentration of material at which the multiplication of an organism is stopped. This degree of bacteriostatic efficacy is significant.
  • Dimethyldodecylphosphine oxide, dimethyloctade'cyl phosphine oxide and diethyloctadecylphosphine .oxid'e were prepared by processes similar to that described in Example II. The essential equations of this process are summarized below.
  • R, R and R" are as noted above.
  • Cloth swatches were soiled with a predetermined amount of artificial lipid soil (a blend of olive oil, stearic acid, oleic acid and tallow fatty alcohol). These soiled swatches were washed in a Tergotometer using water at 140 F. and containing .10% by weight of the product being tested. (Tergotometer testing is described in Detergency Evaluation and Testing, by J. C. Harris, Interscience Publishers, Inc. (1954), page 60.) Swatches are weighed on a dry basis before and after washing. On the basis of the percent residual lipid soil, the lower the percent, the better the detergency performance.
  • artificial lipid soil a blend of olive oil, stearic acid, oleic acid and tallow fatty alcohol
  • dimethyldodecylphosphine oxide is superior in detergency to dodecylbenzenesulfonate; it approaches the performance of one of the best commercially sulfate.
  • the cool water detergency of the phosphine oxides of this invention was evaluated by washing naturally soiled white dress shirts. Shirts were worn by male subjects under ordinary conditions for two normal working days. The degree to which a detergent composition containing a detergent compound to be tested cleaned the collars and cuffs of the coiled shirts, relative to the cleaning degree of a similar composition containing a standard detergent compound was considered a measure of the detergency effectiveness of the test compound.
  • the washing solution used in the test contained 0.03%' organic detergent compound and 0.06% sodium tripolyphosphate. (No fiuorescers, bleaches or antiredeposition agents were used.)
  • the pH of the washing solution was 10 and water of 7 grains per gallon hardness was used.
  • a conventional agitator-type Washer was used.
  • the detergent compound in the standard detergent composition was sodium alkylbenzenesulfonate (the alkyl being derived from tetrapropylene), the most commonly used organic detergent in heavy-duty laundry detergent compositions.
  • the test detergent composition contained the detergent compound to be tested, i.e., compared with the standard composition.
  • dimethyldodecylphosphine oxide showed surprising cool water detergency. Similar results are obtained with dimethyltetradecylphosphine oxide.
  • the surprising cool water detergency of the phosphine oxides of this invention is best seen in aqueous solutions having a temperature in the range of about 60 F. to about 95 F. and the concentration of the active phosphine oxide compound is in the range of about 0.005% to about 0.5% and the washing solution also contains a water soluble inorganic alkaline builder salt or organic alkaline sequestrant builder salt (as hereinbefore described) in the range of about 0.01% to about 1.0%.
  • a 0.436% water solution of this composition was used to wash soiled dishes.
  • the Water was at 115 F. and 7 grain hardness. 40 seconds of mechanical agitation provided more than 1" of stable suds.
  • the phosphine oxides of this invention can be used in effective solid form detergent composition having improved hygroscopicity, thermal stability and both 0001' and hot water detergency characteristics. They have the following formulas:
  • liquid detergent compositions can be made with the preferred G -C alkyldimethylphosphine oxides.
  • Such liquid compositions comprise from about 4% to about 20% of such preferred phosphine oxides, from about 5% to about 15% of an aryl sul-fonate solubilizing agent, e.g., sodium or potassium toluene, benzene or xylene sulfonate, and from about 8% to about 40% of a Water soluble inorganic alkaline builder salt, organic alkaline sequestrant builder salt or mixtures thereof as described above, the balance of the composition being water.
  • an aryl sul-fonate solubilizing agent e.g., sodium or potassium toluene, benzene or xylene sulfonate
  • a Water soluble inorganic alkaline builder salt, organic alkaline sequestrant builder salt or mixtures thereof as described above, the balance of the composition being water.
  • an anionic or nonionic non-soap organic detergent as hereinbefore described can also advantageously be included.
  • sodium silicate as a corrosion inhibitor and additional builder can also be advantageously included as well as minor amounts of such useful additives such as perfume, dyes and opacifiers.
  • the builder salt is potassium pyrophosphate, potassium nitrilo triacetate or potassium ethylenediaminetetraacetate.
  • the following formulation is an example of a homogeneous, heavy-duty liquid laundering composition which has excellent sudsing characteristics and outstanding detergency characteristics in both cool and warm water:
  • a composition with equivalent characteristics can be obtained by using in the above formulation an equivalent amount of potassium nitrilotriacetate instead of the potassium pyrophosphate, an equivalent amount of potassium xylene sulfonate for the toluene sulfonate, and equivalent amount of the condensation product of dodecanol and moles of ethylene oxide instead of the dodecyl benzene sulfonate.
  • Tertiary phosphine oxide compounds having the formula RRRP-+ 0, wherein R is selected from the group consisting of alkyl and monohydroxyalkyl radicals ranging in chain length from 10 to 18 carbon atoms, R and R are each selected from the group consisting of alkyl and monohydroxyalkyl radicals containing from 1 to 3 carbon atoms.
  • Alkyl dimethylphosphine oxides wherein the alkyl radical ranges in chain length from 10 to 18 carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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US173834A 1961-03-17 1962-02-16 Tertiary phosphine oxide compounds Expired - Lifetime US3304330A (en)

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US309841A US3304263A (en) 1961-03-17 1963-09-18 Phosphine oxide detergent composition

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BE (1) BE615204A (de)
CH (1) CH420459A (de)
DE (1) DE1228365B (de)
DK (1) DK116610B (de)
FI (1) FI41422B (de)
FR (1) FR1317586A (de)
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Cited By (8)

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US3467717A (en) * 1966-09-14 1969-09-16 Lever Brothers Ltd Tertiary organophosphine oxides
US3495257A (en) * 1968-06-28 1970-02-10 Hooker Chemical Corp Method for preparing trivinyl phosphine oxides
US3518311A (en) * 1965-04-05 1970-06-30 Monsanto Co Tertiary phosphine sulfides and process for preparing
US3532774A (en) * 1966-09-29 1970-10-06 Monsanto Co Phosphinites,phosphine oxides and process for preparing
US4365094A (en) * 1979-12-28 1982-12-21 Societe Nationale Des Poudres Et Explosifs Process for the synthesis of tertiary phosphine oxides, and new tertiary phosphine oxides
US4452716A (en) * 1982-12-20 1984-06-05 Fmc Corporation Mixed trialkylphosphine oxides as functional fluids
US4575563A (en) * 1984-02-01 1986-03-11 Fmc Corporation Liquid mixtures of trialkylphosphine oxides
US20080098614A1 (en) * 2006-10-03 2008-05-01 Wyeth Lyophilization methods and apparatuses

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US3948980A (en) * 1970-12-30 1976-04-06 Hoechst Aktiengesellschaft Tertiary phosphine
GB1434728A (en) * 1972-09-27 1976-05-05 Wilkinson Sword Ltd Compositions and articles containing phospine oxides having a physiological cooling effect and phosphine oxides for use therein
AU1092276A (en) 1975-02-14 1977-08-18 Procter & Gamble Detergent compositions
US4343914A (en) * 1981-07-22 1982-08-10 Fmc Corporation Flame retardant polyurethane containing alkyl bis(3-hydroxypropyl) phosphine oxide
US6165481A (en) * 1997-12-25 2000-12-26 Nippon Petrochemicals Company, Inc. Highly pure squalane, raw material for pharmaceuticals and cosmetics prepared by using the same and method for producing the same
JP2002537102A (ja) 1999-02-26 2002-11-05 カイロン コーポレイション 吸着された高分子および微粒子を有するミクロエマルジョン
ES2649896T3 (es) 2010-07-06 2018-01-16 Glaxosmithkline Biologicals Sa Emulsiones catiónicas de aceite en agua
CA2840965C (en) 2011-07-06 2021-03-02 Novartis Ag Cationic oil-in-water emulsions
EP2729125B1 (de) 2011-07-06 2017-12-13 GlaxoSmithKline Biologicals SA Öl-in-wasser-emulsionen mit nukleinsäuren

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US3064053A (en) * 1960-09-27 1962-11-13 American Cyanamid Co Phosphine oxides and preparation thereof
US3067258A (en) * 1961-06-14 1962-12-04 American Cyanamid Co Process for preparing organic phosphine oxides and olefins

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US2774786A (en) * 1953-08-10 1956-12-18 Gen Mills Inc Phosphono-ammonium surface active agents
US2784208A (en) * 1955-02-17 1957-03-05 Standard Oil Co Monomethyl esters of aliphatic phosphonic acids
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CA570694A (en) * 1959-02-17 C. Morris Rupert Bis(alkyl)allylphosphine oxides
US2543744A (en) * 1946-04-04 1951-03-06 Gen Aniline & Film Corp Nonfoaming soap composition
US2792348A (en) * 1952-10-21 1957-05-14 Emery Industries Inc Soap composition
US3064053A (en) * 1960-09-27 1962-11-13 American Cyanamid Co Phosphine oxides and preparation thereof
US3067258A (en) * 1961-06-14 1962-12-04 American Cyanamid Co Process for preparing organic phosphine oxides and olefins

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3518311A (en) * 1965-04-05 1970-06-30 Monsanto Co Tertiary phosphine sulfides and process for preparing
US3467717A (en) * 1966-09-14 1969-09-16 Lever Brothers Ltd Tertiary organophosphine oxides
US3532774A (en) * 1966-09-29 1970-10-06 Monsanto Co Phosphinites,phosphine oxides and process for preparing
US3495257A (en) * 1968-06-28 1970-02-10 Hooker Chemical Corp Method for preparing trivinyl phosphine oxides
US4365094A (en) * 1979-12-28 1982-12-21 Societe Nationale Des Poudres Et Explosifs Process for the synthesis of tertiary phosphine oxides, and new tertiary phosphine oxides
US4452716A (en) * 1982-12-20 1984-06-05 Fmc Corporation Mixed trialkylphosphine oxides as functional fluids
US4575563A (en) * 1984-02-01 1986-03-11 Fmc Corporation Liquid mixtures of trialkylphosphine oxides
US20080098614A1 (en) * 2006-10-03 2008-05-01 Wyeth Lyophilization methods and apparatuses

Also Published As

Publication number Publication date
CH420459A (de) 1966-09-15
FR1317586A (de) 1963-05-08
NL276032A (de) 1964-10-12
DE1228365B (de) 1966-11-10
FI41422B (de) 1969-07-31
SE308937B (de) 1969-03-03
US3304263A (en) 1967-02-14
BE615204A (de) 1962-09-17
GB995260A (en) 1965-06-16
DK116610B (da) 1970-01-26

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