WO1999050236A1 - Production of tertiary amine oxides - Google Patents
Production of tertiary amine oxides Download PDFInfo
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- WO1999050236A1 WO1999050236A1 PCT/US1999/005506 US9905506W WO9950236A1 WO 1999050236 A1 WO1999050236 A1 WO 1999050236A1 US 9905506 W US9905506 W US 9905506W WO 9950236 A1 WO9950236 A1 WO 9950236A1
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- reaction
- tertiary amine
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- reaction mixture
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
- C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
Definitions
- This invention relates to novel process technology for producing tertiary amine oxides and to novel and eminently useful tertiary amine oxide compositions which are provided by this invention.
- the process technology of this invention enables the direct synthesis and provision of tertiary amine oxide surfactants having extremely low levels, if any, of nitrosoamines (commonly known as nitrosamines), as well as possessing other important characteristics, including low free amine content.
- amine oxides are produced by combining a tertiary amine and hydrogen peroxide in the presence of water.
- the typical prior art process is an isothermal process wherein the amine and water, and promoter if used, are heated before addition of peroxide in order to initiate the reaction. Because the reaction is exothermic, once the reaction has been initiated by heat input, the reaction mixture must be cooled to control the temperature of the reaction. After the majority of the reaction is completed, additional heat must be added to the system to achieve a final conversion.
- Nitrosamine impurities in amine oxides have long been regarded as harmful impurities by most in the surfactant industry because of suspected carcinogenic and mutagenic properties. See for example "Nitrosamines: Assessing the Relative Risk” in Chemical & Engineering News, pages 20-26, March 31, 1980. Nevertheless, according to U.S. Pat. No. 5,498,791 (March 12, 1996), commercial amine oxides contain between 200-1000 ppb nitrosamines.
- Tertiary amine oxide product produced by Albemarle Corporation heretofore did achieve low levels of nitrosamine, but free amine levels were typically 0.5 wt%. Unfortunately, free amine has a deleterious effect upon the stability of hypochlorite bleaches.
- this invention it is also now possible to provide highly pure tertiary amine oxide products which have very low levels, if any, of nitrosamine and free amine impurities, and very low levels of metal impurities, and because no phosphorus additives are needed in the process, the tertiary amine oxide products of this invention are devoid of phosphorus resulting from use of phosphorus additive. Since it is preferred not to employ organic solvents or diluents in the aqueous reaction medium, this invention also makes it possible to provide tertiary amine oxide products that are devoid of organic impurities resulting from use of organic solvent or diluent in the process.
- a process for producing tertiary amine oxide which comprises oxidizing tertiary amine with hydrogen peroxide in an aqueous reaction medium, the aqueous reaction medium having been formed or being formed from tertiary amine, aqueous hydrogen peroxide, carbon dioxide, and optionally chelating agent and/or additional water, the exothermic oxidation reaction being initiated at a temperature in the range of 15 to 25°C, and while agitating the reaction mixture, allowing the temperature of the reaction mixture to rise adiabatically to a temperature in the range of 50 to 100°C, such that tertiary amine oxide is produced.
- the reaction is conducted in a thermally insulated reactor.
- Products having 30 ppb or less, if any, of nitrosamine impurity and 0.3 wt% or less, typically 0.2 wt% or less, if any, of free amine can be produced by proper conduct of the process of this invention.
- a tenable explanation for the surprisingly low levels, if any, of nitrosamine impurity in the product results from substantially uniform
- the temperature of the reaction mixture continuously rises due to the exothermic nature of the reaction, yet at each given instant of time the temperature is deemed substantially uniform throughout the entire reaction mixture. Whether such uniform temperature conditions also play a role in the formation of product having low free amine contents is not known, but the possibility exists.
- the catalyst acts as a neutralizing agent, the amine, water, and peroxide solution are able to form an emulsion which leads to faster and more uniform reaction initiation and progression.
- another embodiment of this invention simulates to the extent reasonably feasible technically and economically, the conditions that exist during the adiabatic process of this invention.
- a process for producing tertiary amine oxide which comprises oxidizing tertiary amine with hydrogen peroxide in an aqueous reaction medium, the aqueous reaction medium having been formed or being formed from tertiary amine, aqueous hydrogen peroxide, carbon dioxide, and optionally chelating agent and/or additional water, the exothermic oxidation reaction being initiated at a temperature in the range of 1 to 25°C, and while agitating the reaction mixture, applying a controlled limited amount of heat energy to the reaction mixture and maintaining a substantially uniform temperature throughout the agitated reaction mixture whereby at any given moment in time the temperature differential within the reaction mixture is no greater than 5°C, and preferably no greater than 2°C, such that the temperature of the reaction mixture is increased, and preferably is progressively increased, to a maximum temperature in the range of 50 to 100°C, such that tertiary amine oxide is produced, the major amount (i.e., more than 50%) of the heat energy causing the increase in
- reaction initiation temperature By proper selection and coordination of the reaction initiation temperature, the volume of water in the reaction mixture, the amount of heat energy supplied to the reaction mixture, and the rate of agitation of the reaction mixture, it is possible to produce tertiary amine oxides having very low levels of nitrosamine and free amine content without need for use of special additives such as metal carbonates or bicarbonates, and/or phosphorus additives of the prior art.
- Still another embodiment of this invention provides an aqueous solution of tertiary amine oxide wherein the content of tertiary amine oxide is in the range of 25 to 35 wt%; wherein the content of nitrosamine, if any, is 30 ppb (wt/wt) or less; and wherein the content of amine, if any, is 0.3 wt% or less.
- the total content of alkali metal e.g., Na
- the total content of alkaline earth metal, if any, e.g., Mg and Ca
- the total content of alkaline earth metal, if any, is 1 ppm (wt/wt) or less; each foregoing wt%, ppb, and ppm being based on the weight of the solution.
- ppb means parts per billion parts, a billion being 10 9 or a thousand million
- ppm means parts per million parts, a million being 10 6
- wt/wt the parts are parts by weight.
- the solutions of this invention preferably have a content, if any, of no more than
- solutions wherein the content of titanium, if any, is 0.1 ppm (wt/wt) or less; wherein the content of iron, if any, is 1.0 ppm (wt/wt) or less; wherein the content of cobalt, if any, is 0.3 ppm (wt/wt) or less; wherein the content of nickel, if any, is 0.5 ppm (wt/wt) or less; and wherein the content of copper, if any, is 2 ppm (wt/wt) or less, and most preferably 0.5 ppm or less.
- Preferred solutions are those in which the tertiary amine oxide is one or more compounds of the formula
- R'R 2 R 3 N 0 where R 1 is a methyl or ethyl group, R 2 is a primary alkyl group having in the range of 8 to 20 carbon atoms, and R 3 is, independently, a methyl group, an ethyl group, or a primary alkyl group having in the range of 8 to 20 carbon atoms.
- R 1 and R 3 are methyl groups and R 2 is a straight chain primary alkyl group are particularly preferred.
- the groups designated R represent C 8 -C 24 alkyl or alkenyl polyalkyleneoxy groups, C 7 -C 23 esteralkyl or esteralkenyl groups, amidoalkyl or amidoalkenyl groups, and the R ! groups, which may also be the same or different, represent C r C alkyl, alkoxy or hydroxyalkyl, or polyalkyleneoxy groups.
- the polyalkyleneoxy groups are preferably polyethyleneoxy groups or polypropyleneoxy or mixed ethyleneoxy and propyleneoxy groups containing between 1 and 20 ethyleneoxy and/or propy-
- amidoalkyl groups are preferably C 7 -C 23 alkylamidopropyl groups or alkenylamidopropyl groups.
- the amines may comprise cyclic amines such as imidazolines or pyridines, N- substituted piperazines, or N-substituted morpho lines, e.g., N-methyl morpholine.
- Preferred tertiary amines used in the process of this invention are one or more compounds of the formula R'R 2 R 3 N where R 1 is a methyl or ethyl group, R 2 is a primary alkyl group having in the range of 8 to 20 carbon atoms, and R 3 is, independently, a methyl group, an ethyl group, or a primary alkyl group having in the range of 8 to 20 carbon atoms.
- the hydrogen peroxide is typically employed as a water solution of any suitable concentration.
- the hydrogen peroxide is employed as a 30 to 70 wt% aqueous solution.
- Particularly preferred solutions are 30 to 40 wt% aqueous hydrogen peroxide solutions.
- the amount of hydrogen peroxide employed in the reaction should be at least a stoichiometric amount (i.e., at least 1 mole of hydrogen peroxide per mole of tertiary amine).
- an excess amount of hydrogen peroxide is used, and in this case an excess in the range of 1.01 to 1.2 moles of hydrogen peroxide per mole of tertiary amine is preferred.
- Chelating agent An optional, but preferable, component used in the reaction mixtures is at least one suitable chelating agent such as ethylenediamine tetraacetic acid or a water-soluble salt thereof, diethylene- triamine pentaacetic acid or a water-soluble salt thereof, or S,S-ethylenediamine disuccinic acid or a water-soluble salt thereof.
- chelating agents include nitrilotriacetic acid or a water- soluble salt thereof.
- the chelating agent which serves as a sequestrant for metal ions which may be derived by extraction from metallic reactor walls, piping or the like, is preferably a metal-free chelating agent. In this way the chelating agent as added to the reaction mixture does not itself introduce any metal constituent(s).
- a salt it is preferably an ammonium salt, although because of the small amounts of chelating agent used, alkali metal salts such as the sodium salts are acceptable for use.
- the amount of chelating agent used will fall in the range of 0.01 to 0.1 wt%, and preferably in the range of 0.05 to 0.1 wt%, based on the total weight of the reaction mixture.
- ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, and S,S -ethylenediamine disuccinic acid are the three most preferred materials.
- the water used should be free of appreciable quantities of dissolved metals. While it is not necessary to employ deionized or distilled water, such materials can be used if desired. Ordinary tap water is satisfactory provided that it has a metallic content, if any, of not more than 5 ppm. Ordinarily at least a portion of the water employed in producing the reaction medium will be provided by the aqueous hydrogen peroxide solution. However, oftentimes it is desirable to increase the amount of water over and above that provided by the aqueous hydrogen peroxide being used in making up the reaction mixture.
- the amount of water should correspond in quantity to the quantity desired in the finished amine oxide solution to be produced in the process, as this eliminates the need for subsequent operations such as further dilution with water, or distillation of excessive quantities of water from the aqueous product solution produced in the reaction.
- the total amount of water introduced into the reaction mixture should correspond to approximately 70 wt% of the projected total weight of the amine oxide solution being formed.
- An essential ingredient charged to the reaction mixture is carbon dioxide. Although it may be charged in the form of so-called dry ice, it is preferable to introduce the carbon dioxide in gaseous form and to introduce the same at a locus below the surface of the liquid reaction mixture.
- the carbon dioxide serves as a reaction catalyst or reaction promoter. In this connection, the precise chemical make-up of the carbon dioxide-derived catalyst is not known with certainty. It may be that the carbon dioxide itself catalyzes or promotes the reaction. However it is equally possible that the carbon dioxide reacts in situ to form either carbonic acid or some unidentified complex or other substance which serves as the actual catalytic entity.
- this invention is not limited to the particular form or chemical composition of the reaction catalyst or reaction promoter resulting from the introduction into the reaction mixture of carbon dioxide as an ingredient.
- the amount of carbon dioxide introduced into the aqueous reaction mixture should be such as to result in the reaction mixture initially achieving a pH in the range of 7 to 8, and preferably in the range of 7.3 to 7.8.
- the various ingredients making up the reaction mixture can be introduced into the reactor in a number of sequences.
- each of the ingredients can be introduced individually or in any suitable subcombinations and in any suitable order into the reactor in the total quantities to be used with no further feed of any ingredient during the course of the reaction.
- the only preference is that either the carbon dioxide or the aqueous hydrogen peroxide should be the last ingredient introduced into the reaction mixture, as the reaction will be initiated upon the introduction of either such ingredient to the mixture comprising the other such ingredient and the tertiary amine.
- the aqueous reaction medium is formed by mixing together tertiary amine, carbon dioxide, optionally chelating agent, and optionally water, and then introducing aqueous hydrogen peroxide into the reaction mixture to initiate the exothermic reaction.
- the aqueous reaction medium is formed by mixing together tertiary amine, aqueous hydrogen peroxide, and optionally chelating agent and/or additional water, and then introducing carbon dioxide to initiate the exothermic reaction.
- Still another such embodiment involves forming the reaction mixture by introducing tertiary amine, and optionally chelating agent and/or water, into a reactor, and then introducing concurrently or in any sequence, aqueous hydrogen peroxide and carbon dioxide to initiate the exothermic reaction.
- the tertiary amine could be the last ingredient charged to the reaction mixture, however this is less desirable as it could result in excessive premature oxidation of the tertiary amine with adverse consequences.
- the aqueous hydrogen peroxide is introduced portionwise, continuously and/or intermittently, into the reaction mixture initially composed of tertiary amine, carbon dioxide, chelating agent if used, and water if used. Some of the hydrogen peroxide can also be present in the initial reaction mixture. In another such embodiment aqueous hydrogen peroxide and carbon dioxide are concurrently introduced portionwise,
- reaction mixture initially composed of tertiary amine, chelating agent if used, and water if used.
- a portion of the carbon dioxide and/or hydrogen peroxide can be present in the initial reaction mixture.
- Still another variant is to introduce carbon dioxide portionwise, continuously and/or intermittently, into the reaction mixture initially composed of tertiary amine, aqueous hydrogen peroxide, chelating agent if used, and additional water if used.
- the initial reaction mixture may also contain a portion of the carbon dioxide.
- this invention contemplates the addition of the respective ingredients into the reaction mixture being formed in any suitable manner (individually and/or in any suitable subcombination(s), concurrently and/or in any suitable sequence.
- the reactor used in the practice of the process of this invention is provided with thermal insulation of any suitable type.
- thermal insulation having a suitably high R value reduces the extent to which thermal energy can pass into or out of the reaction vessel and thus into or out of the reaction mixture undergoing an adiabatic reaction.
- a jacketed reactor can be employed in which a controlled amount of heat energy is supplied to the reaction mixture by means of the heated fluid flowing through the jacket of the reactor.
- the temperature of the water fed to and flowing through the jacket is correspondingly elevated so that the amount of heat loss or gain through the reactor walls is minimized.
- the exothermic oxidation reaction is initiated at a temperature in the range of 15 to 25 °C, and while agitating the reaction mixture, allowing the temperature of the reaction mixture to rise adiabatically to a temperature in the range of 50 to 100°C, and preferably in the range of 60 to 80°C such that tertiary amine oxide is produced.
- the reaction is initiated at a temperature in the range of 1 to 25°C, and while agitating the reaction mixture and keeping the temperature substantially uniform throughout the entire mixture at each moment in time, a controlled limited amount of heat energy is applied to the reaction mixture to a maximum temperature in the range of 50 to 100°C, such that tertiary amine oxide is produced.
- the reaction can be conducted in an open system at ambient atmospheric pressure, or it can be conducted in a closed system under superatmospheric pressure such as autogenous pressure or externally applied pressure.
- Analytical procedures Any suitable procedure can be used for determining content various impurities in the reaction mixtures produced in the process. For convenience, the following procedures (or other procedures of at least equivalent accuracy) are recommended:
- a sample of amine oxide is reacted with acetic anhydride in the presence of acetic acid under reflux conditions.
- the sample is cooled and titrated potentiometrically with 0.1 N HClO 4 in acetic acid.
- a sample of aqueous amine oxide is digested with sulfuric acid at 380°C. Nitric acid is added as needed to keep the solution clear. The mixture is charred until only 1 mL remains in the beaker. Deionized-distilled water and concentrated nitric acid are added to form a solution. The mixture is allowed to again cool. The resulting solution is analyzed by inductively coupled plasma (ICP) emission spectroscope using a Perkin-Elmer Optima 3000, or equivalent device.
- ICP inductively coupled plasma
- a dilute sample of aqueous amine oxide is reacted with potassium iodide and titrated with sodium thiosulfate.
- a quantitative amount of iodine is formed from the available peroxide in a given sample.
- Total N-nitrosamine content is determined by a chemiluminescence method in which nitrite ions in the sample are destroyed by sulfuric acid, the sample is denitrosated using HBr/acetic acid, and the nitric oxide (NO) liberated from the sample is fed into a chemiluminescence analyzer.
- the nitric oxide reacts with ozone in the analyzer to produce excited NO 2 .
- Albemarle Corporation (200.3 g, 1.08 mol), 35% aqueous hydrogen peroxide (108.1 g, 1.11 mol, 4% molar excess), 409.8 mL of water, and diethylene triamine pentaacetic acid (DTP A) (0.5 g, 1.3 mmol), are added to an thermally insulated round bottom flask.
- the insulation is a mantle of fiberglass wool.
- Carbon dioxide is introduced to the reactor in 1.6 wt% relative the charged amine.
- EXAMPLE 2 A procedure similar to that of Example 1, but in which the hydrogen peroxide is metered into the reaction mixture over time produces like results.
- ADMA ® -10 amine Albemarle Corporation
- DTP A diethylene triamine pentaacetic acid
- the 35% aqueous hydrogen peroxide (108.6 g, 1.12 mol, 4% molar excess) is charged over a period of 35 minutes along with additional carbon dioxide. During that period the temperature rises 54°C. The maximum temperature achieved was 74°C. During the 90-minute cook, the temperature decreased by 11°C. Two hours after the peroxide addition began, the free amine was measured to be 0.21 wt% (99.2% conversion) and the residual hydrogen peroxide was 0.25 wt%. The level of nitrosamine was 10 ppb (wt/wt).
- EXAMPLE 3 Combined in a round bottom flask at ambient temperature (ca. 20°C) were 191.2 grams (0.90 mol) of dimethyl dodecyl amine (ADMA ® - 12 amine, Albemarle Corporation), 393.3 grams of tap water (essentially zero hardness), and 0.5 gram of DTPA. The flask was insulated with a mantle of glass wool. Catalyst was then introduced to the flask through a subsurface dipleg prior to hydrogen peroxide addition. 84.0 (0.94 mol) Grams of 35% hydrogen peroxide (4% excess) was fed over a 40-minute period. The reaction was allowed to proceed adiabatically until the temperature of the reaction mass reached a maximum temperature of 68°C. At this point the reaction mass began to cool because the reaction was essentially completed. Within 3 hours of introduction of catalyst and hydrogen peroxide, the reaction was completed. The total nitrosamine content of the sample was 8 ppb.
- ADMA ® - 12 amine dimethyl dode
- BARLOX 12 amine oxide (Lonza Inc.) (Specification: 29.6 wt% lauryl dimethyl tertiary amine oxide);
- BARLOX 14 amine oxide (Lonza Inc.) (Specification: 31.4 wt% myristyl dimethyl tertiary amine oxide);
- AMMONYX LO amine oxide (Stephan Co.) (Specification: 30.6 wt% lauryl dimethyl tertiary amine oxide);
- AMMONYX MO amine oxide (Specification: 30.1 wt% myristyl dimethyl tertiary amine oxide);
- nitrosamine content of the tertiary amine oxide product compositions of this invention refers to the total nitrosamine content of the product, reported as - NNO species. Such species has a molecular weight of 44. Thus the nitrosamine content, if any of the tertiary amine oxide product compositions of this invention is independent of the organic groups to which the -NNO species is attached.
- reactants and components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another reactant, or a solvent). It matters not what preliminary chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution or reaction medium as such changes, transformations and/or reactions are the natural result of bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure.
- the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical reaction or in forming a mixture to be used in conducting a desired reaction.
- the process of this invention produces "tertiary amine oxide" in an aqueous medium.
- tertiary amine oxide By this is meant that if the water is removed one will recover tertiary amine oxide as a chemical product.
- the "tertiary amine oxide” While the “tertiary amine oxide” is in solution it may possibly be solvated, hydrated, complexed, or otherwise altered in chemical makeup, and if such actually happens, the claims hereinafter are intended to cover any such natural consequence of carrying out the process of this invention in the proper manner as described herein. Thus it matters not if any such solvation, hydration, or other alteration in chemical makeup of the "tertiary amine oxide” occurs while in the aqueous medium as long as the process is being carried out properly as described and claimed herein.
- the product of the process is identified as chemists identify products, and not as lawyers or others might seek to identify them.
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99912490A EP1068179A1 (en) | 1998-04-01 | 1999-03-12 | Production of tertiary amine oxides |
CA002326974A CA2326974A1 (en) | 1998-04-01 | 1999-03-12 | Production of tertiary amine oxides |
JP2000541143A JP2002509913A (en) | 1998-04-01 | 1999-03-12 | Production of tertiary amine oxide |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/053,444 US6080889A (en) | 1998-04-01 | 1998-04-01 | Production of tertiary amine oxides |
US09/150,820 US6166255A (en) | 1998-04-01 | 1998-09-11 | Production of tertiary amine oxides |
US09/053,444 | 1998-09-11 | ||
US09/150,820 | 1998-09-11 |
Publications (1)
Publication Number | Publication Date |
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WO1999050236A1 true WO1999050236A1 (en) | 1999-10-07 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1999/005506 WO1999050236A1 (en) | 1998-04-01 | 1999-03-12 | Production of tertiary amine oxides |
Country Status (5)
Country | Link |
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US (1) | US6166255A (en) |
EP (1) | EP1068179A1 (en) |
JP (1) | JP2002509913A (en) |
CA (1) | CA2326974A1 (en) |
WO (1) | WO1999050236A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014018249A1 (en) * | 2012-07-24 | 2014-01-30 | The Procter & Gamble Company | Continuous process to make amine oxide |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003096048A (en) * | 2001-09-27 | 2003-04-03 | Nof Corp | Production method of amine oxide |
JP4856406B2 (en) * | 2005-08-09 | 2012-01-18 | ライオン・アクゾ株式会社 | Method for producing amine oxide |
US20090286994A1 (en) * | 2008-03-11 | 2009-11-19 | Nanomaterials Discovery Corporation | Process for Synthesizing Nitramine Compounds |
TW202406898A (en) | 2022-06-10 | 2024-02-16 | 德商巴斯夫歐洲公司 | Process for making a substantially nitrosamine-free, substantially peroxide-free, substantially colorless amine oxide, and n-methylmorpholine n-oxide obtainable by the process |
Citations (3)
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US4247480A (en) * | 1978-08-24 | 1981-01-27 | Nissan Chemical Industries Limited | Process for producing amineoxide |
EP0320694A2 (en) * | 1987-12-14 | 1989-06-21 | Ethyl Corporation | Amine oxide process |
EP0426084A1 (en) * | 1989-10-30 | 1991-05-08 | Ethyl Corporation | Amine oxide process |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3332999A (en) * | 1963-12-10 | 1967-07-25 | Ethyl Corp | Process for preparation of amine oxides |
US4970340A (en) * | 1985-07-01 | 1990-11-13 | Ethyl Corporation | Amine oxide process and composition |
FR2590575B1 (en) * | 1985-11-25 | 1988-01-29 | Interox Sa | PROCESS FOR THE MANUFACTURE OF OXIDES OF AROMATIC TERTIARY AMINES AND PRODUCTS THUS OBTAINED |
US4748275A (en) * | 1986-09-08 | 1988-05-31 | Ethyl Corporation | Non-hygroscopic trialkylamine oxides |
AU615471B2 (en) * | 1987-09-08 | 1991-10-03 | Ethyl Corporation | Amine oxide process |
US4942260A (en) * | 1988-08-29 | 1990-07-17 | Ethyl Corporation | Amine oxide process with CO2 and aluminum |
US5130488A (en) * | 1989-04-26 | 1992-07-14 | Ethyl Corporation | Process for preparing tert-amine oxides |
US5075501A (en) * | 1989-10-02 | 1991-12-24 | Ethyl Corporation | Mixed tert-amine oxide dihydrates |
US4960934A (en) * | 1989-10-27 | 1990-10-02 | Ethyl Corporation | Amine oxide process |
US5208374A (en) * | 1989-10-30 | 1993-05-04 | Ethyl Corporation | Amine oxide process |
US5292954A (en) * | 1990-05-17 | 1994-03-08 | Ethyl Corporation | Amine oxide composition and process |
GB9102311D0 (en) * | 1991-02-02 | 1991-03-20 | Albright & Wilson | Nitrosamine inhibition |
GB9202057D0 (en) * | 1992-01-31 | 1992-03-18 | Albright & Wilson | Synergistic inhibition of nitrosamines and nitrites |
US5466870A (en) * | 1993-10-29 | 1995-11-14 | The Procter & Gamble Company | Process for reducing the levels of nitrite contaminants in amine oxide surfactants |
DE19528945A1 (en) * | 1995-08-07 | 1997-02-13 | Hoechst Ag | Process for the preparation of tertiary amine oxides |
-
1998
- 1998-09-11 US US09/150,820 patent/US6166255A/en not_active Expired - Fee Related
-
1999
- 1999-03-12 EP EP99912490A patent/EP1068179A1/en not_active Withdrawn
- 1999-03-12 CA CA002326974A patent/CA2326974A1/en not_active Abandoned
- 1999-03-12 JP JP2000541143A patent/JP2002509913A/en not_active Withdrawn
- 1999-03-12 WO PCT/US1999/005506 patent/WO1999050236A1/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4247480A (en) * | 1978-08-24 | 1981-01-27 | Nissan Chemical Industries Limited | Process for producing amineoxide |
EP0320694A2 (en) * | 1987-12-14 | 1989-06-21 | Ethyl Corporation | Amine oxide process |
EP0426084A1 (en) * | 1989-10-30 | 1991-05-08 | Ethyl Corporation | Amine oxide process |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014018249A1 (en) * | 2012-07-24 | 2014-01-30 | The Procter & Gamble Company | Continuous process to make amine oxide |
Also Published As
Publication number | Publication date |
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US6166255A (en) | 2000-12-26 |
EP1068179A1 (en) | 2001-01-17 |
CA2326974A1 (en) | 1999-10-07 |
JP2002509913A (en) | 2002-04-02 |
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