US2387201A - Mono-acyl ethylene diamines - Google Patents
Mono-acyl ethylene diamines Download PDFInfo
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- US2387201A US2387201A US426487A US42648742A US2387201A US 2387201 A US2387201 A US 2387201A US 426487 A US426487 A US 426487A US 42648742 A US42648742 A US 42648742A US 2387201 A US2387201 A US 2387201A
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- ethylene diamine
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- ethylene
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
Definitions
- This invention relates to new derivatives of ethylene diamine and more particularly it relates to new mono-acyl derivatives of ethylene diamine.
- the invention includes new mono-acyl ethylene diamines as well as a new process for making these compounds.
- the new compounds of the invention are monoacyl ethylene diamines containing from 12 to 14 carbon atoms in the acyl group and include monolauroyl and mono-myristoyl ethylene diamines.
- the invention also includes mixed mono-acyl ethylene diamines in which the acyl group is derived from the fatty acids obtainable from natural oils and waxes which contain a major proportion of fatty acids in the free or combined state having from 12 to 14 carbon atoms, such as, for example, the fatty acids obtainable from bayberry wax, palm kernel oil, and cocoanut oil.
- the new mono-acyl ethylene diamines are solids of characteristic melting point, with strongly basic properties as exemplified by their ability to form characteristic amine hydrochlorides.
- the invention also includes the salts of the aforementioned mono-acyl ethylene diamines, as well as a process by which'such salts may be advantageously prepared.
- Such salts may be prepared in accordance with the invention, by dissolving the mono-acyl ethylene diamine in a solvent in which the salt desired is substantially insoluble, e. g., ether, ispropyl ether, benzene, toluene, etc., and then treating the resulting solution of the mono-acyl ethylene diamine with a substantially anhydrous acid corresponding to the salt desired, e. g., hydrochloric, hydrobromic, ulphuric, etc., to produce the chlorides, bromides, sulphates, etc., respectively.
- These salts are water soluble and have very desirable surface activity characteristics. They may advantageously be used as emulsifying, detergent, wetting, dispersing, or flotation agents; and, in the form of the hydrochloride salts, they may be used with particular advantage as flotation agents in the froth flotation of potassium chloride ores or brines.
- the new process of the invention by which the new mono-acyl ethylene diamine derivatives may be produced comprises heating an excess of ethylene diamine with an ester of a fatty acid containing from 12 to 14 carbon atoms, treating the reaction mixture with a water-immiscible solvent for the mono-acyl ethylene diamine, separating the water-immiscible solvent containing the mono-acyl ethylene diamine dissolved therein from the reaction mixture and evaporating the solvent to recover the mono-acyl ethylene diamine.
- the amount of ethylene diamine reacted with a Q given quantity of an ester is advantageously a substantial excess over the amount needed to form the mono-acyl derivatives; for example, about four to six or more moles of the diamine are used for each mole of fatty acid residue in the ester.
- the ester of a triglyceride about 12 to 18 moles of ethylene diamine are advantageously used per mole of triglyceride.
- the reaction between the ethylen diamine and the ester of the fatty acid is advantageously carried out at temperatures of-about 80 to 100.
- the length of time for the reaction varies, depending upon the particular ester used in the reaction. It may take as much as four, five, or six hours before the reaction is complete.
- the fatty acid esters may be in the form of esters of monoor polyhydric alcohols such as, for example, methanol, ethanol, glycol, glycerol, etc.
- esters as methyl or ethyl laurate or myristate may be used-with advantage.
- esters as bayberry wax, palm kernel oil, or cocoanut oil may be used with advantage, all of these materials containing a major proportion of polyhydric alcohol esters of lauric and myristic acids.
- These mixed acyl derivatives will hereinafter be named by reference to the oil or fat from which the compound has been derived; thus the acyl derivative produced from bayber'ry wax and ethylene diamine will be called bayberry wax-ethylene diamine, etc.
- both mono-acyl ethylene diamines and 'di-acyl ethylene diamines are produced, the amount of the latter present in the reaction products being relatively small.
- the yield of the mono-acyl compound is about or higher, based on the ester, the remainder of the ester being converted to the di-acyl derivative.
- the process of the invention may advantageously be modified by adding to the initial reaction mixture a di-acyl derivative of ethylene diamine having the same acyl groups as in the mono-acyl derivatives which it is desired to produce.
- the amount of the di-acyl derivative added is substantially equal to that which would be produced in the reaction if no di-acyl derivative was added initially. If the process of the invention is carried out in this way the amount of di-acyl ethylene diamine produced in the reaction will be practically negligible, with the result that greater yields of the mono-acyl derivatives will be obtained.
- any suitable water-immiscible solvent for the monoacyl ethylene diamine may be used, such as, for example, ether, di-ethyl ether,l di-propyl ether, butyl ether, benzene, toluene, xylene, chloroform, carbon di-sulphide, etc.
- the di-acyl ethylene diamines and the ethylene diamine are insoluble or so slightly soluble as not to interfere with the recovery of substantially pure mono-acyl ethylene diamines therefrom.
- EXAMPLE 1 Mono-lauroyl ethylene diamine One mole of methyl laurate is mixed with finely divided. Ether is then added and the mixture is thoroughly stirred. At this stage the mixture consists of a solid phase and two layers of liquid, one being an aqueous solution of ethylene diamine and the other an ether solution of monolauroyl ethylene diamine. The solid phase is filtered from the mixture and washed with ether. It consists of dilauroyl ethylene diamine having a melting point of 162-164" C. The filtrate is separated into the lighter'ether layer and the heavier ethylene diamine layer. The excess ethylene diamine is recovered from the latter by distillation. The ether layer on evaporation leaves mono-lauroyl ethylene diamine having a melting point of 51-52 C,
- EXAMPLE 2 Mono-muristoyl ethylene diamine
- One mole of methyl myristate and one-fifth mole of di-myristoyl ethylene diamine are mixed with about 5.6 moles of 70% ethylene diamine and stirred at 100 for about three hours.
- the resulting suspension of solid and viscous liquid is cooled with vigorous stirring to keep the solid finely divided.
- Isop'ropyl ether is then added and the mixture is thoroughly stirred.
- the dimyristoyl ethylene diamine in the reaction product is separated from the reaction mixture by filtration and washed with isopropyl ether.
- the amount of di-myristoyl ethylene diamine recovered is only slightly greater than the onefifth mole originally introduced into the reaction mixture.
- the isopropyl ether layer of the reaction mixture containing the mono-myrlstoyl ethylene diamine upon evaporation to dryness ields mono-myristoyl ethylene diamine having a melting point of 62 C.
- the excess ethylene diamine in the water layer is recovered by distillation.
- the mono-lauroyl and mono-myristoyl ethylene diamines may be readily converted into salts such as the hydrochloride salts by dissolving them in ether and then subjecting them to the action of gaseous hydrogen chloride until no further separation of mono-lauroyl or mono-myrlstoyl ethylene diamine hydrochlorldes takes place.
- the salts may be separated by centrifuging at low temperature and are then dried in vacuo.
- Bayberry was ethylene diamine hydrochlovide 1000 grams oi bayberry wax and 2000 grams of 70% ethylene diamine are treated by the process described in Example 3, to yield a mixture 01' mono-acyl ethylene diamine hydrochlorides consisting principally of the hydrochlorides of monolauroyl ethylene diamine and monomyristoyl ethylene diamine.
- the bayberry wax ethylene diamine hydrochloride has a melting point of about 5055 C.
- the process of producing mono-acyl derivatives of ethylene diamine in which the acyl group contains from 12 to 14 carbon atoms which comprises heating an excess of ethylene diamine with an ester of a fatty acid containing from 12 to 14 carbon atoms and a di-acyl ethylene diamine in which the acyl groups are the same as the acyl group in the mono-acyl derivative desired, treating the reaction mixture with a waterimmiscible solvent for the mono-acyl ethylene diamine, separating the water-immiscible solvent containing mono-acyl ethylene diamine dissolved therein from the reaction mixture, and evaporating the solvent to recover the mono-acyl ethylene diamine.
- the process of producing mixed mono-acyl derivatives of ethylene diamine in which a major proportion of the acyl groups contain from 12 to 14 carbon atoms which comprises heating an excess of ethylene diamine with a natural material of the group consisting of oils and waxes containing a major proportion of esters of fatty acids having from 12 to 14 carbon atoms, treating the reaction mixture with a water-immiscible solvent for the mixed mono-acyl ethylene diamines, separating the water-immiscible solvent containing the mixed mono-acyl ethylene diamines dissolved therein from the reaction mixture, and evaporating the solvent to recover the mixed mono-acyl ethylene diamines.
- the process of producing mono cocoanut oil fatty acid acyl derivative of ethylene diamine which comprises heating an excess of ethylene diamine with cocoanut oil, treating the reaction mixture with a water-immiscible solvent for the mono cocoanut oil fatty acid acyl derivative of ethylene diamine, separating the water-immiscible solvent containing the mono cocoanut oil fatty acid acyl derivative of ethylene diamine dissolved therein from the reaction mixture, and evaporatingthe solvent to recover the mono cocoanut oil fatty acid acyl derivative of ethylene diamine.
- the process of producing mono-bayberry wax fatty acid acyl derivative of ethylene diamine which comprises heating an excess of ethylene diamine with bayberry wax, treating the reaction mixture with a water-immiscible solvent for the mono-bayberry wax fatty acid acyl derivative of ethylene diamine, separating the water-immiscible solvent containing the mono-bayberry wax fatty acid acyl derivative of ethylene diamine dissolved therein from the reaction mixture, and evaporating the solvent to recover the mono-bayberry wax fatty acid acyl derivative of ethylene diamine.
Description
Patented Oct. 16, i945 MONO-ACYL E'IHYLENE DIAMINES Nathan Weiner, West Forest- Hills, N. Y., assignor to Bonneville, Limited,-New York, N. Y., a corporation of Delaware No Drawing. Application January 12, 1942,
Serial No. 426,487
8 Claims.
This invention relates to new derivatives of ethylene diamine and more particularly it relates to new mono-acyl derivatives of ethylene diamine. The invention includes new mono-acyl ethylene diamines as well as a new process for making these compounds.
The new compounds of the invention are monoacyl ethylene diamines containing from 12 to 14 carbon atoms in the acyl group and include monolauroyl and mono-myristoyl ethylene diamines. The invention also includes mixed mono-acyl ethylene diamines in which the acyl group is derived from the fatty acids obtainable from natural oils and waxes which contain a major proportion of fatty acids in the free or combined state having from 12 to 14 carbon atoms, such as, for example, the fatty acids obtainable from bayberry wax, palm kernel oil, and cocoanut oil.
The new mono-acyl ethylene diamines are solids of characteristic melting point, with strongly basic properties as exemplified by their ability to form characteristic amine hydrochlorides.
The invention also includes the salts of the aforementioned mono-acyl ethylene diamines, as well as a process by which'such salts may be advantageously prepared. Such salts may be prepared in accordance with the invention, by dissolving the mono-acyl ethylene diamine in a solvent in which the salt desired is substantially insoluble, e. g., ether, ispropyl ether, benzene, toluene, etc., and then treating the resulting solution of the mono-acyl ethylene diamine with a substantially anhydrous acid corresponding to the salt desired, e. g., hydrochloric, hydrobromic, ulphuric, etc., to produce the chlorides, bromides, sulphates, etc., respectively. These salts are water soluble and have very desirable surface activity characteristics. They may advantageously be used as emulsifying, detergent, wetting, dispersing, or flotation agents; and, in the form of the hydrochloride salts, they may be used with particular advantage as flotation agents in the froth flotation of potassium chloride ores or brines.
The new process of the invention by which the new mono-acyl ethylene diamine derivatives may be produced comprises heating an excess of ethylene diamine with an ester of a fatty acid containing from 12 to 14 carbon atoms, treating the reaction mixture with a water-immiscible solvent for the mono-acyl ethylene diamine, separating the water-immiscible solvent containing the mono-acyl ethylene diamine dissolved therein from the reaction mixture and evaporating the solvent to recover the mono-acyl ethylene diamine. l v
The amount of ethylene diamine reacted with a Q given quantity of an ester is advantageously a substantial excess over the amount needed to form the mono-acyl derivatives; for example, about four to six or more moles of the diamine are used for each mole of fatty acid residue in the ester. Thus, with the ester of a triglyceride about 12 to 18 moles of ethylene diamine are advantageously used per mole of triglyceride.
The reaction between the ethylen diamine and the ester of the fatty acid is advantageously carried out at temperatures of-about 80 to 100. The length of time for the reaction varies, depending upon the particular ester used in the reaction. It may take as much as four, five, or six hours before the reaction is complete.
The fatty acid esters may be in the form of esters of monoor polyhydric alcohols such as, for example, methanol, ethanol, glycol, glycerol, etc. Thus, for example, such esters as methyl or ethyl laurate or myristate may be used-with advantage. To produce acyl derivatives of ethylene diamine such esters as bayberry wax, palm kernel oil, or cocoanut oil may be used with advantage, all of these materials containing a major proportion of polyhydric alcohol esters of lauric and myristic acids. These mixed acyl derivatives will hereinafter be named by reference to the oil or fat from which the compound has been derived; thus the acyl derivative produced from bayber'ry wax and ethylene diamine will be called bayberry wax-ethylene diamine, etc.
In carrying out the process of .the invention both mono-acyl ethylene diamines and 'di-acyl ethylene diamines are produced, the amount of the latter present in the reaction products being relatively small. In general, the yield of the mono-acyl compound is about or higher, based on the ester, the remainder of the ester being converted to the di-acyl derivative. To decrease the amount of di-acyl derivatives formed, the process of the invention may advantageously be modified by adding to the initial reaction mixture a di-acyl derivative of ethylene diamine having the same acyl groups as in the mono-acyl derivatives which it is desired to produce. Advantageously the amount of the di-acyl derivative added is substantially equal to that which would be produced in the reaction if no di-acyl derivative was added initially. If the process of the invention is carried out in this way the amount of di-acyl ethylene diamine produced in the reaction will be practically negligible, with the result that greater yields of the mono-acyl derivatives will be obtained.
In practicing the process of the invention any suitable water-immiscible solvent for the monoacyl ethylene diamine may be used, such as, for example, ether, di-ethyl ether,l di-propyl ether, butyl ether, benzene, toluene, xylene, chloroform, carbon di-sulphide, etc. In these solvents, the di-acyl ethylene diamines and the ethylene diamine are insoluble or so slightly soluble as not to interfere with the recovery of substantially pure mono-acyl ethylene diamines therefrom.
The new process of the invention will be illustrated by the following examples, but it is not limited thereto.
EXAMPLE 1 Mono-lauroyl ethylene diamine One mole of methyl laurate is mixed with finely divided. Ether is then added and the mixture is thoroughly stirred. At this stage the mixture consists of a solid phase and two layers of liquid, one being an aqueous solution of ethylene diamine and the other an ether solution of monolauroyl ethylene diamine. The solid phase is filtered from the mixture and washed with ether. It consists of dilauroyl ethylene diamine having a melting point of 162-164" C. The filtrate is separated into the lighter'ether layer and the heavier ethylene diamine layer. The excess ethylene diamine is recovered from the latter by distillation. The ether layer on evaporation leaves mono-lauroyl ethylene diamine having a melting point of 51-52 C,
EXAMPLE 2 Mono-muristoyl ethylene diamine One mole of methyl myristate and one-fifth mole of di-myristoyl ethylene diamine are mixed with about 5.6 moles of 70% ethylene diamine and stirred at 100 for about three hours. The resulting suspension of solid and viscous liquid is cooled with vigorous stirring to keep the solid finely divided. Isop'ropyl ether is then added and the mixture is thoroughly stirred. The dimyristoyl ethylene diamine in the reaction product is separated from the reaction mixture by filtration and washed with isopropyl ether. The amount of di-myristoyl ethylene diamine recovered is only slightly greater than the onefifth mole originally introduced into the reaction mixture. The isopropyl ether layer of the reaction mixture containing the mono-myrlstoyl ethylene diamine upon evaporation to dryness ields mono-myristoyl ethylene diamine having a melting point of 62 C. The excess ethylene diamine in the water layer is recovered by distillation.
The mono-lauroyl and mono-myristoyl ethylene diamines may be readily converted into salts such as the hydrochloride salts by dissolving them in ether and then subjecting them to the action of gaseous hydrogen chloride until no further separation of mono-lauroyl or mono-myrlstoyl ethylene diamine hydrochlorldes takes place. The salts may be separated by centrifuging at low temperature and are then dried in vacuo.
The preparation of mixed mono-acyl derivatives containing acyl groups of from 12 to 14 carbon atoms is i1lustrated by the following examples EXAMPLE 3 Cocoanut oil ethylene diamine hydrochloride About 1000 grams of cocoanut oil and 2000 grams of 70% ethylene diamine are stirred together vigorously at about C. for about five hours. The resulting almost homogeneous mixture is cooled to about 50 C. Enough ether to give about 10 liters of solution is then added and the solution further cooled to room temperature. The insoluble slush of di-acyl ethylene diamines is then separated by filtration. The ether-1m soluble layer of the filtrate is separated from the ether layer which is then concentrated to about 4 liters. Dry hydrogen chloride gas is then passed through the ether solution until the separation of mixed mono-acyl ethylene diamine EXAMPLE 4 Palm kenwl oil ethylene diamine hydrochloride Exmu: 5.
Bayberry was ethylene diamine hydrochlovide 1000 grams oi bayberry wax and 2000 grams of 70% ethylene diamine are treated by the process described in Example 3, to yield a mixture 01' mono-acyl ethylene diamine hydrochlorides consisting principally of the hydrochlorides of monolauroyl ethylene diamine and monomyristoyl ethylene diamine. The bayberry wax ethylene diamine hydrochloride has a melting point of about 5055 C.
In Examples 3 to 5 inclusive, instead of producing the hydrochlorides the various acyl ethylene diamines may be recovered from the water-immiscible solvent, e. 8., ether, by evaporation, as in Examples 1 and 2, without conversion into hydrochlorides.
Iclaim:
1. The process of producing mono-acyl derivatives of ethylene diamine in which the acyl 'group contains from 12 to 14 carbon atoms, which comprises heating an excess of ethylene diamine with an ester of a fatty acid containing from 12 to 14 carbon atoms, treating the reaction mixture with a water-immiscible solvent for the monoacyl ethylene diamine, separating the water-immiscible solvent containing mono-acyl ethylene diamine dissolved therein from the reaction mixture, and evaporating the solvent to recover the mono-acyl ethylene diamine.
2. The process of producing mono-acyl derivatives of ethylene diamine in which the acyl group contains from 12 to 14 carbon atoms, which comprises heating an excess of ethylene diamine with an ester of a fatty acid containing from 12 to 14 carbon atoms and a di-acyl ethylene diamine in which the acyl groups are the same as the acyl group in the mono-acyl derivative desired, treating the reaction mixture with a waterimmiscible solvent for the mono-acyl ethylene diamine, separating the water-immiscible solvent containing mono-acyl ethylene diamine dissolved therein from the reaction mixture, and evaporating the solvent to recover the mono-acyl ethylene diamine.
3. The process of producing lauroyl ethylene diamine which comprises heating an excess of ethylene diamine with methyl laurate, treating the reaction mixture with a water-immiscible solvent for the mono-lauroyl ethylene diamine, separating the water-immiscible solvent containing mono-lauroyl ethylene diamine dissolved therein from the reaction mixture and evaporating the solvent to recover the mono-acyl ethylene diamine. i
4. The process of producing myristoylethylene diamine which comprises heating an excess of ethylene diamine with methyl myristate, treating the reaction mixture with a water-immiscible solvent for the mono-myristoyl ethylene diamine,
separating the water-immiscible solvent containing mono-myristoyl ethylene diamine dissolved therein from the reaction mixture and evaporating the solvent to recover the mono-acyl ethylene diamine.
5. The process of producing mixed mono-acyl derivatives of ethylene diamine in which a major proportion of the acyl groups contain from 12 to 14 carbon atoms, which comprises heating an excess of ethylene diamine with a natural material of the group consisting of oils and waxes containing a major proportion of esters of fatty acids having from 12 to 14 carbon atoms, treating the reaction mixture with a water-immiscible solvent for the mixed mono-acyl ethylene diamines, separating the water-immiscible solvent containing the mixed mono-acyl ethylene diamines dissolved therein from the reaction mixture, and evaporating the solvent to recover the mixed mono-acyl ethylene diamines.
6. The process of producing mono cocoanut oil fatty acid acyl derivative of ethylene diamine which comprises heating an excess of ethylene diamine with cocoanut oil, treating the reaction mixture with a water-immiscible solvent for the mono cocoanut oil fatty acid acyl derivative of ethylene diamine, separating the water-immiscible solvent containing the mono cocoanut oil fatty acid acyl derivative of ethylene diamine dissolved therein from the reaction mixture, and evaporatingthe solvent to recover the mono cocoanut oil fatty acid acyl derivative of ethylene diamine.
'7. The process of producing mono-bayberry wax fatty acid acyl derivative of ethylene diamine which comprises heating an excess of ethylene diamine with bayberry wax, treating the reaction mixture with a water-immiscible solvent for the mono-bayberry wax fatty acid acyl derivative of ethylene diamine, separating the water-immiscible solvent containing the mono-bayberry wax fatty acid acyl derivative of ethylene diamine dissolved therein from the reaction mixture, and evaporating the solvent to recover the mono-bayberry wax fatty acid acyl derivative of ethylene diamine.
8. The process of producing mono-palm kernel oil-fatty acid acyl derivative of ethylene diamine which comprises heating an excess of ethylene di-. amine with palm kernel oil, treating the reaction mixture with a water-immiscible solvent for the mono-palm kernel oil fatty acid acyl derivative of ethylene diamine, separating th water-immiscible solvent containing the mono-palm kernel oil fatty acid acyl derivative of ethylene diamine dissolved therein from the reaction mixture, and evaporating the solvent to recover the mono-palm kernel oil fatty acid acyl derivative of ethylene diamine.
' NATHAN WEINER.
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| US426487A US2387201A (en) | 1942-01-12 | 1942-01-12 | Mono-acyl ethylene diamines |
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| US426487A US2387201A (en) | 1942-01-12 | 1942-01-12 | Mono-acyl ethylene diamines |
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Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2602805A (en) * | 1947-09-08 | 1952-07-08 | Colgate Palmolive Peet Co | Process of purifying amino compounds and co2 addition product produced thereby |
| US2609931A (en) * | 1948-04-17 | 1952-09-09 | Fram Corp | Method of filtering |
| US2996464A (en) * | 1958-01-20 | 1961-08-15 | Spencer Kellogg And Sons Inc | Thixotropic oil vehicle |
| US2996396A (en) * | 1957-12-11 | 1961-08-15 | Spencer Kellogg And Sons Inc | Thixotropic oil vehicle |
| US3424771A (en) * | 1967-07-11 | 1969-01-28 | Lumin Chem Co | Novel amido derivatives useful as aids in detergent compositions |
| EP0164205A1 (en) * | 1984-04-26 | 1985-12-11 | Johnson & Johnson Baby Products Company | Process for the preparation of monoacyl (poly)alkylene polyamines |
| US4789392A (en) * | 1984-09-13 | 1988-12-06 | The Dow Chemical Company | Froth flotation method |
| US4797202A (en) * | 1984-09-13 | 1989-01-10 | The Dow Chemical Company | Froth flotation method |
| US4822483A (en) * | 1984-09-13 | 1989-04-18 | The Dow Chemical Company | Collector compositions for the froth flotation of mineral values |
| US20100166867A1 (en) * | 2008-11-19 | 2010-07-01 | Adocia | Novel administration form of osteogenic protein complexes |
| US20110014189A1 (en) * | 2008-12-23 | 2011-01-20 | Adocia | Stable pharmaceutical composition comprising at least one monoclonal antibody and at least one amphiphilic polysaccharide comprising hydrophobic substituents |
| WO2011061615A1 (en) | 2009-11-19 | 2011-05-26 | Adocia | Polysaccharide / bmp complexes which are soluble at physiological ph |
| WO2011077405A1 (en) | 2009-12-23 | 2011-06-30 | Adocia | Anionic polysaccharides functionalised by a hydrophobic acid derivative |
| US20110195913A1 (en) * | 2010-02-09 | 2011-08-11 | Adocia | Anionic polysaccharides functionalized by at least two hydrophobic groups carried by an at least trivalent spacer |
| WO2011098962A2 (en) | 2010-02-09 | 2011-08-18 | Adocia | Anionic polysaccharides functionalised by at least two hydrophobic groups supported by an at least trivalent spacer |
| WO2013021143A1 (en) | 2011-08-10 | 2013-02-14 | Adocia | Injectable solution of at least one type of basal insulin |
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| US9198971B2 (en) | 2012-01-09 | 2015-12-01 | Adocia | Injectable solution at pH 7 comprising at least one basal insulin the pI of which is between 5.8 and 8.5 and a substituted co-polyamino acid |
| US9492467B2 (en) | 2011-11-02 | 2016-11-15 | Adocia | Rapid-acting insulin formulation comprising an oligosaccharide |
| US9700599B2 (en) | 2012-11-13 | 2017-07-11 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
| US9795678B2 (en) | 2014-05-14 | 2017-10-24 | Adocia | Fast-acting insulin composition comprising a substituted anionic compound and a polyanionic compound |
| US10449256B2 (en) | 2013-02-12 | 2019-10-22 | Adocia | Injectable solution at pH 7 comprising at least one basal insulin the isoelectric point of which is between 5.8 and 8.5 and a hydrophobized anionic polymer |
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1942
- 1942-01-12 US US426487A patent/US2387201A/en not_active Expired - Lifetime
Cited By (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2602805A (en) * | 1947-09-08 | 1952-07-08 | Colgate Palmolive Peet Co | Process of purifying amino compounds and co2 addition product produced thereby |
| US2609931A (en) * | 1948-04-17 | 1952-09-09 | Fram Corp | Method of filtering |
| US2996396A (en) * | 1957-12-11 | 1961-08-15 | Spencer Kellogg And Sons Inc | Thixotropic oil vehicle |
| US2996464A (en) * | 1958-01-20 | 1961-08-15 | Spencer Kellogg And Sons Inc | Thixotropic oil vehicle |
| US3424771A (en) * | 1967-07-11 | 1969-01-28 | Lumin Chem Co | Novel amido derivatives useful as aids in detergent compositions |
| EP0164205A1 (en) * | 1984-04-26 | 1985-12-11 | Johnson & Johnson Baby Products Company | Process for the preparation of monoacyl (poly)alkylene polyamines |
| US4789392A (en) * | 1984-09-13 | 1988-12-06 | The Dow Chemical Company | Froth flotation method |
| US4797202A (en) * | 1984-09-13 | 1989-01-10 | The Dow Chemical Company | Froth flotation method |
| US4822483A (en) * | 1984-09-13 | 1989-04-18 | The Dow Chemical Company | Collector compositions for the froth flotation of mineral values |
| US8546356B2 (en) | 2008-11-19 | 2013-10-01 | Adocia | Administration form of osteogenic protein complexes |
| US20100166867A1 (en) * | 2008-11-19 | 2010-07-01 | Adocia | Novel administration form of osteogenic protein complexes |
| US20110014189A1 (en) * | 2008-12-23 | 2011-01-20 | Adocia | Stable pharmaceutical composition comprising at least one monoclonal antibody and at least one amphiphilic polysaccharide comprising hydrophobic substituents |
| WO2011061615A1 (en) | 2009-11-19 | 2011-05-26 | Adocia | Polysaccharide / bmp complexes which are soluble at physiological ph |
| US20110178011A1 (en) * | 2009-11-19 | 2011-07-21 | Adocia | Polysaccharide/BMP complexes which are soluble at physiological pH |
| WO2011077405A1 (en) | 2009-12-23 | 2011-06-30 | Adocia | Anionic polysaccharides functionalised by a hydrophobic acid derivative |
| US20110172166A1 (en) * | 2009-12-23 | 2011-07-14 | Adocia | Anionic polysaccharides functionalized by a hydrophobic acid derivative |
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| US9115218B2 (en) | 2010-02-09 | 2015-08-25 | Adocia | Anionic polysaccharides functionalized by at least two hydrophobic groups carried by an at least trivalent spacer |
| US20110195913A1 (en) * | 2010-02-09 | 2011-08-11 | Adocia | Anionic polysaccharides functionalized by at least two hydrophobic groups carried by an at least trivalent spacer |
| WO2011098962A2 (en) | 2010-02-09 | 2011-08-18 | Adocia | Anionic polysaccharides functionalised by at least two hydrophobic groups supported by an at least trivalent spacer |
| WO2013021143A1 (en) | 2011-08-10 | 2013-02-14 | Adocia | Injectable solution of at least one type of basal insulin |
| US9089476B2 (en) | 2011-08-10 | 2015-07-28 | Adocia | Injectable solution at pH 7 comprising at least one basal insulin whose PI is between 5.8 and 8.5 |
| EP3053590A1 (en) | 2011-08-10 | 2016-08-10 | Adocia | Injectable solution of at least one type of basal insulin |
| US9492467B2 (en) | 2011-11-02 | 2016-11-15 | Adocia | Rapid-acting insulin formulation comprising an oligosaccharide |
| US10335489B2 (en) | 2012-01-09 | 2019-07-02 | Adocia | Injectable solution at pH 7 comprising at least one basal insulin the pi of which is between 5.8 and 8.5 and a substituted co-polyamino acid |
| US9198971B2 (en) | 2012-01-09 | 2015-12-01 | Adocia | Injectable solution at pH 7 comprising at least one basal insulin the pI of which is between 5.8 and 8.5 and a substituted co-polyamino acid |
| US10583175B2 (en) | 2012-11-13 | 2020-03-10 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
| US9700599B2 (en) | 2012-11-13 | 2017-07-11 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
| WO2014076422A1 (en) | 2012-11-13 | 2014-05-22 | Adocia | Substituted anionic compounds consisting of a backbone consisting of a discrete number of saccharide units |
| US10646551B2 (en) | 2012-11-13 | 2020-05-12 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
| US10881716B2 (en) | 2012-11-13 | 2021-01-05 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
| US11324808B2 (en) | 2012-11-13 | 2022-05-10 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
| US10449256B2 (en) | 2013-02-12 | 2019-10-22 | Adocia | Injectable solution at pH 7 comprising at least one basal insulin the isoelectric point of which is between 5.8 and 8.5 and a hydrophobized anionic polymer |
| WO2014124993A1 (en) | 2013-02-12 | 2014-08-21 | Adocia | Injectable solution at ph 7 comprising at least one basal insulin having an isoelectric point of between 5.8 and 8.5, and a hydrophobised anionic polymer |
| US9795678B2 (en) | 2014-05-14 | 2017-10-24 | Adocia | Fast-acting insulin composition comprising a substituted anionic compound and a polyanionic compound |
| US10525133B2 (en) | 2014-05-14 | 2020-01-07 | Adocia | Aqueous composition comprising at least one protein and one solubilizing agent, preparation thereof and uses thereof |
| US10792335B2 (en) | 2015-11-16 | 2020-10-06 | Adocia | Rapid-acting insulin composition comprising a substituted citrate |
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