US2816920A - Production of zwitterion of detergent amino acids - Google Patents
Production of zwitterion of detergent amino acids Download PDFInfo
- Publication number
- US2816920A US2816920A US527861A US52786155A US2816920A US 2816920 A US2816920 A US 2816920A US 527861 A US527861 A US 527861A US 52786155 A US52786155 A US 52786155A US 2816920 A US2816920 A US 2816920A
- Authority
- US
- United States
- Prior art keywords
- zwitterion
- detergent
- amino acids
- phase
- production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000001413 amino acids Chemical class 0.000 title description 9
- 239000003599 detergent Substances 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000002253 acid Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- -1 ALKALI METAL SALT Chemical class 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical class [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000012074 organic phase Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- REQSRTKARPEAIW-TVPGTPATSA-N (Z)-2-(dodecylamino)but-2-enoic acid Chemical compound C(CCCCCCCCCCC)N/C(/C(=O)O)=C\C REQSRTKARPEAIW-TVPGTPATSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAOHKACVOFGZOI-UHFFFAOYSA-N Fominoben hydrochloride Chemical compound [Cl-].ClC=1C=CC=C(NC(=O)C=2C=CC=CC=2)C=1CN(C)CC(=O)[NH+]1CCOCC1 ZAOHKACVOFGZOI-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000012550 audit Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229960004594 fominoben Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- TXBCHPGETQLSGV-UHFFFAOYSA-M sodium;2-(dodecylamino)propanoate Chemical compound [Na+].CCCCCCCCCCCCNC(C)C([O-])=O TXBCHPGETQLSGV-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
Definitions
- Detergent materials of the above formula are frequently made in the form of the sodium or potassium salts and are frequently the hydrolysis products of the corresponding esters or nitriles.
- the sodium salt of compounds of this type is generally quite alkaline in reaction.
- sodium dodecylaminopropionate in a 10% aqueous solution has a pH in excess of 12. This is too alkaline for uses in which the material comes in contact with human skin as, for example, in the case of shampoos.
- Neutralization with mineral acid to an accept able pH level produces considerable inorganic salt. This inorganic salt frequently cannot be tolerated because of solubility and viscosity considerations.
- the zwitterion can be precipitated but in a semi-solid form which is extremely difficult to handle and to purify. Considerable inorganic salt and mineral acid are occluded within the semi-solid mass. The zwitterion thus produced is difiicult to obtain in a salt-free form because the physical form makes washing very tedious.
- an object of the present invention to provide a novel process of producing the zwitterion of the above detergent amino acids and of purifying the zwitterion by a simple series of operations.
- the upper phase comprises a 20-50% aqueous solution containing virtually all of the detergent material contaminated to a slight degree with sodium sulfate dissolved in the solution.
- This phase is a slightly viscous, clear and readily handled solution.
- the lower aqueous phase is a solution of sodium sulfate containing only a trace of the de- United States PateiitffO 2,816,920 PatentedDec. 17, 1957 tergent amino acid.
- the separation is rapid and com- "plete withsno emulsionrproblemsand yieldstapproximately 'sionetparta'of organic phase td';2+3:-:parts sofaaqueousji phase.
- This organic phase may be iused'trlirectly ifondhe: production of other salts of the amino acid where a slight amount of sodium sulfate ormther inorganic saltmay be tolerated. It is preferred, however,.to isolate thezwit- ".terion in.si1bstatitially; purejorm. ffThis mayreadily be accomplishedipyf addingthe organic phase slowly. to: a quantity of water 'ab'out2'3"times"that of the organic phase, while.;thewater is being well agitated. "The zwit- .teriori .i s ;.precipitated.as. alinely 'dividedfflocculent semisolid.
- sulfuric acid is the preferred acid in that it is less expensive, less corrosive, and requires less accurate control
- other known non-oxidizing mineral acids such as hydrochloric and phosphoric may also be used with essentially the same results.
- Example 1 A solution of 20.9 lbs. of sodium p-dodecylaminopropionate in 88 lbs. of water was prepared in .a 20 gallon autoclave equipped with an anchor stirrer. To this solution was added slowly and with agitation a solution of 5.2 lbs. of concentrated sulfuric acid in 15 lbs. of water to yield a mixture having a pH of approximately 4.0. Phase separation occurred almost immediately and, upon discontinuing the agitation, the organic phase floated to the top of the aqueous phase and the latter was separated by decantation, sampled for analysis and discarded. The upper organic phase weighed 50 lbs. and was Washed by pouring it in the form of a thin stream into 15 gallons of water under agitation.
- the organic phase was again permitted to float .and was separated by decantation.
- the organic phase was subjected to 2 additional washings with 10 gallons of water each.
- the wash waters were sampled for analysis and then discarded.
- the final product was approximately solids and had an ash content of less than 0.5%.
- the following table gives the analyses of the original aqueous phase and the various wash waters.
- Example 2 Solution Percent Percent Percent Percent loss solids ash organic
- Example 2 The process of Example 1 was repeated with fl,fi'-dodecylaminobispropionate. The zwitterion was obtained in essen y t e S as reported in Example '1.
- Example I The process of Example'l'was carried out substituting .an equivalent quantity of hydrochlaric acid for the sulacid. The results obtained were'essentiallythe same.
- R is an' aliphatichydrocarbon group containing from 8- 22'carbon atoms
- R' is selected from the group consisting of hydrogen and'methyl
- m is not greater than .1 audit is at least 1 and not more than Z'but is 1 when R is CH and the sum of m and his equal to 2
- Me is alkali metal which comprises" adding a] nonoxidizing mineral acid to an aqueous solution of said alkali metal salt to produce a pH within the rangejof'3.5 to' 5.5 while agitating the solution, discontinuing theagitation to per- 25 mit the precipitated zwitterion thus formed to separate as an aqueous solution in the form of'a' distinct phase and separating the zwi-tterion phase.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
PRODUCTION OF ZWITTERION OFsDETERGENT .AMINO ACIDS ...DonaldtLitAndersen,.Minneapolis, Minn., assignorto "General'Mills,"Inc., a corporation of Delaware No Drawing. .-Applicaflon-August 11, 1955 Serial No." 527,861
6 Claims. (Cl. 260-534) The present invention relates to the production of the zwitteriotljfromi the: salts 10f." ceirtaint detergent: amino acids apresent invention -isdirected are those having*=the-.-foli lowing formula:
"-in*which R- is an aliphatic" hydrocarbon;group-containing from 8-22 carbon atoms and is de'rivdfronradetergent forming fatty acid, R is H or CH Me is alkali metal, m is or 1, n is 1 or 2 but 1 when R is CH;, and the sum of m and n is 2.
Detergent materials of the above formula are frequently made in the form of the sodium or potassium salts and are frequently the hydrolysis products of the corresponding esters or nitriles. The sodium salt of compounds of this type is generally quite alkaline in reaction. For example, sodium dodecylaminopropionate in a 10% aqueous solution has a pH in excess of 12. This is too alkaline for uses in which the material comes in contact with human skin as, for example, in the case of shampoos. Neutralization with mineral acid to an accept able pH level produces considerable inorganic salt. This inorganic salt frequently cannot be tolerated because of solubility and viscosity considerations.
For these reasons it is frequently desirable to convert the sodium or potassium salt to some other more desir able salt and for this purpose the free acid form of the compound is a desirable starting material.
When an excess of mineral acid is added to solutions of the sodium salts of the above detergent amino acids, the zwitterion can be precipitated but in a semi-solid form which is extremely difficult to handle and to purify. Considerable inorganic salt and mineral acid are occluded within the semi-solid mass. The zwitterion thus produced is difiicult to obtain in a salt-free form because the physical form makes washing very tedious.
It has now been discovered that the zwitterion of the detergent amino acids can readily be obtained and purified by a unique procedure.
It is, therefore, an object of the present invention to provide a novel process of producing the zwitterion of the above detergent amino acids and of purifying the zwitterion by a simple series of operations.
It has been discovered that by a careful neutralization of a 10-30% aqueous solution of an alkali metal salt of a detergent amino acid of the above type, by means of sulfuric acid to a pH within the range of 3.5 to 5.5, there results a rapid and complete separation of the reaction mixture into 2 phases. The upper phase comprises a 20-50% aqueous solution containing virtually all of the detergent material contaminated to a slight degree with sodium sulfate dissolved in the solution. This phase is a slightly viscous, clear and readily handled solution. The lower aqueous phase is a solution of sodium sulfate containing only a trace of the de- United States PateiitffO 2,816,920 PatentedDec. 17, 1957 tergent amino acid. The separation is rapid and com- "plete withsno emulsionrproblemsand yieldstapproximately 'sionetparta'of organic phase td';2+3:-:parts sofaaqueousji phase.
This organic phase may be iused'trlirectly ifondhe: production of other salts of the amino acid where a slight amount of sodium sulfate ormther inorganic saltmay be tolerated. It is preferred, however,.to isolate thezwit- ".terion in.si1bstatitially; purejorm. ffThis mayreadily be accomplishedipyf addingthe organic phase slowly. to: a quantity of water 'ab'out2'3"times"that of the organic phase, while.;thewater is being well agitated. "The zwit- .teriori .i s ;.precipitated.as. alinely 'dividedfflocculent semisolid. "The particles 'bf'Tthis' floccillent 'clispersion" remain suspended 'asll'orig as a'gitation' is continued. .When jagiytaltionli is discontinued, the; particles float; to "the. surface "asia fairly compact mass. LTheexcess water may. bedecant'd..afid.the compact, mass may'j be mesu'spefiddQ-in a dde'd wash water. byjsimple agitation. Washing and sfdecaritingmayibe repe'atedanynumber bf times toyield .a;pro"duct which is s'ubstaritiallylfree. fromlinorgahic s'alts, Without. any (significant loss. or. the. zwitterion. '-A .total of 3,. such twa'shings isusually .sjfifiicien't .to.-leech,.out.-i1irtually all oflthe inorganic-salt. "Upon. completion ofjthe washing; the zwitterion maybelseparated.by'idecantation after which residual amounts "of" free water may' be removed by kneading or pressing. As an alternative, the residual water may be removed by melting the zwitterion and then decanting any free water. The resultant prodnot in either event is a gelatinous solid containing approximately 35% water, and is insoluble in water but soluble in alkaline materials.
While sulfuric acid is the preferred acid in that it is less expensive, less corrosive, and requires less accurate control, other known non-oxidizing mineral acids such as hydrochloric and phosphoric may also be used with essentially the same results.
Example 1 A solution of 20.9 lbs. of sodium p-dodecylaminopropionate in 88 lbs. of water was prepared in .a 20 gallon autoclave equipped with an anchor stirrer. To this solution was added slowly and with agitation a solution of 5.2 lbs. of concentrated sulfuric acid in 15 lbs. of water to yield a mixture having a pH of approximately 4.0. Phase separation occurred almost immediately and, upon discontinuing the agitation, the organic phase floated to the top of the aqueous phase and the latter was separated by decantation, sampled for analysis and discarded. The upper organic phase weighed 50 lbs. and was Washed by pouring it in the form of a thin stream into 15 gallons of water under agitation. The organic phase was again permitted to float .and was separated by decantation. The organic phase was subjected to 2 additional washings with 10 gallons of water each. The wash waters were sampled for analysis and then discarded. The final product was approximately solids and had an ash content of less than 0.5%. The following table gives the analyses of the original aqueous phase and the various wash waters.
Solution Percent Percent Percent loss solids ash organic Example 2 The process of Example 1 was repeated with fl,fi'-dodecylaminobispropionate. The zwitterion was obtained in essen y t e S as reported in Example '1.
r -"x A H. A
field and purity tor the zwitterion reported in Example 1,
1 process of Example 1' was repeated: on
dodecylaminocrotonate with essentially the same results Example I The process of Example'l'was carried out substituting .an equivalent quantity of hydrochlaric acid for the sulacid. The results obtained were'essentiallythe same.
I claim as my invention:
1.'Process of prep'armg a zwitterion of acornpound "having the formula RNHMCHRCHfiOOMeL, in
' which R is an' aliphatichydrocarbon group containing from 8- 22'carbon atoms,' R' is selected from the group consisting of hydrogen and'methyl, m is not greater than .1 audit is at least 1 and not more than Z'but is 1 when R is CH and the sum of m and his equal to 2 and Me is alkali metal which comprises" adding a] nonoxidizing mineral acid to an aqueous solution of said alkali metal salt to produce a pH within the rangejof'3.5 to' 5.5 while agitating the solution, discontinuing theagitation to per- 25 mit the precipitated zwitterion thus formed to separate as an aqueous solution in the form of'a' distinct phase and separating the zwi-tterion phase.
2. A process according to claim lin which the mineral acid is sulfuric acid.
3. A process according to claim 1 in which the separated zwitterion is further purified by dispersing the zwitterion 5 in water with agitation, discontinuing the agitation and 2,605,284 Hess July 29, 1952 2,617,823 Wolff et a1 Nov. 11, 1952 2,683,739 Weidman July 13, 1954 OTHER REFERENCES Degering, An Outline of Organic Nitrogen Compounds (1945), page 23 1. i
Claims (1)
1. PROCESS OF PREPARING A ZWITTERION OF A COMPOUND HAVING THE FORMULA RNHM(CHRCH2COOME)N IN WHICH R IS AN ALIPHATIC HYDROCARBON GROUP CONTAINING FROM 8-22 CARBON ATOMS, R'' IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND METHYL M IS NOT GREATER THAN 1 AND N IS AT LEAST 1 AND NOT MORE THAN 2 BUT IS 1 WHEN R'' IS CH3 AND THE SUM OF M AND N IS EQUAL TO 2 AND ME IS ALKALI METAL WHICH COMPRISES ADDING A NONOXIDIZING MINERAL ACID TO AN AQUEOUS SOLUTION OF SAID ALKALI METAL SALT TO PRODUCE A PH WITHIN THE RANGE OF 3.5 TO 5.5 WHILE AGITATING THE SOLUTION, DISCONTINUING THE AGITATION TO PERMIT THE PRECIPITATED ZWITTERION THUS FORMED TO SEPARATE AS AN AQUEOUS SOLUTION IN THE FORM OF A DISTINCT PHASE AND SEPARATING THE ZWITTERION PHASE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US527861A US2816920A (en) | 1955-08-11 | 1955-08-11 | Production of zwitterion of detergent amino acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US527861A US2816920A (en) | 1955-08-11 | 1955-08-11 | Production of zwitterion of detergent amino acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2816920A true US2816920A (en) | 1957-12-17 |
Family
ID=24103233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US527861A Expired - Lifetime US2816920A (en) | 1955-08-11 | 1955-08-11 | Production of zwitterion of detergent amino acids |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2816920A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2993071A (en) * | 1959-03-10 | 1961-07-18 | Gen Mills Inc | Purification of salts of detergent amino acids |
| US3142568A (en) * | 1961-03-13 | 1964-07-28 | Du Pont | Photographic emulsions, elements, and processes |
| US3250784A (en) * | 1963-12-23 | 1966-05-10 | Gen Aniline & Film Corp | Pyrrolidonyl-gamma-butyramide and process of preparing |
| US3300338A (en) * | 1964-02-20 | 1967-01-24 | Martin L Fein | Process for treating washable leather |
| US3341460A (en) * | 1963-07-15 | 1967-09-12 | Colgate Palmolive Co | Shampoo composition |
| US3725473A (en) * | 1969-11-28 | 1973-04-03 | Colgate Palmolive Co | N-(2-hydroxyhydrocarbonyl) iminodicarboxylates |
| US4258063A (en) * | 1978-06-23 | 1981-03-24 | Henkel Corporation | Self-emulsifying cosmetic base |
| US5597513A (en) * | 1990-05-15 | 1997-01-28 | Cohen; Elliot | Demulsifier composition and method of use |
| US5922909A (en) * | 1998-03-31 | 1999-07-13 | Akzo Nobel Nv | Process for the selective control of Zwitterionic amphoteric compositions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2605284A (en) * | 1946-09-09 | 1952-07-29 | Stuart Company | Process of separating crystalline amino acids mixtures from natural proteins |
| US2617823A (en) * | 1949-02-16 | 1952-11-11 | Staley Mfg Co A E | Isolation of amino acids |
| US2683739A (en) * | 1952-03-03 | 1954-07-13 | Int Minerals & Chem Corp | Process for the crystallization of l-glutamic acid |
-
1955
- 1955-08-11 US US527861A patent/US2816920A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2605284A (en) * | 1946-09-09 | 1952-07-29 | Stuart Company | Process of separating crystalline amino acids mixtures from natural proteins |
| US2617823A (en) * | 1949-02-16 | 1952-11-11 | Staley Mfg Co A E | Isolation of amino acids |
| US2683739A (en) * | 1952-03-03 | 1954-07-13 | Int Minerals & Chem Corp | Process for the crystallization of l-glutamic acid |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2993071A (en) * | 1959-03-10 | 1961-07-18 | Gen Mills Inc | Purification of salts of detergent amino acids |
| US3142568A (en) * | 1961-03-13 | 1964-07-28 | Du Pont | Photographic emulsions, elements, and processes |
| US3341460A (en) * | 1963-07-15 | 1967-09-12 | Colgate Palmolive Co | Shampoo composition |
| US3250784A (en) * | 1963-12-23 | 1966-05-10 | Gen Aniline & Film Corp | Pyrrolidonyl-gamma-butyramide and process of preparing |
| US3300338A (en) * | 1964-02-20 | 1967-01-24 | Martin L Fein | Process for treating washable leather |
| US3725473A (en) * | 1969-11-28 | 1973-04-03 | Colgate Palmolive Co | N-(2-hydroxyhydrocarbonyl) iminodicarboxylates |
| US4258063A (en) * | 1978-06-23 | 1981-03-24 | Henkel Corporation | Self-emulsifying cosmetic base |
| US5597513A (en) * | 1990-05-15 | 1997-01-28 | Cohen; Elliot | Demulsifier composition and method of use |
| US5922909A (en) * | 1998-03-31 | 1999-07-13 | Akzo Nobel Nv | Process for the selective control of Zwitterionic amphoteric compositions |
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