US2416052A - Stabilized soap - Google Patents

Stabilized soap Download PDF

Info

Publication number
US2416052A
US2416052A US583637A US58363745A US2416052A US 2416052 A US2416052 A US 2416052A US 583637 A US583637 A US 583637A US 58363745 A US58363745 A US 58363745A US 2416052 A US2416052 A US 2416052A
Authority
US
United States
Prior art keywords
soap
acid
mercaptopropionic
mercaptopropionic acid
salts
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
Application number
US583637A
Inventor
Myers F Gribbins
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US583637A priority Critical patent/US2416052A/en
Application granted granted Critical
Publication of US2416052A publication Critical patent/US2416052A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/32—Organic compounds, e.g. vitamins containing sulfur
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/045—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps containing substances which prevent the deterioration of soaps, e.g. light or heat stabilisers or antioxidants

Definitions

  • the present invention relates to stabilized soaps, to the manufacture of stabilized soap and soap products and especially stabilized soap and soap products made from ingredients, one or more of which ordinarily deteriorate or develop rancidity in a relatively short time and particularly to soap stabilization by substituted beta mercaptopropionic acid or its derivatives.
  • soaps tend to become rancid and discolor after storage. It is not definitely known just what causes the deterioration but it has been suggested that it may be due to oxidation or chemical decomposition. Such deterioration is highly objectionable as it renders the soaps unattractive by blanketing in many instances the perfumes of the soap discoloring it and/or leaving an objectionable rancid odor on the skin or the article being cleaned. Many attempts have been made to overcome this deterioration, the addition of various substances having been proposed to inhibit or retard it.
  • An object of the present invention is to provide stabilized soaps. Another object is to provide compounds to be incorporated in the salts of fatty acids Which will retard or inhibit their deterioration or prolong the period during which the salts are not rancid, which period is commonly referred to as the induction period, the salts so treated being free from the disadvantageous properties of compounds heretofore employed for this purpose. Still another object is to provide substituted beta mercaptopropionic acids and their esters as soap rancidity inhibitors. Other objects and advantages of the invention will appear hereinafter.
  • aryl groups phenyl, naphthyl, benzyl; and such groups as p methoxy phenyl, p hydroxy phenyl and cyclohexyl, which gives respectively:
  • HOOCCHzCHzSCHzCHaCHzOH 1. 3-methoxymethyl mercaptopropionic acid HOOCCHzCHzSCHzOCHs e. 3-methoxy'ethyl mercaptopropionic acid HOOCCHzCHzSCI-IzCI-IzOCI-Is f. 3-ethoxyethyl mercaptopropionic acid HOOCCHzCHzSCI-IzCHzOCzHs g.
  • Example-3 hydrozcyethyl mercaptopropionic acid preparation 2'7 parts (0.35M) mercapto glycol (HSCHzCHzOI-I) is added to 19 parts (0.35M) of acrylonitrile in the presence of 0.5 part piperidine.
  • the reaction mixture is topped to remove unreacted mat-erials and then heated in an excess of concentrated HCl ('75 parts) for 1 hour.
  • the by-product NH4C1 precipitates out and is removed by filtration. Excess HCl and H20 are removed by vacuum treatment.
  • a sulfur-hydrocarbon group such, e. g., as: mercaptoethyl, mercaptopropyl, mercaptobutyl, mercaptoisobutyl, mercaptohexyl and ethiaethyl, which gives respectively:
  • Ethiaethyl mercaptopropionic acid HOOCCH2CH2SCH2CH2SC2H5
  • the type reaction is identical to that indicated in Section 1. Specifically, it involves the addition of molar amounts of dimercaptans to acrylonitrile,'followed by acid or alkaline hydrolysis of the nitrile group.
  • a sulfurand oxygenated-hydrocarbon group such, e. g., as: Carboxyethiaethyl,
  • Solubility in water 20 0. very slightly soluble. Solubility in fat 20 0.: slightly soluble. Appearance: odorless white crystals.
  • Solubility in water 20 C. slightly soluble. Solubility in fat 20 0.: slightly soluble. Appearance: white crystals.
  • 'I'hesestabilizers may be incorporated in the soap in any suitable manner such, for example, as by simple mixing in proper proportions into the liquid or gel-like soap, by grinding, malaxing, or thoroughly and uniformly distributing it into the more or less solid soaps, the latter being subsequently formed'intc solid cakes or other shapes.
  • the stabilizers may be added at any convenient stage in the process of soap manufacture, care being exercised not to add it at a stage which will result in decomposition, leaching, or deterioration of the stabilizing agent. If desired, for example, these agents may be added during the well known crutching operation.
  • the stabilizers may be present in the soap to the extent of as little a 0.005%.
  • the optimum amount to be used may be determined for any agent or mixture by preparing a series of compositions containing selected amounts for example from 0.005% to say 5% of the agent or mixture such as 0.001, 0.01, 0.1, 1.0, 2.5, and 5% or a more comprehensive memori with smaller diiferentials if desired, placing these compositions under controlled storage conditions for the number of days the composition is to be maintained in the stabilized state.
  • the composition that contains the minimum amount of stabilizing agent is the amount that should be used to stabilize the soap for the selected period. Amounts ranging from .01 to about 2% give excellent stability to the soap.
  • the stabilizers may be used in soaps generally for there are few if any that do not require some stabilization.
  • the strong laundry soaps rancidify leaving undesirable odors.
  • the delicate, more highly purified facial soaps likewise rancidify to destroy the perfume used.
  • the soaps that can be stabilized by these agents are included the alkali metal and alkaline earth metal as well as the heavy metal salts of the higher fatty acids and mixtures of salts of such acid and complex alcohols obtained by the saponiflcation of the marine, vegetable, and animal oils and fats.
  • the stabilizers are effective in watersoluble, water-insoluble and metallic soaps; the so-called mineral oil soaps, i.
  • soaps which are used without water as a coolant in the machine tool industries and with water in the form of an emulsion as a coolant for cutting tools and as an insecticide spray; and in cosmetics compositions generally containing soaps which are used in tooth pastes, faceand body creams, e c.
  • the surprising and unexpected stabilizing effect of the substituted beta mercaptopropionic acids and their derivatives is clearly demonstrated by the following tests.
  • the test involves the examination of soap with and without the stabilizer for color, peroxide value and odor. The color is determined by visual examination; the peroxide value as included in the Swift test (Oil and Soap 10, -109, 1933), and the odor by placing aliquot portions of the soap with and without stabilizer in stoppered flasks of equal size, storing them under a constant temperature of about 50 C. At the end of each day, the stopper was remove and any odor indicating rancidity noted. The soap was combined with the stabilizer by malaxing the soap at about room temperature with the stabilizer. Table I tabulates the result of observations.
  • the stabilizers described under the 5 groups and their equivalents may be used as the acid, ester or salt.
  • the esters may be included the methyl, ethyl N- and iso-propyl, N- and iso-butyl and the higher straight and branched chain alkyl esters as well as the alicyclic ester cyclohexyl.
  • the salts are included the alkali metal and alkaline earth metal salts and particularly the sodium, potassium, calcium and magnesium salts.
  • Soap stabilized against rancidity b a compound selected from the group consisting of 3-hydrocarbon substituted mercaptopropionic acids, their esters and salts.
  • Soap stabilized against rancidity by a compound selected from the group consisting of 3-oxygenated hydrocarbon substituted mercaptopropionic acids, their esters and salts.
  • Soap stabilized against rancidity by a compound selected from the group consisting of 3- sulfur-hydrocarbon substituted mercaptopropicnic acids, their esters and salts.
  • Soap stabilized against rancidity by a compound selected from the group consisting of 3-su1furand oxygenated-hydrocarbon substituted mercaptopropionic acids, their esters, and salts.
  • a soap comprising a water soluble salt of a higher fatty acid stabilized against deterioration and development of rancidity by having incor- 8 porated therein more than 0.005% of a compound selected from the group consisting of S-hydrocarbon substituted mercaptopropionic acids, their esters and salts.
  • a soap comprising MYERS F. G'RI'BBINS.

Description

Patented Feb. 18, 1947 STAPILIZED SOAP Myers F. Gribbins, Wilmington, Dcl., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 19, 1945, Serial No. 583,637
14 Claims.
The present invention relates to stabilized soaps, to the manufacture of stabilized soap and soap products and especially stabilized soap and soap products made from ingredients, one or more of which ordinarily deteriorate or develop rancidity in a relatively short time and particularly to soap stabilization by substituted beta mercaptopropionic acid or its derivatives.
It is well known that soaps tend to become rancid and discolor after storage. It is not definitely known just what causes the deterioration but it has been suggested that it may be due to oxidation or chemical decomposition. Such deterioration is highly objectionable as it renders the soaps unattractive by blanketing in many instances the perfumes of the soap discoloring it and/or leaving an objectionable rancid odor on the skin or the article being cleaned. Many attempts have been made to overcome this deterioration, the addition of various substances having been proposed to inhibit or retard it.
An object of the present invention is to provide stabilized soaps. Another object is to provide compounds to be incorporated in the salts of fatty acids Which will retard or inhibit their deterioration or prolong the period during which the salts are not rancid, which period is commonly referred to as the induction period, the salts so treated being free from the disadvantageous properties of compounds heretofore employed for this purpose. Still another object is to provide substituted beta mercaptopropionic acids and their esters as soap rancidity inhibitors. Other objects and advantages of the invention will appear hereinafter.
These objects may be accomplished in accordance with the invention by stabilizing liquid, jell-like and cake soap against rancidity by the incorporation therein of substituted beta mercaptopropionic acids or esters, by which is meant compounds containing the group ikyl groups: methyl, ethyl, propyl, butyl, lauryl,
and the aryl groups: phenyl, naphthyl, benzyl; and such groups as p methoxy phenyl, p hydroxy phenyl and cyclohexyl, which gives respectively:
a. B-methyl mercaptopropionic acid b. 3-ethyl mereaptopropionic acid c. 3-propy1mercaptopropionic acid 3-butyl mercaptopropionic acid 3-laury1 mercaptopropionic acid B-phenyl mercaptopropionic acid 3-benzyl mercaptopropionic acid 3-naphthyl mercaptopropionic acid B-(p methoxy) phenyl mercaptopropionic acid 3-(p hydroxy) phenyl mercaptopropionic acid 3-cyclohexyl mercaptopropionic acid Compounds of this type may'be prepared by the addition of mercaptans to acrylonitrile followed by acid or alkaline hydrolysis of the nitrile group to produce the desired product.
6. f. h. i. 7'. k.
Example.-3-ethylmercaptopropionic acid preparation 3-ethyl mercaptopropionic acid properties: Formula: CHsCHz-S-CHzCHzCOOH. Molecular Weight: 134. Boiling point: 93 C./2 mm. Neutral equivalent: 134. Solubility in water 20 C.: slightly soluble. Solubility in fats 20 C.: fairly soluble. Appearance: water white liquid.
HOOCCHzCHzSCHzCHaCHzOH :1. 3-methoxymethyl mercaptopropionic acid HOOCCHzCHzSCHzOCHs e. 3-methoxy'ethyl mercaptopropionic acid HOOCCHzCHzSCI-IzCI-IzOCI-Is f. 3-ethoxyethyl mercaptopropionic acid HOOCCHzCHzSCI-IzCHzOCzHs g. 3-carboxymethyl mercaptopropionic acid HOOCCHzCHzSCI-IzCOOH ht B-carboxyethyl mercaptopropionic acid (betabeta thio-dipropionic acid) HOOCCHzCHzSCHzCHzCOOH i. 3-carboxypropyl mercaptopropionic acid HOOCCHzCHzSCHzCHzCHzCOOH a. B-carboxybutyl mercaptopropionic acid HOOCCH2CH2SCH2CH2CH2COOH k. 3-aldehydoethyl mercaptopropionic acid HOOCCHzCHzSCHzCHzCHO The type reaction is identical to that indicated in section 1. Specifically, oxygenated mercaptans are added to acrylonitrile and the nitrile group hydrolyzed by acid or alkaline treatment.
Example-3 hydrozcyethyl mercaptopropionic acid preparation 2'7 parts (0.35M) mercapto glycol (HSCHzCHzOI-I) is added to 19 parts (0.35M) of acrylonitrile in the presence of 0.5 part piperidine. The reaction mixture is topped to remove unreacted mat-erials and then heated in an excess of concentrated HCl ('75 parts) for 1 hour. The by-product NH4C1 precipitates out and is removed by filtration. Excess HCl and H20 are removed by vacuum treatment. The product,
HOCI-IzCI-IzSCHzCHzCOOI-I is a water white, thick liquid which decomposes on distillation. Neutral equivalent=l50.
3. A sulfur-hydrocarbon group such, e. g., as: mercaptoethyl, mercaptopropyl, mercaptobutyl, mercaptoisobutyl, mercaptohexyl and ethiaethyl, which gives respectively:
a. 3-mercaptoethyl mercaptopropionic acid HOOCCH2CH2SCH2CH2SH b. 3-mercaptopropyl mercaptopropionic acid HOOCCH2CH2SCH2CH2CH2SH c. 3-mercaptobutyl mercaptopropionic acid HOOCCH2CH2SCH2CH2CH2CH2SH d. 3-mercaptoisobutyl mercaptopropionic acid nooccnzcmscmomcnsn e. 3-mercaptohexyl mercaptopropionic acid HOOCCHzCHzSCeHmSH ,f. Ethiaethyl mercaptopropionic acid HOOCCH2CH2SCH2CH2SC2H5 The type reaction is identical to that indicated in Section 1. Specifically, it involves the addition of molar amounts of dimercaptans to acrylonitrile,'followed by acid or alkaline hydrolysis of the nitrile group.
Ezample.6-mercapto 4 thiaheamnoic acid preparation To a solution of 329 parts (3.5M) ethanedithiol and 2 parts piperidine in 450 parts ethyl alcohol, 185.5 parts (3.5M) acrylonitrile is added dropwise over a period of 1 hour. Reaction tempera ture is maintained between 40-50 C. A precipitate of the di-addition product forms and is removed by filtration. Distillation of the filtrate gives the desired product HSCH2CH2SCH2CH2CN boiling point 139-141 C./6 mm. in about 26% yield. Heating 20 parts of this nitrile in parts concentrated HCl for 2 hours (in steam bath) produces the final product, a light yellow liquid, boiling point 142-1 13 C./2 mm. Neutral equivalent=166.
4. A sulfurand oxygenated-hydrocarbon group such, e. g., as: Carboxyethiaethyl,
-CH: .CH2SCH2CH2COOH Carboxyethiaethdithiaethyl,
I -CH2CH2SSCH2CH2SCH2CHzCOOH Carboxyethiaisobutyl, V
-CH2CH2CH (CH3) SCHzCHzCOOI-I and Carboxyethiapropyl,
which gives respectively:
a. 4,7-dithiasebacic acid HOOCCH2CH2S-CH2CH2SCH2CH2COOH b. 4,7,8,l1-tetrathiatetradecandioic acid c. 5 methyl-4,8-dithiaundecandioic acid HOOCCHzCHzSCHzCI-IzCH CH3) SCHzCI-IzCOOH d. 4,1l-dithiatetradecanedioic acid HOOCCH2CH2S(CH2) eSCHzCHzCOOH Type reaction is identical to that indicated in. Section 1. Specifically, it involves the addition of 2 moles acrylonitrile and 1 mole of a dimercaptan to give a sulfur containing dinitrile which can be hydrolyzed by acid or alkaline treatments.
Example.-4,7-dithiasebacic acid preparation Formula: I
HOOCCH2CH2SCH2CH2--SCH2CH2COOH Molecular weight: 236.
M. P.: 151 C.
Neutral equivalent: 118.
Solubility in water 20 0.: very slightly soluble. Solubility in fat 20 0.: slightly soluble. Appearance: odorless white crystals.
5. Or a sulfur-,
nitrogen-hydrocarbon group. such, e. g., as: 3-benzothiazyl mercaptopropionic acid CS-GHaCHsCOOH Emample.-3-benzothiazyl mercaptopropionic acid preparation To a solution of 167 parts (1M) mercaptobenzoties:
Formula Molecular weight: 239.
M. P.: 149-l50 C.
Neutral equivalent: 239.
Solubility in water 20 C.: slightly soluble. Solubility in fat 20 0.: slightly soluble. Appearance: white crystals.
'I'hesestabilizers may be incorporated in the soap in any suitable manner such, for example, as by simple mixing in proper proportions into the liquid or gel-like soap, by grinding, malaxing, or thoroughly and uniformly distributing it into the more or less solid soaps, the latter being subsequently formed'intc solid cakes or other shapes. Alternatively the stabilizers may be added at any convenient stage in the process of soap manufacture, care being exercised not to add it at a stage which will result in decomposition, leaching, or deterioration of the stabilizing agent. If desired, for example, these agents may be added during the well known crutching operation.
The stabilizers may be present in the soap to the extent of as little a 0.005%. The inhibiting powers of the particular agent used, or if a mixture is used, then the power of the mixture of agents will determine the exact amount that should be used for any desired duration of stabilization. The optimum amount to be used may be determined for any agent or mixture by preparing a series of compositions containing selected amounts for example from 0.005% to say 5% of the agent or mixture such as 0.001, 0.01, 0.1, 1.0, 2.5, and 5% or a more comprehensive serie with smaller diiferentials if desired, placing these compositions under controlled storage conditions for the number of days the composition is to be maintained in the stabilized state. The composition that contains the minimum amount of stabilizing agent is the amount that should be used to stabilize the soap for the selected period. Amounts ranging from .01 to about 2% give excellent stability to the soap.
The stabilizers may be used in soaps generally for there are few if any that do not require some stabilization. The strong laundry soaps rancidify leaving undesirable odors. The delicate, more highly purified facial soaps likewise rancidify to destroy the perfume used. As example of the soaps that can be stabilized by these agents are included the alkali metal and alkaline earth metal as well as the heavy metal salts of the higher fatty acids and mixtures of salts of such acid and complex alcohols obtained by the saponiflcation of the marine, vegetable, and animal oils and fats. The stabilizers are effective in watersoluble, water-insoluble and metallic soaps; the so-called mineral oil soaps, i. e., the water-soluble mineral oils and the like which are generally mixture of mineral oils and oil soluble. soaps which are used without water as a coolant in the machine tool industries and with water in the form of an emulsion as a coolant for cutting tools and as an insecticide spray; and in cosmetics compositions generally containing soaps which are used in tooth pastes, faceand body creams, e c.
The surprising and unexpected stabilizing effect of the substituted beta mercaptopropionic acids and their derivatives is clearly demonstrated by the following tests. The test involves the examination of soap with and without the stabilizer for color, peroxide value and odor. The color is determined by visual examination; the peroxide value as included in the Swift test (Oil and Soap 10, -109, 1933), and the odor by placing aliquot portions of the soap with and without stabilizer in stoppered flasks of equal size, storing them under a constant temperature of about 50 C. At the end of each day, the stopper was remove and any odor indicating rancidity noted. The soap was combined with the stabilizer by malaxing the soap at about room temperature with the stabilizer. Table I tabulates the result of observations.
Table I Peroxide Treatment Days Color value Odor 1 White... 1.8 None. 1 .do 2. 4 Do. 4 Brown 9. 2 Rancid. 4 White.. 2. 8 None. 10 Brown 21. 0 Rancid. 10 mi. 2. 8 Slightly rancid.
A. Soap with no stabilizer. B. Soap with 1% thiodipropionic acid.
The stabilizers described under the 5 groups and their equivalents may be used as the acid, ester or salt. Generally as specific examples of the esters may be included the methyl, ethyl N- and iso-propyl, N- and iso-butyl and the higher straight and branched chain alkyl esters as well as the alicyclic ester cyclohexyl. As specific examples of the salts are included the alkali metal and alkaline earth metal salts and particularly the sodium, potassium, calcium and magnesium salts.
I claim:
1. A process which comprises protecting soap against rancidity by incorporating therein a compound selected from the group consisting of 3-hydrocarbon substituted mercaptopropionie acids, their esters and salts.
2. A process which comprises protecting soap against rancidity by incorporating therein a compound selected from the group consisting of 3-oxygenatecrhydrocarbon substituted mercaptopropionic acids. their esters and salts.
3. A process whicicomprises protecting soap 7 against rancidity by incorporating therein a com pound selected from. the group consisting 01 v 3-sulfur hydrocarbon substituted mercapto-propionic acids, their esters and salts.
4. A process which comprises protecting soap against rancidity by incorporating therein a compound selected from the group consisting of 3-sulfurand oxygenated-hydrocarbon substituted mercaptopropionic acids, their esters and salts.
5. Soap stabilized against rancidity b a compound selected from the group consisting of 3-hydrocarbon substituted mercaptopropionic acids, their esters and salts.
6. Soap stabilized against rancidity by a compound selected from the group consisting of 3-oxygenated hydrocarbon substituted mercaptopropionic acids, their esters and salts.
7. Soap stabilized against rancidity by a compound selected from the group consisting of 3- sulfur-hydrocarbon substituted mercaptopropicnic acids, their esters and salts.
8. Soap stabilized against rancidity by a compound selected from the group consisting of 3-su1furand oxygenated-hydrocarbon substituted mercaptopropionic acids, their esters, and salts.
9. A soap comprising a water soluble salt of a higher fatty acid stabilized against deterioration and development of rancidity by having incor- 8 porated therein more than 0.005% of a compound selected from the group consisting of S-hydrocarbon substituted mercaptopropionic acids, their esters and salts.
10. A soap comprising MYERS F. G'RI'BBINS.
REFERENCES crrEn The following references are of record in the file of this patent: w
UNITED STATES PATENTS Name Date Gribbin et a1. Apr. 9, 1946 Number v a water soluble salt 01 of a higher fatty acid stabilized against deterioraand r
US583637A 1945-03-19 1945-03-19 Stabilized soap Expired - Lifetime US2416052A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US583637A US2416052A (en) 1945-03-19 1945-03-19 Stabilized soap

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US583637A US2416052A (en) 1945-03-19 1945-03-19 Stabilized soap

Publications (1)

Publication Number Publication Date
US2416052A true US2416052A (en) 1947-02-18

Family

ID=24333960

Family Applications (1)

Application Number Title Priority Date Filing Date
US583637A Expired - Lifetime US2416052A (en) 1945-03-19 1945-03-19 Stabilized soap

Country Status (1)

Country Link
US (1) US2416052A (en)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2497320A (en) * 1946-02-12 1950-02-14 Du Pont Stabilized milk products
US2535875A (en) * 1947-09-03 1950-12-26 Goodrich Co B F Plant growth regulants
US2535876A (en) * 1947-09-03 1950-12-26 Goodrich Co B F Beta-(heterocyclic-thio) propionic acid and derivatives as plant stimulants
US2564106A (en) * 1948-10-29 1951-08-14 Du Pont Food antioxidants
US2579679A (en) * 1949-09-22 1951-12-25 Abbott Lab Stable vitamin b12 composition
US2940933A (en) * 1956-09-26 1960-06-14 Sun Oil Co Mineral oil antioxidant
US3227692A (en) * 1958-12-12 1966-01-04 Eastman Kodak Co Polymeric lactones containing thioether atoms
US4026814A (en) * 1974-09-09 1977-05-31 Lever Brothers Company Oxido-reductase in soap
US4032564A (en) * 1974-09-09 1977-06-28 Zoecon Corporation Esters of cyclopropylalkanols
US4119788A (en) * 1976-10-07 1978-10-10 International Flavors & Fragrances Inc. α-Oxy(oxo) sulfides and ethers
US4231956A (en) * 1978-08-28 1980-11-04 Exxon Research & Engineering Co. Process for preparation of thioethers
US4349468A (en) * 1977-12-23 1982-09-14 Adeka Argus Chemical Co., Ltd. Stabilizer for polyolefin resin
US4374945A (en) * 1981-03-11 1983-02-22 Witco Chemical Corporation Thioglycolate and thiopropionate secondary stabilizers
US4532031A (en) * 1982-06-21 1985-07-30 American Cyanamid Company Froth flotation process
US4604417A (en) * 1984-12-10 1986-08-05 The Goodyear Tire & Rubber Company Polymerizable thioester synergists
US4652670A (en) * 1985-08-23 1987-03-24 International Flavors & Fragrances Inc. Cycloalkyl esters of mercaptoalkanoic acids
US4701548A (en) * 1985-09-20 1987-10-20 International Flavors & Fragrances Inc. Thioalkanoic acid esters of phenylalkanols
US4739105A (en) * 1985-12-06 1988-04-19 International Flavors & Frangrances Inc. Esters of alkylthioalkanoic acids and uses thereof in augmenting or enhancing the aroma or taste of foodstuffs
US5055606A (en) * 1989-08-16 1991-10-08 Witco Corporation Alkylthiopropionic pentaerythritol esters and solvent refining thereof
US5057622A (en) * 1989-08-16 1991-10-15 Witco Corporation 3-alkylthiopropionic acids and derivatives
EP0844238A1 (en) * 1996-11-25 1998-05-27 Nippon Shokubai Co., Ltd. Process for production of sulfide group-containing mercaptocarboxylic acid and ester thereof
US20090062285A1 (en) * 2007-08-30 2009-03-05 National Sun Yat-Sen University Sulfur-containing compound, method of preparation and pharmaceutical uses thereof
US20090203817A1 (en) * 2006-04-13 2009-08-13 Stretanski Joseph A Stabilized spandex compositions

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2397960A (en) * 1944-08-28 1946-04-09 Du Pont Food antioxidants

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2397960A (en) * 1944-08-28 1946-04-09 Du Pont Food antioxidants

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2497320A (en) * 1946-02-12 1950-02-14 Du Pont Stabilized milk products
US2535875A (en) * 1947-09-03 1950-12-26 Goodrich Co B F Plant growth regulants
US2535876A (en) * 1947-09-03 1950-12-26 Goodrich Co B F Beta-(heterocyclic-thio) propionic acid and derivatives as plant stimulants
US2564106A (en) * 1948-10-29 1951-08-14 Du Pont Food antioxidants
US2579679A (en) * 1949-09-22 1951-12-25 Abbott Lab Stable vitamin b12 composition
US2940933A (en) * 1956-09-26 1960-06-14 Sun Oil Co Mineral oil antioxidant
US3227692A (en) * 1958-12-12 1966-01-04 Eastman Kodak Co Polymeric lactones containing thioether atoms
US4026814A (en) * 1974-09-09 1977-05-31 Lever Brothers Company Oxido-reductase in soap
US4032564A (en) * 1974-09-09 1977-06-28 Zoecon Corporation Esters of cyclopropylalkanols
US4119788A (en) * 1976-10-07 1978-10-10 International Flavors & Fragrances Inc. α-Oxy(oxo) sulfides and ethers
US4349468A (en) * 1977-12-23 1982-09-14 Adeka Argus Chemical Co., Ltd. Stabilizer for polyolefin resin
US4231956A (en) * 1978-08-28 1980-11-04 Exxon Research & Engineering Co. Process for preparation of thioethers
US4374945A (en) * 1981-03-11 1983-02-22 Witco Chemical Corporation Thioglycolate and thiopropionate secondary stabilizers
US4532031A (en) * 1982-06-21 1985-07-30 American Cyanamid Company Froth flotation process
US4604417A (en) * 1984-12-10 1986-08-05 The Goodyear Tire & Rubber Company Polymerizable thioester synergists
US4652670A (en) * 1985-08-23 1987-03-24 International Flavors & Fragrances Inc. Cycloalkyl esters of mercaptoalkanoic acids
US4701548A (en) * 1985-09-20 1987-10-20 International Flavors & Fragrances Inc. Thioalkanoic acid esters of phenylalkanols
US4739105A (en) * 1985-12-06 1988-04-19 International Flavors & Frangrances Inc. Esters of alkylthioalkanoic acids and uses thereof in augmenting or enhancing the aroma or taste of foodstuffs
US5057622A (en) * 1989-08-16 1991-10-15 Witco Corporation 3-alkylthiopropionic acids and derivatives
US5055606A (en) * 1989-08-16 1991-10-08 Witco Corporation Alkylthiopropionic pentaerythritol esters and solvent refining thereof
US5198486A (en) * 1989-08-16 1993-03-30 Witco Corporation S-alkylthiopropionic acids and derivatives
EP0844238A1 (en) * 1996-11-25 1998-05-27 Nippon Shokubai Co., Ltd. Process for production of sulfide group-containing mercaptocarboxylic acid and ester thereof
US20090203817A1 (en) * 2006-04-13 2009-08-13 Stretanski Joseph A Stabilized spandex compositions
US20090062285A1 (en) * 2007-08-30 2009-03-05 National Sun Yat-Sen University Sulfur-containing compound, method of preparation and pharmaceutical uses thereof
JP2009108028A (en) * 2007-08-30 2009-05-21 National Sun Yat-Sen Univ Sulfur-containing compound, its preparation method and pharmaceutical use
EP2030968A3 (en) * 2007-08-30 2010-01-13 National Sun Yat-Sen University Sulfur-containing compound, method of preparation and pharmaceutical uses thereof
US8399661B2 (en) 2007-08-30 2013-03-19 National Sun Yat-Sen University Sulfur-containing compound, method of preparation and pharmaceutical uses thereof

Similar Documents

Publication Publication Date Title
US2416052A (en) Stabilized soap
US2397960A (en) Food antioxidants
US3630934A (en) Mildness additive
US2468012A (en) Beta amino propionates
US2773068A (en) Substitution derivatives of imidazoline alkanoic quaternary ammonium hydroxide and process of preparing same
US1906484A (en) Soap preparation
US3449430A (en) Amino oxides
JP2015519451A (en) Use of N-methyl-N-acyl glucamine as a low temperature stabilizer in surfactant solutions
US2959547A (en) Aqueous coolant for metal working machines
US2154341A (en) Stabilization of fatty acid compounds
US2226177A (en) Deodorant
US3344018A (en) Biocidal quaternary ammonium sulfamates
EP0386826B1 (en) Amidated fatty acid mixtures and use thereof as thickeners
US2004873A (en) Thiosulphate esters and their production
US3745181A (en) Process for the preparation of surfactants
US2333093A (en) Cosmetic preparation
US3097229A (en) Cycloaliphatic chlorocarbanilates
US2427717A (en) Cosmetic preparation containing triethanol amine salts of sulfurized fatty acids
US2874185A (en) N-myristyl-3-hydroxybutylamines and their salts
US2730502A (en) Antiseptic detergent composition
US2795554A (en) Antiseptic soap composition
US2813112A (en) Soap composition
US2798046A (en) Antiseptic soap composition
US2971917A (en) Stabilized soap composition
US3103467A (en) Method of controlling bacterial