US2668851A - Surface active agents - Google Patents

Surface active agents Download PDF

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Publication number
US2668851A
US2668851A US303433A US30343352A US2668851A US 2668851 A US2668851 A US 2668851A US 303433 A US303433 A US 303433A US 30343352 A US30343352 A US 30343352A US 2668851 A US2668851 A US 2668851A
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United States
Prior art keywords
product
surface active
fatty
active agents
dynes
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Expired - Lifetime
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US303433A
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Kendrick R Eilar
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General Mills Inc
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General Mills Inc
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/03—Organic sulfoxy compound containing
    • Y10S516/05—Organic amine, amide, or n-base containing

Definitions

  • These compounds may, be preparedby the reaction of a fatty polyaminehaving the formula RNHwnHznNHnH in which the various symbols have the above significance, either with an alkali metal or ammoniumv sulfite or bisulfite and a carbonyl compound capableof forming a bisulfite addition product, or with such; an addition product itself.
  • the fatty polyamineszhaving the above formula mayg'be'madeby variousprocesses well known to those skilled in the art.
  • the fatty polyamines may beeither saturated or unsaturated; Typical fattypolyamines which' may be employed are
  • the carbonyl compounds capable of forming bisulfite addition products include lower aldehydes and methyl ketones as well as other ketones such as cyclohexanone. Suitable carbonyl compounds include formaldehyde, acetaldehyde, acetone and the like.
  • the preferred carbonyl compounds are those containing from 1-6 carbon atoms.
  • the sulfite compound may be either an 2;. alkali. metal; onammonium; sulfite or:-bisulfite. Typical. examples include Na-HSOa, K2303; and; NHiI-ISOa.
  • the sulfi-te or-bisulfitecompoundand; thencarbonyl. compoundu may be added; tot-he re-.
  • alkanesulfonategroups introduced depends upon the relative proportions of the reactants. At: least. onealkanesulfonate group is introduced, and as. many may be introduced as. there are, active, hydrogens in the,.
  • Suitable solvent for from l-i' hours at -100 C may be used as such, orifv itisdesiredto obtainthe product. as a dry solid, this may be done by. adding, to the col.--- lected. reaction mixture a liquidv in which the.
  • Suitable solvents include ethyleneglycol and suitable precipitants include acetone, methanol, ethanol, acetonitrile.
  • the fatty polyamine may be water-sol. uble, in which case water; may be. used as. the reaction solvent.
  • the product was composed principally of the following compound:
  • Example 2 'y-Tallowaminopropylamine (7.7 g.) was substituted for the 'y-dodecylaminopropylamine in Example 1, and absolute methanol was substituted for acetonitrile.
  • the product weighed 13 g. and gave a surface active aqueous solution; at a concentration of 0.25% it gave 110 mm. of foam in the Ross-Miles test and had a surface tension of 37.2 dynes/cm. and an interfacial tension of 21.6 dynes/cm.
  • the product was composed principally of the following:
  • Example 3 Example 1 was repeated substituting sodium 2-hydroxy-2-propanesulfonate (6.5 g.) for the hydroxymethanesulfonate and acetone for the acetonitrile.
  • the product thus obtained was composed principally of the following compound:
  • This material gave aqueous solutions which foamed when shaken, although its solubility was limited to about 0.1%.
  • Example 4 To a solution of 20.8 g. of sodium bisulfite and 16.2 g. of 37% aqueous formaldehyde in 60 ml. of water was added 17.6 g. of N-dodecyl diethylenetriamine having the structure The solution was heated on the steam bath until it became clear and homogeneous. It was then cooled and to it was added 400 ml. of absolute methanol with rapid stirring. After standing for 30 minutes, the white precipitate was removed by filtration and washed with methanol.
  • the product was highly surface active in aqueous solution; at a concentration of 0.25%, it gave 138 mm. of foam in the Ross-Miles test, a wetting time of 77.2 sec. in the canvas disc test.
  • the surface tension of the solution was 32.6 dynes/cm., the interfacial tension 3.8 dynes/cm., and the pH was 9.8.
  • the structure of this product is CHzSOaNa CnHIsNC2H4-N-C2H4-NH His 0 aNa 0 H18 O :Na
  • Example 5 Octadecylaminopropylamine was substituted for the dodecyl homolog of Example 1.
  • the product was a strong surface tension de- 4 pressant, a 0.5% solution having a surface tension of 35.7 dynes/cm. and interfacial tension of 11.5 dynes/cm.
  • CisHmNCsHaN HsSOaNa CHzSOaNfl I claim as my invention: 1. Compounds having the following formula:
  • R is a fatty alkyl group containing from 8-22 carbon atoms
  • R is selected from the group consisting of hydrogen and C(R")2SO:M
  • R" is selected from the group consisting of hydrogen and lower alkyl groups
  • M is selected from the group consisting of alkali metal and ammonium
  • n is from 2 to 6
  • m is from 1 to 6, with the proviso that at least one of the groups R is C(R")2SO3M.
  • T represents the mixed fatty groups of tallow fatty acids.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Patented Feb. 9, 1954 UNITED- S-TATES QFFIEE SURFACE ACTIVEiAG'ENTSL Kendrick R. Eilar, Minneapolis, Minn., assignor to General Mills, Inc., a corporation of De'laware No Drawing. Application August 8, 1952', SQI'iaIYNO. 303,433..
6. Claims (Cl. 260-513) R is C(R)2SO3M. These compounds are in-,--
expensive surface active agentsywhich may be used as wetting agents, foaming agents, detergents, emulsifiers and the like.
It is, therefore, an object'of the present invention to provide-novel: compounds having the above formula.
It is another object of the present invention to provide a novelprocess of producing such compounds.
These compoundsmay, be preparedby the reaction of a fatty polyaminehaving the formula RNHwnHznNHnH in which the various symbols have the above significance, either with an alkali metal or ammoniumv sulfite or bisulfite and a carbonyl compound capableof forming a bisulfite addition product, or with such; an addition product itself.
The fatty polyamineszhaving the above formula mayg'be'madeby variousprocesses well known to those skilled in the art. The fatty polyamines which-@mam-be us drinclude. those. derived. from the mixedfatty acids of a. fator, oil, from selected fractions of such'fatty acids or any isolated fatty acid. The fatty polyamines may beeither saturated or unsaturated; Typical fattypolyamines which' may be employed are The carbonyl compounds capable of forming bisulfite addition products include lower aldehydes and methyl ketones as well as other ketones such as cyclohexanone. Suitable carbonyl compounds include formaldehyde, acetaldehyde, acetone and the like. The preferred carbonyl compounds are those containing from 1-6 carbon atoms. The sulfite compound may be either an 2;. alkali. metal; onammonium; sulfite or:-bisulfite. Typical. examples include Na-HSOa, K2303; and; NHiI-ISOa. The sulfi-te or-bisulfitecompoundand; thencarbonyl. compoundumay be added; tot-he re-.
.. action mixturezas such, or theymayxbe firstcomebined to give the corresponding hydroxyalkanersulfonate.
The number of alkanesulfonategroups introduced depends upon the relative proportions of the reactants. At: least. onealkanesulfonate group is introduced, and as. many may be introduced as. there are, active, hydrogens in the,.
fatty polyamine. The methodof preparation;
consists of heating the reactants together in a;
suitable solvent for from l-i' hours at -100 C. The resulting solution may be used as such, orifv itisdesiredto obtainthe product. as a dry solid, this may be done by. adding, to the col.--- lected. reaction mixture a liquidv in which the.
solvent is soluble but. in. which. the product... is.
insoluble. Suitable solvents include ethyleneglycol and suitable precipitants include acetone, methanol, ethanol, acetonitrile. In some in-. stances, the fatty polyamine may be water-sol. uble, in which case water; may be. used as. the reaction solvent.
Example 1' v-Dodecylaminopropylamine,
(5'22";g.) was dissolved in 12 ml. of ethylene glycol: Sodium hydroxymethane. sulfonate monohy- 0.25% solution gave136 mm. of foamin the Ross-Miles test, a. wetting time of 52.3; sec. in the;
canvas disc wetting test, and had a surface tension of 26.3 dynes per centimeter and an interfacial tension against mineral oil of 1.4 dynes per centimeter. The solution had a pH of 10.5 and was stable for several days without hydrolysis.
The product was composed principally of the following compound:
CHzSOaNa Example 2 'y-Tallowaminopropylamine (7.7 g.) was substituted for the 'y-dodecylaminopropylamine in Example 1, and absolute methanol was substituted for acetonitrile. The product weighed 13 g. and gave a surface active aqueous solution; at a concentration of 0.25% it gave 110 mm. of foam in the Ross-Miles test and had a surface tension of 37.2 dynes/cm. and an interfacial tension of 21.6 dynes/cm.
The product was composed principally of the following:
CHzSOINa RNC3H5N HzSOaNa CHzSOaNa where R represents the mixed fatty groups of tallow fatty acids.
Example 3 Example 1 was repeated substituting sodium 2-hydroxy-2-propanesulfonate (6.5 g.) for the hydroxymethanesulfonate and acetone for the acetonitrile. The product thus obtained was composed principally of the following compound:
This material gave aqueous solutions which foamed when shaken, although its solubility was limited to about 0.1%.
Example 4 To a solution of 20.8 g. of sodium bisulfite and 16.2 g. of 37% aqueous formaldehyde in 60 ml. of water was added 17.6 g. of N-dodecyl diethylenetriamine having the structure The solution was heated on the steam bath until it became clear and homogeneous. It was then cooled and to it was added 400 ml. of absolute methanol with rapid stirring. After standing for 30 minutes, the white precipitate was removed by filtration and washed with methanol.
The product was highly surface active in aqueous solution; at a concentration of 0.25%, it gave 138 mm. of foam in the Ross-Miles test, a wetting time of 77.2 sec. in the canvas disc test. The surface tension of the solution was 32.6 dynes/cm., the interfacial tension 3.8 dynes/cm., and the pH was 9.8. The structure of this product is CHzSOaNa CnHIsNC2H4-N-C2H4-NH His 0 aNa 0 H18 O :Na
Example 5 'y Octadecylaminopropylamine was substituted for the dodecyl homolog of Example 1. The product was a strong surface tension de- 4 pressant, a 0.5% solution having a surface tension of 35.7 dynes/cm. and interfacial tension of 11.5 dynes/cm.
The product consisted chiefly of a compound of the structure:
CHzSOcNa CisHmNCsHaN HsSOaNa CHzSOaNfl I claim as my invention: 1. Compounds having the following formula:
RN( Cn InN)- in which R is a fatty alkyl group containing from 8-22 carbon atoms, R is selected from the group consisting of hydrogen and C(R")2SO:M, in which R" is selected from the group consisting of hydrogen and lower alkyl groups, M is selected from the group consisting of alkali metal and ammonium, n is from 2 to 6 and m is from 1 to 6, with the proviso that at least one of the groups R is C(R")2SO3M.
2. The following compound:
CHQSOGNa C 12H25NC aHaN CHzSOaNa CHzSOaNa 3. The following compound:
0HS03Na TNCaHeN CH2SO3Na .CHiSOaNfl in which T represents the mixed fatty groups of tallow fatty acids.
4. The following compound:
CH: C 12H25N-C aHoNHl S O :Na
CHaOSOaNa 0H:
5. The following compound:
CHzSOzNa 1zH25NC2H4NC2 4-NH CHzSOaNa HzSOaNa 6. The following compound: v
' CHzGOaNa CmHavNCaHaN 0111s OaNa CHzSOsNB KENDRICK R. EILAR.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,207,603 Wesche July 9, 1940 2,532,391 Bersworth Dec. 5, 1950 FOREIGN PATENTS Number Country Date 452,584 Great Britain Aug. 25, 1936

Claims (1)

1. COMPOUNDS HAVING THE FOLLOWING FORMULA:
US303433A 1952-08-08 1952-08-08 Surface active agents Expired - Lifetime US2668851A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3210410A (en) * 1959-09-30 1965-10-05 Monsanto Co Ether derivatives of n-alkylamino-alkanesulfonate salts

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB452584A (en) * 1935-02-25 1936-08-25 Ig Farbenindustrie Ag Improvements in or relating to the manufacture of aminosulphonic acids
US2207603A (en) * 1938-05-23 1940-07-09 Ig Farbenindustrie Ag Manufacture of aliphatic aminosulphonic acids
US2532391A (en) * 1947-03-15 1950-12-05 Frederick C Bersworth Alkylene polyamine derivatives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB452584A (en) * 1935-02-25 1936-08-25 Ig Farbenindustrie Ag Improvements in or relating to the manufacture of aminosulphonic acids
US2207603A (en) * 1938-05-23 1940-07-09 Ig Farbenindustrie Ag Manufacture of aliphatic aminosulphonic acids
US2532391A (en) * 1947-03-15 1950-12-05 Frederick C Bersworth Alkylene polyamine derivatives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3210410A (en) * 1959-09-30 1965-10-05 Monsanto Co Ether derivatives of n-alkylamino-alkanesulfonate salts

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