US3404183A - Mono-and dialkoxyalkyl quaternary ammonium compounds - Google Patents

Mono-and dialkoxyalkyl quaternary ammonium compounds Download PDF

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Publication number
US3404183A
US3404183A US544415A US54441566A US3404183A US 3404183 A US3404183 A US 3404183A US 544415 A US544415 A US 544415A US 54441566 A US54441566 A US 54441566A US 3404183 A US3404183 A US 3404183A
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United States
Prior art keywords
quaternary ammonium
ammonium compounds
carbon atoms
reaction
amine
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Expired - Lifetime
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US544415A
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English (en)
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Graham K Hughes
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Ashland LLC
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Ashland Oil Inc
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Priority to US544415A priority Critical patent/US3404183A/en
Priority to DE19671593746 priority patent/DE1593746A1/de
Priority to FR103029A priority patent/FR1519287A/fr
Priority to BE697359D priority patent/BE697359A/xx
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Publication of US3404183A publication Critical patent/US3404183A/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions
    • 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
    • Y10S516/07—Organic amine, amide, or n-base containing
    • 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
    • Y10S516/905—Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
    • Y10S516/907—The agent contains organic compound containing phosphorus, e.g. lecithin
    • 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
    • Y10S516/905—Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
    • Y10S516/907—The agent contains organic compound containing phosphorus, e.g. lecithin
    • Y10S516/908—The compound contains repeating -OCnH2n-, i.e. repeating unsubstituted oxyalkylene
    • 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
    • Y10S516/905—Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
    • Y10S516/909—The agent contains organic compound containing sulfoxy*
    • Y10S516/91—The compound contains nitrogen, except if present solely as NH4+
    • 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
    • Y10S516/905—Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
    • Y10S516/914—The agent contains organic compound containing nitrogen, except if present solely as NH4+
    • 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
    • Y10S516/905—Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
    • Y10S516/914—The agent contains organic compound containing nitrogen, except if present solely as NH4+
    • Y10S516/916—The compound contains repeating -OCnH2n-, i.e. repeating unsubstituted oxyalkylene

Definitions

  • the present invention relates to novel quaternary ammonium compounds and to methods for their preparation.
  • the novel quaternary ammonium compounds are useful as surfactants and are of particular value as fabric softeners.
  • the quaternary ammonium compounds of the present invention have the general formula:
  • R and R are the same or different lower alkyl radicals having from 1 to 4 carbon atoms;
  • X is an anion and preferably a halogen having an atomic weight of 35.5 to 127;
  • R is a monovalent radical in which the sum of oxygen and carbon atoms is from 14 to 22 and preferably from 16 to 18 and which has the formula:
  • R R R-o-orr 31rin which R is an alkyl radical or an alkoxyalkyl radical containing up to two oxyalkylene groups of 2 to 3 carbon atoms, and R" is hydrogen or methyl and can be the same or different; and wherein R is R or an alkyl radical of 14 to 22 carbon atoms and preferably 16 to 18 carbon atoms.
  • the preferred quaternary ammonium compounds of the present invention have the formula:
  • the quaternary ammonium compounds of the present invention can be prepared by a process employing the following reactions:
  • the cyanoalkylation of the alcohol (Reaction A) is carried out in the liquid phase at atmospheric pressure and at temperatures between 0 to 100 C. and preferably between 50 to C.
  • inert solvents can be employed, it is, in general, preferable to carry out the reaction in bulk.
  • Catalytic concentrations of an alkali metal e.g., 0.01 to 1.0% by weight of the alcohol, are dissolved in the alcohol by heating to temperatures of to C.
  • the mixture is cooled to about 50 to 55 C. and the ethylenically unsaturated nitrile is added slowly to the alcohol at a rate such that the reaction temperature does not rise substantially above 70 C.
  • the amount of the ethylenically unsaturated nitrile employed is generally slightly in excess, e.g., 5 to 20% over the stoichiometric amount of nitrile required.
  • the reaction is preferably permitted to stand for 6 to 20 hours, which results in higher yields of the ether nitrile.
  • the alkali metal is then neutralized and the ether nitrile distilled out of the reaction mixture. A high yield of the pure ether nitrile is obtained.
  • the ether nitrile is then hydrogenated to the amine, employing hydrogenation techniques heretofore developed for the hydrogenation of nitriles. Particularly preferred is the hydrogenation of the ether nitrile with a Raney nickel or palladium catalyst.
  • the hydrogenation is normally conducted as a two-step process. In the first step, the nitrile is converted to a primary amine in the presence of NH In the second step, the amine is sparged with hydrogen and converted to the secondary amine which can contain minor concentrations of tertiary amine.
  • a mixture of the ether nitrile and a nitrile having the formula R CN, wherein R has the above-indicated meaning can be reacted together to form a mixed secondary amine.
  • the secondary amine is then reacted with a lower alkyl halide to result in the quaternary ammonium compound.
  • the quaternization of the amine is a well-known reaction and thus requires no further detailed description. Minor quantities of tertiary amine formed together with the secondary amine are converted along with the secondary amine to a quaternary ammonium compound.
  • the quaternary ammonium compounds derived from the tertiary amines do not deleteriously affect the utility of the quaternary ammonium compound derived from the secondary amine and hence separation of the secondary and tertiary amines formed in the hydrogenation step is unnecessary. The separation of such would significantly add to the cost of producing the novel quaternary ammonium compounds of the present invention.
  • Alcohols which can be employed to form the novel quaternary ammonium compounds of the present invention include: decanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, branched hexadecanol, secondary decanol, secondary pentadecanol, ethoxylated dodecanol, propoxylated dodecanol, diethoxylated octanol, dipropoxylated octanol, diethoxylated decanol, and dipropoxylated decanol.
  • the unsaturated nitriles employed include acrylonitrile, methacrylonitrile, and crotononitrile.
  • the secondary amines are reacted with such lower alkyl halides as: methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, and butyl chloride.
  • novel quaternary ammonium compounds of the present invention are surfactants and are particularly useful as fabric softeners.
  • the novel quaternary ammonium compounds can be handled, shipped, and stored in liquid form without requiring excessive amounts of diluent, disperse more readily in water particularly cold water than fabric softeners heretofore developed, form clear fluid dispersions, and exhibit a higher degree of compatability with salts and anionic detergents than obtained with fabric softeners heretofore developed.
  • Example 1 (A) Into a reaction flask equipped with dropping funnel, agitator and thermometer is charged 828 g. of a C to C alcohol mixture, and 0.83 g. of sodium. The mixture is heated to 95 C. with agitation until the sodium has dissolved. The solution is then cooled down to 55 C. and the addition of 223.0 g. of acrylonitrile started. The addition is continued for a period of 90 minutes While the temperature is maintained at 55 to 60 C. On completion of the addition, agitation of the reaction mixture is continued for another hour. The reaction mixture is then neutralized by the addition of 2.15 g. of acetic acid and filtered. The reaction product is distilled at 150 to 190 C. and 0.2 mm. Hg pressure, to result in 930 g. of C C -alkoxyethylnitrile.
  • liquid product comprising mainly di(alkoxypropyl)amine in which the alkoxy group contains from 12 to 15 carbon atoms and a minor proportion of the corresponding tri(alkoxypropyl) amine.
  • the quaternary ammonium compound is readily dispersed in cold Water and when employed at a 0.1% level in the rinse water of a washing machine cycle, improves the flufliness and softness of towels to a greater extent than similarly treated towels employing a commercially available fabric softener.
  • the quaternary ammonium compound is further tested for compatability with zinc nitrate used in textile applications by mixing equal amounts of a 5% dispersion of the quaternary ammonium compound in water with a 5% zinc nitrate solution.
  • the quaternary ammonium compound can be maintained in the mixture in the form of a dispersion with slight agitation without forming a.precipitate.
  • Example 2 Into a 2-liter Parr bomb is charged 325 g. of alkoxyethylnitrile in which the alkoxy group contains from 12 to 15 carbon atoms, 325 g. of hard tallow nitrile, and 26.0 g. of a nickel hydrogenation catalyst commercially available as Girdler G 49-B.
  • the reaction vessel is purged, heated to 100 F. and pressured to 100 p.s.i. with NH and then heated to 290 F. and pressured with hydrogen to 510 p.s.i.
  • the reaction is agitated and maintained at that pressure and a temperature of 290 to 300 F. for about one hour.
  • the reaction mixture is then vented, heated to 350 F.
  • Example 3 (A) Into a reaction flask equipped with dropping funnel, agitator and thermometer is charged 800 g. of tridecyl alcohol and 0.8 g. of sodium. The mixture is heated to C. with agitation until the sodium has dissolved. The solution is then cooled down to 56 C. and the addition of 223 g. of acrylonitrile started. The addition is continued for a period of about one hour while the temperature is maintained at 55 to 60 C. On completion of the addition, agitation of the reaction mixture is continued for another hour. The reaction mixture is then neutralized by the addition of 2.1 g. of acetic acid, and filtered. The reaction product is distilled over at 160 to 210 C. and a pressure of 0.1 mm. Hg to result in 880 g. of tridecyloxyethyl nitrile.
  • the quaternary ammonium compound is readily dispersible in water at concentration levels of 5%, forms clear solutions at the 40% level, and does not freeze at temperatures above 40 F.
  • Example 4 Following the procedure of Example 3, diethoxylated C to C aliphatic alcohol is reacted with acrylonitrile, the resulting ether nitrile hydrogenated to the corresponding secondary amine, and the secondary amine reacted with methyl chloride to form di(alkyldiethoxypropyl)dimethyl ammonium chloride, in which the alkyl groups have from 8 to 10. carbon atoms.
  • Example 5 Following the procedure of Example 3, a mixture of C and C straight chain alcohol (commercially available as Alfol 1214) is reacted with methacrylonitrile, the resulting ether nitrile hydrogenated to the corresponding secondary amine, and the secondary amine reacted with methyl chloride to form di(alkoxy-Z-methylpropyl)dimethyl ammonium chloride in which the alkoxy groups have 12 and 14 carbon atoms.
  • Example 6 Following the procedure of Example 3, a mixture of dipropoxylated C to C alcohols, in which the alcohols are derived from coconut oil, is reacted with acrylonitrile, the resulting ether nitrile hydrogenated to the corresponding secondary amine, and the secondary amine reacted with methyl chloride to form di(alkyldipropoxypropyl)dimethyl ammonium chloride, in which the alkyl groups have from 8 to 10 carbon atoms.
  • Example 7 The procedure of Example 3(C) is repeated, employing ethyl bromide instead of methyl chloride, and di(tridecyloxypropyl)diethyl ammonium bromide is obtained.
  • the quaternary ammonium halides illustrated in the examples are readily converted to hydroxides, sulfates, nitrates, phosphates, acetates, formates, and sulfonates by metathesis reactions employing techniques heretofore developed in the art.
  • the utility of the quaternary ammonium compounds is not limited to their use as fabric softeners as illustrated in the examples and that the quaternary ammonium compounds have utility in a wide range of applications based on their surfactant properties.
  • R and R are lower alkyl radicals having 1 to 4 carbon atoms
  • X is an anion selected from the group consisting of halogen, hydroxide, sulfate, nitrate, phosphate, acetate, formate and sulfonate
  • R is a monovalent radical in which the sum of oxygen and carbon atoms is from 14 to 22, and which has the formula:
  • R ' is an alkyl or an alkoxyalkyl radical con- 7 taining up to two oxyalkylene groups of 2 to 3 carbon atoms, and R" is hydrogen or methyl; and wherein R is R or an alkyl radical of 14 to 22 carbon atoms.
  • R is R
  • R is an alkyl diethoxy radical in which said alkyl group contains 8 to 10 carbon atoms
  • both R" are hydrogen
  • R and R are methyl.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US544415A 1966-04-22 1966-04-22 Mono-and dialkoxyalkyl quaternary ammonium compounds Expired - Lifetime US3404183A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US544415A US3404183A (en) 1966-04-22 1966-04-22 Mono-and dialkoxyalkyl quaternary ammonium compounds
DE19671593746 DE1593746A1 (de) 1966-04-22 1967-04-15 Verfahren zur Herstellung neuer quaternaerer Ammoniumverbindungen
FR103029A FR1519287A (fr) 1966-04-22 1967-04-17 Nouveaux composés d'ammonium quaternaire et leur préparation
BE697359D BE697359A (en0) 1966-04-22 1967-04-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2256234A1 (de) * 1971-11-19 1973-05-24 Mo Och Domsjoe Ab Kationische oberflaechenaktive verbindungen, verfahren zu ihrer herstellung und ihre verwendung fuer die behandlung von textilmaterialien
US4137180A (en) * 1976-07-02 1979-01-30 Lever Brothers Company Fabric treatment materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3126522A1 (de) * 1981-07-04 1983-01-20 Basf Ag, 6700 Ludwigshafen Quaternaere ammoniumsalze und verfahren zu ihrer herstellung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2087132A (en) * 1933-04-13 1937-07-13 Alba Pharmaceutical Company In Quaternary ammonium compounds
US2810720A (en) * 1955-07-19 1957-10-22 Rohm & Haas Quaternary ammonium compounds
US2810721A (en) * 1955-07-28 1957-10-22 Rohm & Haas Quaternary ammonium compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2087132A (en) * 1933-04-13 1937-07-13 Alba Pharmaceutical Company In Quaternary ammonium compounds
US2810720A (en) * 1955-07-19 1957-10-22 Rohm & Haas Quaternary ammonium compounds
US2810721A (en) * 1955-07-28 1957-10-22 Rohm & Haas Quaternary ammonium compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2256234A1 (de) * 1971-11-19 1973-05-24 Mo Och Domsjoe Ab Kationische oberflaechenaktive verbindungen, verfahren zu ihrer herstellung und ihre verwendung fuer die behandlung von textilmaterialien
US4137180A (en) * 1976-07-02 1979-01-30 Lever Brothers Company Fabric treatment materials

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BE697359A (en0) 1967-10-23
DE1593746A1 (de) 1971-02-25

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