US3632623A - Beta-carbamyl-beta-hydroxyethyl)-alkylammonium salts - Google Patents

Beta-carbamyl-beta-hydroxyethyl)-alkylammonium salts Download PDF

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Publication number
US3632623A
US3632623A US776794A US3632623DA US3632623A US 3632623 A US3632623 A US 3632623A US 776794 A US776794 A US 776794A US 3632623D A US3632623D A US 3632623DA US 3632623 A US3632623 A US 3632623A
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United States
Prior art keywords
formula
agents
acid
substance
radical
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US776794A
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English (en)
Inventor
Friedrich Becke
Friedrich Fuchs
Reinhold Kohlhaupt
Bruno Sander
Josef Thewis
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BASF SE
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BASF SE
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Priority claimed from DE19671643498 external-priority patent/DE1643498A1/de
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    • 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
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
    • 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
    • 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

Definitions

  • Cationactive substances i.e. substances which contain a long chain aliphatic hydrocarbon radical and moreover one or more cationic hydrophilic groups, for example quaternary ammonium groups to ensure good solubility or dispersability in water are required for many industrial applications.
  • These substances may serve for example as emulsifiers and as fat-liquoring agents or softening agent for fibrous materials such as leather, paper and textile material.
  • Prior art agents of this type have the disadvantage that in spite of a content of at least one hydrophilic group in all they have a clearly hydrophobic character. No satisfactory attempt has yet been made to combine fatliquoring or softening effect and hydrophilic effect in one and the same substance.
  • 'It is an object of this invention to provide a cationic surfactant which is universally applicable and a process for the manufacture of the same.
  • Another object of the invention is to provide new cationic substances which exert a fat liquoring or softening effect on fibrous material and at the same time have a pronounced hydrophilic character.
  • a further object of the invention is to provide substances which can be used as cationic fat liquoring agents for leather or as emulsifiers for such agents.
  • Yet another object of the invention is to provide new substances which improve the absorptivity of paper.
  • Another object of the invention is to provide outstandingly etfective rewetting agents for fibrous materials, particularly for textile fibrous materials, i.e. substances which impart to the fibrous material treated therewith the property of being wetted again very rapidly with water or aqueous liquids after the material has been dried.
  • R denotes an aliphatic hydrocarbon radical particularly an alkyl or alkenyl radical having eight to twenty. preferably tweleve to eighteen, carbon atoms
  • R denotes a hydrogen atom
  • R denotes a hydrogen atom
  • X denotes the anion of an inorganic or organic acid
  • n denotes the valency of this anion which is preferably from 1 to 4.
  • R denotes an aliphatic hydrocarbon radical having eight to twenty, preferably twelve to eighteen, carbon atoms and R denotes a hydrogen atom or an aliphatic hydrocarbon radical having one to four carbon atoms is reacted with glycidamide in a molar ratio of from 1:1 to 1:2 and the intermediate obtained is allowed to react with an inorganic or organic acid or with a quaternizing agent which introduces an aliphatic hydrocarbon radical, particularly an alkyl or alkenyl radical having one to four, preferably one or two, carbon atoms or an aromaticaliphatic hydrocarbon radical, particularly an aralkyl or aralkenyl radical having seven to twelve carbon atoms, preferably a benzyl radical.
  • the hydrocarbon radicals R and R in Formula 11 may be linear or branched, saturated or unsaturated.
  • the starting material for the process according to this invention may be a single amine having the Formula II or a mixture of amines such as are recovered from natural fats or by amination of oxoalcohols.
  • amines having the Formula II are octaylamine, decylamines, dodecyl amine, tridecylarnine, tetradecylamine, palmitylamine, stearylamine, methylstearylamine, oleylamine, ethyl palm kernel oil amine, arachylamine and coconut oil amine.
  • the primary amines, i.e. those in which R denotes a hydrogen atom, are preferred.
  • Amines having the Formula II are reacted (by known methods for the addition of amines to epoxy compounds) with glycidamide in a molar ratio of from 1:1 to 1:2. It has proved to be very suitable to place the glycidamide in the form of a to 50% aqueous or alcoholic solution, preferably in solution in methanol, in a reactor and to add to it at from to 80 C. the amine having the Formula II with or Without a solvent. As a rule the reaction lasts from one hour to five hours. The end of the reaction can be ascertained by oxirane determination in the reaction mixture.
  • the intermediate having the Formula III is converted in the second stage of the process according to this invention by a conventional method into either its secondary or tertiary ammonium salts (Formula I with both R and R denoting hydrogen atoms or with R alone denoting a hydrogen atom) with either an inorganic or organic acid, or into its tertiary or quaternary ammonium salts (Formula I with only R denoting a hydrogen atom or with both R and R denoting other than hydrogen atoms) with a quaternizing agent.
  • the reaction may be carried out under the conditions given for the first stage of the process by direct addition of the amount of acid or quaternizing agent theoretically required to the reaction mixture after the first stage of the process is over. It is also possible however first to isolate the intermediate having the Formula III, to dissolve it again in water and/ or alcohol, preferably in methanol, to form a 10 to 50% solution and then to add the acid or quaternizing agent to the solution at from 30 to 80 C.
  • the acids used for the second stage of the process are preferably strong or medium strength inorganic or organic acids, for example sulfuric acid, nitric acid, phosphori acid, hydrobromic acid, hydrochloric acid, formic acid, oxalic acid, maleic acid, citric acid, nitrilotriacetic acid, ethylenediaminotetracetic acid and acetic acid.
  • strong or medium strength inorganic or organic acids for example sulfuric acid, nitric acid, phosphori acid, hydrobromic acid, hydrochloric acid, formic acid, oxalic acid, maleic acid, citric acid, nitrilotriacetic acid, ethylenediaminotetracetic acid and acetic acid.
  • quaternizing agents are alkyl, alkenyl or aralkyl esters of strong acids.
  • alkyl, alkenyl, aralkyl and aralkenyl chlorides, bromides and iodides such as methyl chloride, ethyl chloride, methyl iodide, n-butyl iodide, allyl chloride, methallyl chloride, benzyl chloride and benzyl bromide, benzyl chloride bearing methyl or ethyl groups as nuclear substituents, phenylallyl bromide, dialkyl esters of sulfuric acid such as diethyl sulfate, methylethyl sulfate, methyl n-dodecyl sulfate and preferably dimethyl sulfate and esters of p-toluenesulfonic acid, such as methyl p-toluenesulfonate.
  • bromides and iodides such as methyl chloride, ethyl chloride, methyl io
  • the anion in the substances having the Formula I obtained from the intermediates (III) may be replaced by any other anion by precipitating the hydroxide of the' substance (I) by adding an alkali metal hydroxide to an aqueous solution of the substance (I), filtering it off, washing it and then dissolving it in the desired acid to form the salt.
  • the anion in a substance having the Formula I may be exchanged by reacting a substance having the Formula I which is dissolved in a solvent with an acid which forms a salt which is sparingly soluble in this solvent.
  • the anion which has been introduced by reaction of the intermediate (III) is left in the substance having the Formula I. This is particularly advantageous because in general the anion has only a minor effect on the properties of the substance having the Formula I.
  • the substances having the Formula I are valuable fatliquoring auxiliaries for leather and also outstanding emulsifiers in the production of cationic fat-liquoring agents for leather. They are eminently suitable for increasing the absorptivity of paper and as flotation agents for the dressing of ores.
  • Substances having the formed (I), particularly those in which R denotes CH CH(OH)CONH moreover have the advantage on account of their strong hydrophilic property that they are capable of forming relatively highly concentrated aqueous solutions which still have low viscosity at room temperature even With a content of active substance of 30% and which can be diluted at will for use by pouring in water without heating.
  • Commercially available cationic brightening agents on the other hand form more or less thick pastes in aqueous solutions from an active substance content of about 15% and these pastes have to be carefully dissolved in hot Water to convert them into formulations ready for use.
  • the agents are generally applied to the fibrous material from aqueous solution by single or repeated dipping, padding or spraying.
  • Aqueous solutions which contain from 0.1 to 10 grams per liter of substances having the Formula I have proved to be very suitable.
  • Fibrous materials which may be successfully treated with the substances having the Formula I include especially textile material of any organic fibrous material, for example of hydrophilic fibers such as cotton and rayon staple fiber, of hydrophobic fibers such as polyamide, polyester, polyacrylonitrile, cellulose ester and olefin fibers and mixtures of such fibers.
  • hydrophilic fibers such as cotton and rayon staple fiber
  • hydrophobic fibers such as polyamide, polyester, polyacrylonitrile, cellulose ester and olefin fibers and mixtures of such fibers.
  • the product (I) is obtained sometimes as crystals and sometimes in pasty form.
  • the yields (percent) are given under Y and the melting points under M.P., d. denoting decomposition.
  • CH2CH(OH)C ONH2 (see Example 4) is dissolved in 1700 parts of methanol and twice the molar amount of commercial perchloric acid is added. A precipitate is formed which is filtered 01f, washed with methanol and dried. It consists of 530 parts (95% of the theory) of a substance having the formula:
  • R denotes a mixture of alkyl radicals from coconut oil amine (C to C mainly C and C (see Example 13).
  • LH -GEHOED-C ONH2 (see Example 4) at a liquor ratio of :1 for ten minutes at C., and then hydroextractcd and dried at 80 C.
  • a material is obtained which has a soft, pleasant handle and whose rewettability and consequently absorptivity have only undergone insignificant change as compared with unbrightened material.
  • the known method of laying a specimen on the surface of water is used as a measure of the rewettabil ity.
  • Test material treated with the methosulfate of the triethanolamine ester of stearic acid to which the same amount has been applied floats on the surface of water even after five minutes without being wetted.
  • EXAMPLE 21 Cotton tricot, which has been bleached in known manner with bleaching powder liquor and hydrogen peroxide, is treated under the conditions specified in Example 20 with an aqueous solution of 0.3 g./liter of the substance having the formula:
  • the textile has a soft and smooth handle, is resilient and voluminous. Sumersion time is 5.2 seconds, that of an untreated specimen is 4.5 seconds.
  • a prior art cationic compound having comparable softening effect (obtained from 1 mole of oleylamine and 2 moles of ethylene oxide followed by quaternization with dimethyl sulfate) impairs the rewettability of this cotton tricot to such an extent that in the test for rewettability the test specimen is still floating on the surface of the water after five minutes.
  • EXAMPLE 22 Raw cotton towelling is treated with an aqueous solution of 0.5 g./ liter of the substance obtained accoding to Example 7 under the conditions specified in Example 20 and dried.
  • the material has a soft, agreeable handle and has become absorptive by the treatment.
  • the raw cotton fabric which has not been after-treated floats on the surface of water even after five minutes in the rewettability test owing to its content of cotton wax
  • a sample of the fabric treated in accordance with the invention sinks after tweny-five seconds.
  • EXAMPLE 23 Charmeuse of polycaprolactam fibers is treated under the conditions described in Example 20 with an aqueous solution of 1 g./liter of the substance obtained according to Example 2.
  • the treated textile material has a soft and smooth handle and is clearly superior in rewettability to an untreated comparison material for it sinks in the rewetting test after about ten seconds whereas the untreated material remains floating even after tWo minutes.
  • EXAMPLE 24 Cotton yarn in the form of X-spools is treated in a dyeing machine under the conditions described in Example 20 with an aqueous solution of 1 g./liter of the substance obtained according to Example 11.
  • the yarn treated in this way may be woven and knitted without trouble owing to the softness and smoothness brought about by the treatment. Owing to its pronounced hydrophilic character, the yarn is suitable for the production of tricot which after finishing off needs no additional finish with brightening or hydrophilic agents.
  • R n wherein R denotes an alkyl or alkenyl group having eight to twenty carbon atoms, R denotes a hydrogen atom, an alkyl group having one to four carbon atoms or the radical CH CH(OH)CO-NH R denotes a hydrogen atom, an alkyl or alkenyl group having one to four carbon atoms or an aralkyl or aralkenyl group having seven to twelve carbon atoms, X is chloride, bromide, iodide, mono-alkyl sulfate or the anion of sulfuric acid, nitric acid, phosphoric acid, formic acid, oxalic acid, maleic acid, citric acid, nitrilotriacetic acid, ethylenediaminetetracetic acid, acetic acid or p-toluene-sulfonic acid.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US776794A 1967-11-21 1968-11-18 Beta-carbamyl-beta-hydroxyethyl)-alkylammonium salts Expired - Lifetime US3632623A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DEB0095493 1967-11-21
DE19671643498 DE1643498A1 (de) 1966-09-24 1967-11-21 Neue Aminoalkohole und Verfahren zur Herstellung derselben
DE1643698 1967-11-21

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US (1) US3632623A (enrdf_load_stackoverflow)
BE (1) BE724247A (enrdf_load_stackoverflow)
FR (1) FR1592740A (enrdf_load_stackoverflow)
GB (1) GB1211040A (enrdf_load_stackoverflow)
NL (1) NL6816569A (enrdf_load_stackoverflow)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962332A (en) * 1974-12-11 1976-06-08 Celanese Corporation Bis-quaternary ammonium compounds and polymers
US4038303A (en) * 1971-04-16 1977-07-26 Colgate-Palmolive Company Quaternary ammonium carbamide compounds
US4039565A (en) * 1975-06-26 1977-08-02 Ashland Oil, Inc. Quaternized amidoamines
US4254053A (en) * 1978-07-10 1981-03-03 Claudio Cavazza Process for manufacturing D camphorate of L carnitinamide and D camphorate of D carnitinamide
US5584858A (en) * 1994-11-14 1996-12-17 United States Surgical Corporation Tubing fluid
US10595527B2 (en) 2017-12-12 2020-03-24 International Business Machines Corporation Antimicrobial polymers capable of supramolecular assembly
US10653142B2 (en) 2017-12-12 2020-05-19 International Business Machines Corporation Polymers with antimicrobial functionalities
US10667514B2 (en) 2017-12-12 2020-06-02 International Business Machines Corporation Antimicrobial ionene compositions with a variety of functional groups
US10687528B2 (en) 2017-12-12 2020-06-23 International Business Machines Corporation Antimicrobial polymers with enhanced functionalities
US10687530B2 (en) 2017-12-12 2020-06-23 International Business Machines Corporation Hydrophilic polymers with antimicrobial functionalities
US10743537B2 (en) * 2017-12-12 2020-08-18 International Business Machines Corporation Monomer compositions with antimicrobial functionality
US10836864B2 (en) 2017-12-12 2020-11-17 International Business Machines Corporation Chemical compositions with antimicrobial functionality

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4038303A (en) * 1971-04-16 1977-07-26 Colgate-Palmolive Company Quaternary ammonium carbamide compounds
US3962332A (en) * 1974-12-11 1976-06-08 Celanese Corporation Bis-quaternary ammonium compounds and polymers
US4039565A (en) * 1975-06-26 1977-08-02 Ashland Oil, Inc. Quaternized amidoamines
US4254053A (en) * 1978-07-10 1981-03-03 Claudio Cavazza Process for manufacturing D camphorate of L carnitinamide and D camphorate of D carnitinamide
US5584858A (en) * 1994-11-14 1996-12-17 United States Surgical Corporation Tubing fluid
US10687528B2 (en) 2017-12-12 2020-06-23 International Business Machines Corporation Antimicrobial polymers with enhanced functionalities
US10653142B2 (en) 2017-12-12 2020-05-19 International Business Machines Corporation Polymers with antimicrobial functionalities
US10667514B2 (en) 2017-12-12 2020-06-02 International Business Machines Corporation Antimicrobial ionene compositions with a variety of functional groups
US10595527B2 (en) 2017-12-12 2020-03-24 International Business Machines Corporation Antimicrobial polymers capable of supramolecular assembly
US10687530B2 (en) 2017-12-12 2020-06-23 International Business Machines Corporation Hydrophilic polymers with antimicrobial functionalities
US10743537B2 (en) * 2017-12-12 2020-08-18 International Business Machines Corporation Monomer compositions with antimicrobial functionality
US10836864B2 (en) 2017-12-12 2020-11-17 International Business Machines Corporation Chemical compositions with antimicrobial functionality
US11006628B2 (en) 2017-12-12 2021-05-18 International Business Machines Corporation Antimicrobial polymers capable of supramolecular assembly
US11058110B2 (en) 2017-12-12 2021-07-13 International Business Machines Corporation Polymers with antimicrobial functionalities
GB2583426B (en) * 2017-12-12 2022-07-27 Ibm Monomer compositions with antimicrobial functionality
US11525036B2 (en) 2017-12-12 2022-12-13 International Business Machines Corporation Chemical compositions with antimicrobial functionality
US11617367B2 (en) 2017-12-12 2023-04-04 International Business Machines Corporation Antimicrobial polymers capable of supramolecular assembly
US11723363B2 (en) 2017-12-12 2023-08-15 International Business Machines Corporation Polymers with antimicrobial functionalities

Also Published As

Publication number Publication date
FR1592740A (enrdf_load_stackoverflow) 1970-05-19
BE724247A (enrdf_load_stackoverflow) 1969-05-21
GB1211040A (en) 1970-11-04
NL6816569A (enrdf_load_stackoverflow) 1969-05-23

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