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WO1991017975A1 - Nouveaux composes contenant de l'azote, procede de preparation et d'utilisation de ces derniers - Google Patents

Nouveaux composes contenant de l'azote, procede de preparation et d'utilisation de ces derniers Download PDF

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Publication number
WO1991017975A1
WO1991017975A1 PCT/SE1991/000345 SE9100345W WO9117975A1 WO 1991017975 A1 WO1991017975 A1 WO 1991017975A1 SE 9100345 W SE9100345 W SE 9100345W WO 9117975 A1 WO9117975 A1 WO 9117975A1
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group
chr
alkyl
groups
compounds
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PCT/SE1991/000345
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English (en)
Inventor
Claes Göran AXBERG
Bengt-Arne Thorstensson
Jan Walding
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Berol Nobel Ab
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Application filed by Berol Nobel Ab filed Critical Berol Nobel Ab
Priority to BR919106444A priority Critical patent/BR9106444A/pt
Priority to JP3509626A priority patent/JPH0819619B2/ja
Publication of WO1991017975A1 publication Critical patent/WO1991017975A1/fr
Priority to NO924444A priority patent/NO924444D0/no
Priority to FI925300A priority patent/FI925300A/fi

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • 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
    • C07C229/10—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 acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/12—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 acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/40—Monoamines or polyamines; Salts thereof
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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

Definitions

  • New nitrogen containing compounds a process for their preparation and use of the compounds
  • the present invention relates to new tertiary amines and to new quaternary ammonium compounds. More particularly the invention relates to new such compounds which are characteristic in that they contain two longer hydrophobic hydrocarbon groups and at least one ester group which can be hydrolysed thereby conferring to the compounds a differ ⁇ ent ionic character than the original one.
  • the invention also relates to a method for the preparation of the new compounds, to the use of the compounds, among other things as conditioning agents for textiles, and to compositions containing the compounds.
  • Tertiary amines and quaternary ammonium compounds containing two longer hydrophobic hydrocarbon groups, alkyl and/or alkenyl groups are per se well-known ' compounds and known for use as, among other things, bactericides and textile softeners.
  • Didecyl dimethyl ammonium chloride is often used as bactericide and the compound most commonly used as textile softener is di-(hydrogenated tallow alkyl) dimethyl ammonium chloride, which has a very satisfactory textile softening effect.
  • Quaternary ammonium compounds of this type and the corresponding tertiary amines are, however, less advantageous from a biological point of view due to their slow degradation and to a certain toxicity to aquatic organisms.
  • the present invention relates to new tertiary amines and quaternary ammonium compounds which are characteristic in that they contain two longer hydrophobic hydrocarbon groups and at least one ester group which can be hydrolyzed and as hydrolysis product hereby confer to the nitrogen containing compounds another ionic character than the original one.
  • the nitrogen containing hydrolysis products have a substantially lower toxicity to aquatic organisms.
  • the present invention thus relates to new tertiary amines and quaternary ammonium compounds as defined in the patent claims.
  • the compounds can be characterized by the general formulae ), respectively,
  • R are alkyl or alkenyl groups having from 7 to 24 carbon atoms, or from 8 to 24 carbon atoms when the compounds do not contain groups A or other substituents, which can be straight or branched, and R j _ is an alkyl group with l to 4 carbon atoms.
  • the ester group —C(O)—0— ⁇ _ can be hydrolyzed to —C(0)—0 ⁇ whereby compounds of different ionic character are obtained.
  • the tertiary amines of formula (I) ⁇ containing the ester group are in themselves slightly cationic at normal pH values since they are protonated at a pH below about 9.
  • Compounds of ampholytic character, ie compounds which, dependent on the pH, have a net charge which is positive, zero or negative, are obtained at hydrolysis.
  • the quaternary ammonium compounds of formula (II) are cationic and give at the ester hydrolysis the corresponding struc ⁇ ture of betaine type, ie compounds of the formula
  • the new compounds can thus be used in the form wherein they have the desired affinity to the substrates which are considered by being cationic and then, after use, at a pH change be transformed into compounds which do not have cationic character and which thereby are considerably less toxic to aquatic organisms such as fish, daphnia, algae etc..
  • the compounds of the present invention have bac ⁇ tericidal and conditioning effect through the two groups R which are longer, straight or branched, alkyl and/or alkenyl groups.
  • the groups R can also be substituted and contain a hydroxyl group as a substituent and optionally also contain an ether bond.
  • the quaternary ammonium compounds are preferred.
  • the two groups R are both suitably alkyl groups with 7 to 12 carbon atoms, or 8 to 12 carbon atoms for compounds which do not contain groups A or other substituents.
  • the groups R are suitably alkyl or alkenyl groups with 13 to 22 carbon atoms, or from 14 to 22 carbon atoms for compounds which do not contain groups A or other substituents. It is of course
  • R groups can be technical mixtures of alkyl and/or alkenyl .group ' s with different number of carbon atoms originating from natural materials such as tallow, hydrogenated tallow, palm oil, coconut oil, palm kernel oil etc.. Another very suitable natural material is rapeseed oil which gives fatty acid groups with mainly C18 groups.
  • R]_ is an alkyl group with 1 to 4 carbon atoms, such as a methyl-, ethyl-, propyl- or isopropyl group.
  • the hydrocarbon chain between the nitrogen and the ester group in the compounds is the group -(CR'R , , ) n - where n is an integer of 1 to 4 and R' " and R' ' independent of each other are hydrogen, alkyl- or hydroxy ⁇ alkyl groups with 1 to 3 carbon atoms or hydroxyl groups.
  • the group -(CR'R 1 ') ! ⁇ - may also be a group substituted with an oxo group, and then preferably the group -(CH2 ⁇ C(0)- CH2)-.
  • the group -(CR'R'') n - is suitably a straight, unsub- stituted alkylene group with 1 to 4 carbon atoms or such a group substituted with an alkyl, hydroxyalkyl or hydroxyl group. It is preferred that the nitrogen atom in the compounds and the ester group in question are separated by a straight alkylene group with 1 to 4 carbon atoms and particularly by a ethylene group.
  • R2 is an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms. R is suitably a methyl group or a hydroxyethyl group, preferably a methyl group.
  • X in the quaternary ammonium compounds is an anion.
  • X can be any anion which does not have a negative influence on the effect of the compounds in the particular use of them.
  • Suitable anions are halides, especially chloride and bromide, alkyl sulfates such as methyl sulfate and ethyl sulfate, alkyl phosphates such as dimethyl phosphate.
  • Chloride ions are the preferred anions.
  • the tertiary amines can of course, as is conventional, be in the form of salts, of inorganic or organic acids, for example in the form of hydrochlorides or acetates.
  • a in the tertiary amines and the quaternary ammonium compounds represents a group containing an ester function or an amido function, which can be present in the com ⁇ pounds.
  • m is 0 or 1.
  • the compounds according to the invention can, if they contain groups A, contain one or two such groups.
  • the groups A can be four different types of groups containing an ester function or a group containing an amido function according to the following:
  • the quaternary ammonium compounds can also contain one A group which is an ester containing group and one A group which contains an amido function.
  • quaternary ammonium com ⁇ pounds containing a hydroxyl substituent can be mentioned compounds of formula [R ⁇ -CH(OH)-CH 2 ] (CR'R") n -C(0)-0-R 1 X " (III) wherein R x is an alkyl or alkenyl group with from 6 to 22 carbon atoms, and particularly those wherein R' and R' ' are hydrogen, n is 1, ⁇ _ and R2 and X are as earlier defined.
  • quaternary ammonium compounds containing ether bonds and hydroxyl groups can be mentioned those of formula [R-0-CH 2 -CH(OH)-CH 2 ] (CR'R' ' ) n -C(0)-0-R ⁇ X ⁇ (IV) wherein R is a previously defined and particularly those wherein R' and R' ' are hydrogen, n is 1, R ] _ and R2 and X are as earlier defined.
  • R is a previously defined and particularly those wherein R' and R' ' are hydrogen, n is 1, R ] _ and R2 and X are as earlier defined.
  • quaternary ammonium compounds containing an A group of type 5 ie an amido function, can be mentioned those of formula
  • the quaternary ammonium compounds are preferred, but all details on substituents etc. given above and in the following are of course also applicable to the amines. It is particularly preferred that the compounds contain a methyl group as group R j _, since it has been found that the compounds then undergo hydrolysis more rapidly thus giving more rapid toxicity decrease. At the preparation of the compounds a certain trans-esterification will occur so that the product may also contain R ⁇ _ groups originating from the used solvent, such as isopropyl groups or ethyl groups. By use of eg shorter reaction times, lower temperatures etc transesterification can be controlled and yield of product with desired group increased.
  • R j _ group in compounds can also be obtained using solvent giving trans-esterification with the same R ⁇ _ group.
  • the reaction can be carried out at temperatures of from about 50°C to about 150°C and during times of from about 12 hours to about 48 hours.
  • the reaction is suitably carried out in a solvent selected from groups lower alcohols, such as ethanol and isopropanol, glycols, polyglycols and glycol ethers.
  • the tertiary amines can be used as such, or in the form of salts, for the given purposes.
  • the tertiary amines are also intermediates for the preparation of the quaternary ammonium compounds according to the invention.
  • the tertiary amines can hereby be quater- nized, with conventional quaternizing agents such as methyl chloride, methyl bromide, dimethyl sulfate, diethyl sul ⁇ fate, to quaternary ammonium compounds of formula II.
  • the quaternary ammonium compounds can be prepared from tertiary amines of the formula [R-(A) m ]2-NR2 which are quaternized by reaction with an alkyl ester of haloalkanoic acid, or substituted haloalkanoic acid, of the formula X-(CR'R' ' ) n COOR ⁇ _, wherein R]_, R' , R' ' and n have the above given definitions and X is a halogen, preferably chlorine.
  • Suitable reaction conditions and solvents are those given for the reaction between secondary amine and alkyl ester of unsaturated carboxylic acid. The reaction times can, however, usually be kept within the range of from about 2 hours to about 24 hours.
  • reaction between methyl imino diacetic acid and a fatty alcohol for groups A of type 1) reaction between methyl diethanol amine and fatty acids, or fatty acid esters, such as methyl esters or triglycerides, for groups A of type 2) and reaction between methyl diethanol amine and fatty alkyl chloroformiate for group A of type 3) .
  • Quaternary ammonium compounds of formula (III) can for example be prepared by reacting a lower alkylamine, for example methylamine, with ⁇ -epoxides with longer aliphatic groups and subsequent quaternization of the obtained tertiary amine with alkyl ester of haloalkanoic acid, or substituted haloalkanoic acid.
  • Quaternary ammonium compounds of formula (IV) can be prepared by reaction between fatty alcohol and epichloro- hydrin. The obtained reaction product is then reacted with lower alkylamine followed by quaternization with alkyl ester of haloalkanoic acid, or substituted haloalkanoic acid.
  • Quaternary ammonium compounds of formula (V) can for example be prepared by the reaction of aminoethyl ethanol amine or diethylene triamine and fatty acids or fatty acid esters, such as methyl esters or triglycerides. The thus obtained reaction product is then reacted with ethylene oxide and is subsequently quaternized with an alkyl ester of a haloalkanoic acid, or substituted haloalkanoic acid.
  • Quaternary ammonium compounds of formula (VI) can for example be synthesized by reaction between epichlorohydrin and fatty acids or fatty acid esters, eg methyl esters or triglycerides.
  • Quaternary ammonium compounds containing a group -(CR'R'') n - which is sub ⁇ stituted with an oxo group, preferably the group -(CH2- C(0)-CH 2 )-, can be produced by reaction of a dialkyl methyl amine with methyl-4-halo-3-oxo-butanoate. At the production of the present amines and quaternary ammonium compounds a certain hydrolysis of the formed ester product may occur.
  • the present compounds can thus be used as produced, ie as obtained reaction mixture containing hydrolysis product.
  • the invention also relates to reaction mixture products produced as disclosed above.
  • the obtained reaction mixture products can also contain amines or quaternary ammonium compounds, respectively, which do not contain the ester group, as the compounds of the present invention do.
  • the presence of such compounds do not have a negative influence on the effect at use, but it is of course desired to suppress the amounts of such compounds in order to get as good properties as possible with regard to environmental properties, ie degradation and toxicity.
  • the present invention also relates to the use of the ertiary amines, the quaternary ammonium compounds and the reaction mixture products of the above given definitions as bactericides and as conditioning agents, ie as agents whic confer antistatic and/or softening effect.
  • conditioning agents ie as agents whic confer antistatic and/or softening effect.
  • conditioners the compounds are primarily used for textile materials, and especially for the softening effect they give, but they ca also be used in hair care products, in which a softenin and/or antistatic effect is often desired.
  • R are alkyl groups with 7 to 12, or 8 to 12
  • carbon atoms are preferably used, while it for use as conditioners is preferred to use such compounds in which the R groups are alkyl and/or alkenyl groups with 13 to 22, or 14 to 22, carbon atoms.
  • the compounds are employed in conventional manner in the given fields of utilization.
  • the compounds can be used for example in the food industry and in hospitals for disinfection of equip- ment. They are hereby used in aqueous solutions and often combined with nonionic tensides in order that also a cleaning effect will be obtained.
  • the compounds are used as conditioners for textile materials they.are like ⁇ wise used in conventional manner.
  • Textile softeners are normally added to the rinsing water after washing in the form aqueous or water/solvent containing formulations, to a dosage corresponding to up to about 5 g active substance per kg dry material, and allowed to have effect on the textile materials during shorter periods of time, usually from 5 to 10 minutes.
  • the compounds according to the invention should suitably at use be added by means of an aqueous formulation which has a pH value not exceeding 4.5.
  • the pH is suitably within the range of from 2.0 to 4.5 and preferably within the range from 2.5 to 4. At these pH values the compounds are essentially present in the form in which they have affinity to the treated materials, as discussed above.
  • the invention also relates to compositions containing the new compounds which are particularly suitable for use as textile softeners.
  • the compositions are water and/or solvent containing formulations containing the active compounds, suitably in an amount of at least 1 per cent by weight.
  • the compositions can either be concentrated pro ⁇ ducts which contain higher amounts of active substance, suitably from about 50 to about 90 per cent by weight, in solvent or a mixture of water and solvent.
  • Solvents are here primarily such which have been used at the preparation of the compounds, ie lower alcohols, such as ethanol and isopropanol, glycols, polyglycols and glycol ethers, or other suitable solvents, inert or others, as discussed earlier.
  • the compositions can also be diluted products intended for direct used.
  • compositions in this case suitably contain the compounds in amounts of from 1 to about 40 per cent by weight and are aqueous formulations, which may also contain solvents, suitably such as mentioned above, in smaller amounts, such as up to 20 per cent by weight based on the combination of active substance and water.
  • Compositions containing water or water and solvent should suitably have the above given pH values so that the compounds will not undergo any substantial hydrolysis in the compositions. At dilution with water a pH below 4.5 is usually obtained.
  • Mineral acids such as hydrochloric acid and sulfuric acid, as well as organic acids, such as for example lactic acid, citric acid and benzoic acid, can be added to adjust the pH to the desired value.
  • the composi ⁇ tions containing water or water and solvent can of course also contain other per se known softeners and for this type of product conventional additives such as emulsifiers, vis ⁇ cosity modifiers which for example can be inorganic elec- trolytes such as sodium chloride or calcium chloride, dye, perfumes, foam suppressing agents, optical brighteners etc
  • emulsifiers for example can be inorganic elec- trolytes such as sodium chloride or calcium chloride, dye, perfumes, foam suppressing agents, optical brighteners etc
  • vis ⁇ cosity modifiers which for example can be inorganic elec- trolytes such as sodium chloride or calcium chloride, dye, perfumes, foam suppressing agents, optical brighteners etc
  • the invention is further illustrated in the following examples. Parts and per cent relate to parts by weight and per cent by weight, respectively, unless otherwise stated.
  • the resulting product had a total amine number of less than 1 compared to 50.9 for the original amine/isopropanol mixture, a dry solids content of 75.6% and contained 25.4% dialkylbetaine iso- propyl ester, 20.0% dialkylbetaine methyl ester, 5.6% dialkylbetaine and 3.6% unreacted dialkyl methyl amine.
  • Example 2
  • the softening effect of the reaction product in example 1 was evaluated by treating clean cotton terry towels with aqueous dispersions of the reaction product and with di-(hydrogenated tallow alkyl) dimethyl ammonium chloride (DHTDMAC) , respectively.
  • the dispersions contained an amount of product corresponding to 0.5 grams of dry• substance per kg of textiles.
  • the treatment of the towels was carried out under agitation during 5 minutes, after which time the towels were dried.
  • a reference sample was included, treated in the same way as above, but with pure water only.
  • Example 3 A part of the reaction product in example 1 was hydrolysed by dispersion in water at a concentration of 5% dry substance and subsequently increasing the pH of the dispersion to 10 and the temperature to 60°C for 2 hours.
  • the organic material now containing the dialkyl betaine and only trace amounts of the dialkyl betaine ester, was then extracted into an organic phase, separated off, evaporated to dryness and diluted with isopropyl alcohol to
  • the reaction product was cooled down and a further 123 grams of isopropanol were added, giving a product with a dry solids content of 75.3% and containing 16.0% dialkylbetaine isopropyl-ester, 32.3% dialkylbetaine methyl ester, 4.5% dialkylbetaine and 2.7% unreacted dialkyl methyl amine.
  • the product in example 6 was tested for acute toxi ⁇ city to Rainbow Trout (Oncorhynchus mykiss) in a semistatic test according to OECD Guideline No 202, and was found to have a 96 hours LC 5Q value as high as 19 ppm.
  • This example shows a simulated primary degradation.
  • An aqueous dispersion made from the reaction product in example 6 and containing 0.5% dry solids was adjusted to pH 7 with a potassium hydroxide solution and was kept at that pH by means of a pH-stat unit providing intermittent addition of potassium hydroxide solution as needed to keep the pH constant. Samples were taken at intervals and the relative amounts of dialkyl betaine and dialkyl betaine esters were determined. The results were as follows:
  • This example shows the preparation of a quaternary ammonium compound containing a group A containing an ester group.
  • 105.8 grams of a diester amine obtained by reaction of 1 mole of methyl diethanol amine and 1.85 moles of tallow fatty acid and with a total amine number of 66.0 were mixed with 48 grams of isopropyl alcohol in a closed reactor.
  • 30 grams of the methyl ester of monobromo acetic acid were added.
  • the temperature was increased to 60°C and the temperature was then kept con ⁇ stant for 20 hours. At this point a further 0.6 grams of methyl ester of monobromo acetic acid were added and the reaction continued for 5 hours.
  • the total amine number of the reaction product was then 3.6 compared to 45.4 for the initial amine/isopropanol mixture.
  • the reaction mixture obtained in example 10 was evapo ⁇ rated under vacuum to total dryness and subsequently diluted with isopropanol to 50% dry solids content.
  • the bactericidal effect of this product against Escherichia coli NCTC 8196 was then evaluated in a modified B.S. 3286 suspension test in an aqueous medium containing 300 ppm hardness according to A.O.A.C. (Official Methods of Analysis of the Association of Official Analytical Chemists). It was found that a kill in excess of 99.999% was obtained at a dosage level of 100 ppm of active matter as dry solids.
  • This example shows the preparation of pure methyl ester quaternary ammonium compound.
  • 152 grams of di- (hydrogenated tallow alkyl) methyl amine with a total amine number of 71.6 mg HCl/g were mixed with 83 grams of methanol. The mixture was then heated to 60°C and 42 grams of monochloro acetic acid methyl ester were added. The temperature was increased to about 90°C and the reaction mixture was refluxed for 11 hours, after which time additionally 2 grams of monochloro acetic acid methyl ester were added and the reaction mixture was refluxed for another 2 hours.
  • the resulting product had a total amine number of 3.7, a dry solids content of 68.9% and contained 60.9% dialkylbetaine methyl ester, 2.5% dialkylbetaine and 2.8% unreacted dialkyl methyl amine.
  • Example 13
  • Example 13 0.75 ppm
  • Example 15
  • This example shows the preparation of a quaternary ammonium compound of formula (VI).
  • 12.4 grams of methyl amine (as 33% in ethanol) were added slowly during 3 hours while the temperature was kept between 45 and 60°C.
  • the tempera ⁇ ture was then kept at 60°C during 4 hours, at which time additionally 0.22 grams of methyl amine (as 33%) were added and the reaction was continued for another 4.5 hours.
  • the obtained reaction mixture containing the desired di-(3- alkoxy-2-hydroxypropyl) methyl amine had a total amine value of 42.1 mg HCl/g.
  • reaction product obtained 20 grams of the above obtained reaction product were mixed with 5.8 grams of isopropanol and heated to 80°C and then 3.36 grams of monochloro acetic acid methyl ester were added. The mixture was refluxed at 90°C for 10 hours, after which time an additional 0.26 grams of monochloro acetic acid methyl ester were added and the reaction mixture was refluxed for further 3 hours.
  • the reaction product obtained had a total amine number of 3.6 mg HCl/g.

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  • Pyridine Compounds (AREA)

Abstract

L'invention concerne des composés d'amines tertiaires et des composés d'ammonium quaternaire qui se caractérisent par le fait qu'ils contiennent deux plus longs groupes alkyle ou alcényle et au moins un groupe ester qu'on peut hydrolyser et qui peut donc conférer aux composés un caractère ionique différent de celui d'origine. Les composés d'amines tertiaires et les composés d'ammonium quaternaire sont utiles, entre autre choses, en tant que bactéricides et assouplissants pour les textiles. Les composés d'amines tertiaires et les composés d'ammonium quaternaire correspondent respectivement aux formules générales (I) et (II), où R représente un groupe alkyle ou alcényle droit ou ramifié ayant de 7 à 24 atomes de carbone, R1 représente un groupe alkyle ayant de 1 à 4 atomes de carbone, n est un entier variant de 1 à 4 et R' et R'' représentent indépendamment l'un de l'autre, hydrogène, des groupes alkyle ou des groupes hydroxy-alkyle ayant de 1 à 3 atones de carbone ou des groupes hydroxyle, m vaut 0 ou 1 et A représente un groupe renfermant ester ou un groupe contenant une fonction amido et est un groupe 1) -(O-CH2-CHR''')p-O-C(O)-(CH2)q-, 2) -C(O)O-CHR'''-CH2-(O-CHR'''-CH2)p-, (3) -(O-CH2-CHR''')p-O-C(O)-O-CHR'''-CH2-(O-CHR'''-CH2)p-, (4) -C(O)-O-CH2-C(OH)H-CH2- ou 5) -C(O)-NH-(CH2)z-, dans lequel R''' représente hydrogène ou un groupe méthyle, p varie de 0 à 5, q vaut 1 ou 2 et z vaut 2 ou 3, ce qui fait que, par conséquent, le nombre total de groupes alkylénéoxyde dans les groupes de type 3 ne dépasse pas 5, R2 représente un groupe alkyle ou hydroxyalkyle ayant de 1 à 4 atomes de carbone et X représente un anion.
PCT/SE1991/000345 1990-05-23 1991-05-15 Nouveaux composes contenant de l'azote, procede de preparation et d'utilisation de ces derniers WO1991017975A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR919106444A BR9106444A (pt) 1990-05-23 1991-05-15 Minas terciarias e compostos de amonio quaternario,processo para a preparacao da mistura da reacao contendo solvente e composicoes contendo agua e/ou solvente
JP3509626A JPH0819619B2 (ja) 1990-05-23 1991-05-15 繊維製品の柔軟剤組成物およびそれを用いた繊維材料の柔軟化方法
NO924444A NO924444D0 (no) 1990-05-23 1992-11-18 Nitrogeninneholdende forbindelser, fremgangsmaate ved deres fremstilling og anvendelse av forbindelsene
FI925300A FI925300A (fi) 1990-05-23 1992-11-20 Nya kvaevehaltiga foereningar, foerfarande foer deras framstaellning och anvaendning av foereningarna

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9001862-3 1990-05-23
SE9001862A SE9001862D0 (sv) 1990-05-23 1990-05-23 Nya kvaeveinnehaallande foereningar, foerfarande foer deras framstaellning samt anvaendning av foereningarna

Publications (1)

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WO1991017975A1 true WO1991017975A1 (fr) 1991-11-28

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EP (1) EP0530278A1 (fr)
JP (1) JPH0819619B2 (fr)
CN (1) CN1056682A (fr)
AU (1) AU7904291A (fr)
BR (1) BR9106444A (fr)
CA (1) CA2083503A1 (fr)
FI (1) FI925300A (fr)
HU (1) HU9203660D0 (fr)
SE (1) SE9001862D0 (fr)
WO (1) WO1991017975A1 (fr)
ZA (1) ZA913719B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993025648A1 (fr) * 1992-06-10 1993-12-23 The Procter & Gamble Company Compositions et composes adoucissants, biodegradables et stables, pour tissus
FR2695800A1 (fr) * 1992-09-23 1994-03-25 Inst Textile De France Composé antiseptique.
EP0643128A1 (fr) * 1993-09-10 1995-03-15 Kao Corporation Compositions adoucinants aqueuses, nouveau sel d'ammonium quaternaire et procédé pour la préparation de ce sel
WO1996003970A1 (fr) * 1994-08-05 1996-02-15 Witco Corporation Compositions traitantes quaternaires biodegradables pour les cheveux et la peau

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Publication number Priority date Publication date Assignee Title
DE2708823A1 (de) * 1976-04-13 1977-11-03 Dyk & Co Inc Van Quarternaere fettsaeurehalogenalkanoate von dialkylaminopropylamiden
EP0021431A2 (fr) * 1979-07-03 1981-01-07 Hoechst Aktiengesellschaft Di-esters quaternaires d'alkylamino-di-alkyl-acides carboxyliques, procédé pour leur préparation et leur utilisation
DE2936121A1 (de) * 1979-09-07 1981-03-26 Hoechst Ag, 65929 Frankfurt Quaternaere ester von hydroxialkylamidoaminen, verfahren zu deren herstellung und deren verwendung als waescheweichspuelmittel
DE3505269A1 (de) * 1985-02-15 1986-08-21 Hoechst Ag, 6230 Frankfurt Quarternaere alkylamidobetainester, ein verfahren zu ihrer herstellung und ihre verwendung in waescheweichspuelmitteln
GB2188653A (en) * 1986-04-02 1987-10-07 Procter & Gamble Biodegradable fabric softeners
EP0353580A2 (fr) * 1988-08-05 1990-02-07 Th. Goldschmidt AG Procédé pour la préparation de solutions aqueuses fluides concentrées de bétaine

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2708823A1 (de) * 1976-04-13 1977-11-03 Dyk & Co Inc Van Quarternaere fettsaeurehalogenalkanoate von dialkylaminopropylamiden
EP0021431A2 (fr) * 1979-07-03 1981-01-07 Hoechst Aktiengesellschaft Di-esters quaternaires d'alkylamino-di-alkyl-acides carboxyliques, procédé pour leur préparation et leur utilisation
DE2936121A1 (de) * 1979-09-07 1981-03-26 Hoechst Ag, 65929 Frankfurt Quaternaere ester von hydroxialkylamidoaminen, verfahren zu deren herstellung und deren verwendung als waescheweichspuelmittel
DE3505269A1 (de) * 1985-02-15 1986-08-21 Hoechst Ag, 6230 Frankfurt Quarternaere alkylamidobetainester, ein verfahren zu ihrer herstellung und ihre verwendung in waescheweichspuelmitteln
GB2188653A (en) * 1986-04-02 1987-10-07 Procter & Gamble Biodegradable fabric softeners
EP0353580A2 (fr) * 1988-08-05 1990-02-07 Th. Goldschmidt AG Procédé pour la préparation de solutions aqueuses fluides concentrées de bétaine

Non-Patent Citations (1)

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Title
PATENT ABSTRACTS OF JAPAN, Vol. 13, No. 156, C585, Abstract of JP 63-312399, publ. 1988-12-20 (KAO CORP). *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993025648A1 (fr) * 1992-06-10 1993-12-23 The Procter & Gamble Company Compositions et composes adoucissants, biodegradables et stables, pour tissus
FR2695800A1 (fr) * 1992-09-23 1994-03-25 Inst Textile De France Composé antiseptique.
EP0643128A1 (fr) * 1993-09-10 1995-03-15 Kao Corporation Compositions adoucinants aqueuses, nouveau sel d'ammonium quaternaire et procédé pour la préparation de ce sel
US5476597A (en) * 1993-09-10 1995-12-19 Kao Corporation Liquid softener composition, novel quaternary ammonium salt, and process for the preparation of said salt
US5580481A (en) * 1993-09-10 1996-12-03 Kao Corporation Aqueous fabric softener composition, novel quaternary ammonium salt, and process for the preparation of said salt
WO1996003970A1 (fr) * 1994-08-05 1996-02-15 Witco Corporation Compositions traitantes quaternaires biodegradables pour les cheveux et la peau
US5552137A (en) * 1994-08-05 1996-09-03 Witco Corporation Biodegradable quaternary hair conditioners
US5610187A (en) * 1994-08-05 1997-03-11 Witco Corporation Biodegradable quaternary hair and skin conditioners

Also Published As

Publication number Publication date
EP0530278A1 (fr) 1993-03-10
SE9001862D0 (sv) 1990-05-23
JPH0819619B2 (ja) 1996-02-28
AU7904291A (en) 1991-12-10
BR9106444A (pt) 1993-05-18
HU9203660D0 (en) 1993-03-29
FI925300A0 (fi) 1992-11-20
CA2083503A1 (fr) 1991-11-24
JPH05505621A (ja) 1993-08-19
FI925300A (fi) 1992-11-20
CN1056682A (zh) 1991-12-04
ZA913719B (en) 1992-02-26

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