EP0043046A1 - Utilisation de polyhydroxyalcoylpolyamines pour l'adoucissement du tissu - Google Patents

Utilisation de polyhydroxyalcoylpolyamines pour l'adoucissement du tissu Download PDF

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Publication number
EP0043046A1
EP0043046A1 EP19810104719 EP81104719A EP0043046A1 EP 0043046 A1 EP0043046 A1 EP 0043046A1 EP 19810104719 EP19810104719 EP 19810104719 EP 81104719 A EP81104719 A EP 81104719A EP 0043046 A1 EP0043046 A1 EP 0043046A1
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EP
European Patent Office
Prior art keywords
acid
group
polyhydroxyalkyl
epoxyalkane
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19810104719
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German (de)
English (en)
Inventor
Horst Dr. Rutzen
Hans-Ulrich Dr. Jäger
Martin Dr. Bischoff
Klaus Dr. Hachmann
Peter Dr. Nikolaus
Rolf Dr. Puchta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0043046A1 publication Critical patent/EP0043046A1/fr
Withdrawn legal-status Critical Current

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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

Definitions

  • the present invention relates to reaction products of epoxyalkanes with polyaminoalkanes, their salts with organic or inorganic acids and the addition products of alkylene oxide onto the reaction products or their salts.
  • the invention further relates to a process for the preparation of these compounds and their use as textile softeners.
  • the epoxyalkanes to be used as starting materials are available in large quantities. They are obtained in a known manner from the corresponding olefins or olefin mixtures.
  • the epoxyalkanes with a terminal epoxy group are obtained via 1,2-monoolefins, which are obtained, for example, by polymerizing ethylene with organic aluminum compounds as catalysts or by thermal cracking of paraffin hydrocarbons.
  • epoxyalkanes examples include the compounds 1,2-epoxyhexane, 1,2-epoxy-octane, -1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2- Epoxyoctadecane and 1,2-epoxyyeosan.
  • Epoxy mixtures are also suitable, such as C 12/14 -1,2-epoxy with approx. 70 weight percent C 12 - and approx. 30 weight percent C 14 -epoxyalkane or C 16/18 -1,2-epoxy with approx. 40 weight percent C16 and about 60 weight percent C 18 epoxyalkane.
  • the internal epoxyalkanes are obtained, for example, by epoxidizing olefins or olefin mixtures which are prepared by catalytic dehydrogenation or by chlorination / dehydrogenation of linear paraffin hydrocarbons. Monoolefins with an internal double bond can also be prepared by isomerization of X-olefins.
  • Suitable internal epoxyalkanes of a C 11/14 olefin fraction contain approx. 22% by weight of C 11 -, approx. 30% by weight of C 12 -, approx. 26% by weight of C 13 -, approx. 22% by weight of C 14 epoxy alkane.
  • a likewise suitable epoxyalkane mixture of a C 15/18 olefin fraction contains approximately 26 percent by weight of C 15 , approximately 35 percent by weight of C 16 , approximately 32 percent by weight of C 17 and approximately 7 percent by weight of C 18 epoxyalkane.
  • Preferred epoxyalkanes (a) have a terminal epoxy group, and particularly valuable polyhydroxyalkylpolyamines are obtained when starting from epoxyalkanes having 10 to 18, in particular 12 to 14, carbon atoms in the molecule.
  • Suitable polyaminoalkanes have two or more N-H groups in the molecule. These N-H groups are separated from one another by at least two carbon atoms, each N-H group having at least one N-H bond. This N-H bond enables the polyaminoalkanes to react with the epoxyalkanes.
  • Such polyaminoalkanes are commercially available products. The simplest compound of this type is ethylenediamine.
  • Preferred polyaminoalkanes are, for example, propylene diamine, diethylene diamine, dipropylene triamine, symmetrical methyl dipropylene triamine, triethylene tetramine, tripropylene tetramine and tetraethylene pentamine.
  • dipropylenetriamine is a particularly suitable compound.
  • the molar ratio in the reaction of epoxyalkanes (a) with polyaminoalkane (b) depends on the number of carbon atoms in the epoxyalkane molecule; it is generally between 5: 1 and 2: 1 for the ratio of (a): (b), with a ratio of about 5: 1 for the reaction of C 6 -epoxyalkane and for the reaction of C 14 - or longer chain epoxyalkane selects a ratio (a): (b) of about 2: 1 in order to obtain particularly suitable polyhydroxyalkyl polyamines.
  • the ratio (a): (b) lies between these two limit values.
  • Particularly interesting polyhydroxyalkyl polyamines are the products produced by reacting an epoxyalkane with 12 to 14 carbon atoms in the molecule and terminal epoxy group with dipropylenetriamine in a molar ratio of 2: 1.
  • polyhydroxyalkyl polyamines are mixed with an excess of organic or inorganic acid, excellent water-soluble salts of the polyhydroxyalkyl polyamines are obtained.
  • 1 to 5 acid equivalents preferably about 1 to 2 acid equivalents, are used per nitrogen atom in the polyaminoalkane used.
  • Suitable acids are, for example, formic acid, acetic acid, citric acid, tartaric acid, adipic acid, maleic acid, succinic acid, diglycolic acid, malic acid, lactic acid, amidosulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, of which formic acid is particularly preferred.
  • aqueous solution containing 8 percent by weight of polyhydroxyalkylpolyamine becomes clear; this is generally a number of equivalents of the above acids corresponding to the number of nitrogen atoms in the polyhydroxyalkylpolyamine molecule. In some cases, a lesser or greater amount of acid is required to achieve clear solubility.
  • Particularly interesting compounds are those polyhydroxyalkyl polyamine salts which have been prepared by reacting an epoxyalkane with 12 to 14 carbon atoms in the molecule and terminal epoxy group with dipropylenetriamine in a molar ratio of 2: 1 and in which the salt formation has been carried out with formic acid.
  • a further modification of the properties of the neutralized polyhydroxyalkyl polyamines is possible by adding alkylene oxide, in particular ethylene oxide and / or propylene oxide.
  • alkylene oxide in particular ethylene oxide and / or propylene oxide.
  • Compounds which are particularly balanced with regard to these properties contain at least 1 mol of ethylene oxide and / or propylene oxide per NH group of the polyhydroxyalkylpolyamine.
  • add-on compounds which are formed by reacting x mol of C12-C14 epoxyalkane with a terminal epoxy group Mol of dipropylenetriamine were prepared, with these reaction products being followed by 3 Mol ethylene oxide were added and finally the salt formation was carried out with 1.5 2 mol formic acid, particularly valuable properties.
  • Another object of the invention is a process for the preparation of the new compounds. This process is characterized in that 2 to 5 moles of epoxyalkane with 6 to 20 carbon atoms in the molecule and with terminal or internal epoxy group with 1 mole of polyaminoalkane with two or more NH groups in the molecule at temperatures between 60 and 250 ° C.
  • alkylene oxide When ethylene oxide and / or propylene oxide are added in the autoclave, about 1 mol of alkylene oxide is generally added per N-H group of the polyaminoalkane used for the reaction with the epoxyalkane. If you want to achieve pronounced effects, more moles of alkylene oxide can be added per nitrogen atom, with about 5, preferably about 3 to 4, moles of alkylene oxide per N-H group being an upper limit with regard to optimal properties of the new compounds.
  • ethylene oxide By adding ethylene oxide, the solubility of the compounds in water can be increased and the absorbency of the textiles treated with these compounds can be improved, while the softness of the treated textiles can be increased by adding propylene oxide. Both ethylene oxide and propylene oxide can be added to establish special combinations of properties.
  • the compounds are advantageously neutralized after the addition of alkylene oxide. As already mentioned, it is important that the temperature in the neutralization batch is not exceeded.
  • the salts of the polyhydroxyalkyl polyamines according to the invention and their alkylene oxide addition products dissolve in water in any concentration and form clear, stable solutions.
  • the solutions can also contain water-miscible solvents, e.g. short chain alcohols such as ethanol, isopropyl alcohol, propylene glycol or butylene glycol.
  • the pH of the solutions depends on the type and amount of the organic or inorganic acid used for salt formation. If textiles are treated with the compounds according to the invention in a washing or rinsing cycle or in a tumbler, they have a pleasantly soft feel and good electrostatic properties after drying. The absorbency of the treated textiles is excellent.
  • the use of the new compounds prepared by the process according to the invention as softening and antistatic agents is therefore a further subject of the invention, the application in concentrated or diluted form, e.g. for post-washing in commercial or household washing machines or in separate fleets.
  • the new compounds are used, for example, in a liquid laundry aftertreatment in amounts of 2 to 15, preferably 2 to 10 percent by weight of the new compounds, which are dissolved in a liquid carrier medium.
  • this agent can contain at least one further compound from the group of emulsifier, dye, fragrance, preservative, viscosity adjuster and possibly other customary additives.
  • nonionic surfactants are particularly suitable as emulsifiers. These include products that owe their hydrophilic properties to the presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, alkylolamide groups and, quite generally, an accumulation of hydroxyl groups.
  • Such nonionics contain at least one hydrophobic radical of 8 to 26, preferably 10 to 20 and in particular 12 to 18 carbon atoms in the molecule, and at least one nonionic water-solubilizing group.
  • the preferably saturated hydrophobic residue is usually aliphatic, possibly also alicyclic in nature; it can be connected to the water-solubilizing groups directly or via intermediate links. Intermediate links are e.g.
  • Benzene rings carboxylic acid ester or carbonamide groups, ether or ester-like residues of polyhydric alcohols, such as e.g. those of ethylene glycol, propylene glycol, glycerol or corresponding polyether esters.
  • ethylene oxide and / or glycide onto fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid or sulfonic acid amides, these nonionics being 4 to 100, preferably 6 to 40 and in particular 8 to 20 ether residues, especially May contain ethylene glycol ether residues per molecule.
  • propylene or butylene glycol ether residues or polyether chains can be present in these polyether chains or at their ends.
  • Nonionics also includes products obtained from water-insoluble polypropylene glycols or from water-insoluble propoxylated lower aliphatic alcohols containing 1 to 8, preferably 3 to 6 carbon atoms, or from water-insoluble propoxylated alkenediamines by ethoxylating them to water solubility.
  • Nonionics also include fatty acid or sulfonic acid alkylolamines, e.g. from mono- or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, e.g. derive the glycamine. They can be replaced by amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.
  • the capillary-active amine oxides include e.g. the products derived from higher tertiary amines containing a hydrophobic alkyl radical and two shorter alkyl and / or alkylol radicals each containing up to 4 carbon atoms.
  • suitable nonionic dispersants may also be water-soluble or water-emulsifiable or dispersible compounds which either do not contain any hydrophobic radicals in the sense of the nonionic surfactants described above, or in which the nature or the number of hydrophilic groups is sufficient to achieve one complete water solubility is not sufficient.
  • the former include e.g. solid or liquid polyethylene glycols, which can be regarded as condensation polymers of ethylene oxide with ethylene glycol or water, ethylene oxide adducts of glycerol and other polyalcohols, etc .; to the latter. belong e.g. Fatty acid partial glycerides or not or not completely water-soluble alkoxylation products, e.g. those with 2 to 5 ethylene glycol ether residues in the molecule.
  • Another possible use of the new compounds consists in a concentrated agent with 30 to 85 percent by weight of the new compounds, in combination with 5 to 25 percent by weight of an emulsifier and at least one further compound from the group of dye, perfume, preservative, viscosity adjuster, liquid carrier medium.
  • Water is primarily used as the liquid carrier medium, but alcoholic or aqueous / alcoholic carrier media which contain lower alcohols or glycols having 2 to 6 carbon atoms, such as ethanol, isopropanol, ethyl glycol monobutyl ether, or consist entirely of them are also possible.
  • These concentrated products can either be used in correspondingly small amounts for post-wash treatment in the last rinsing bath or they are used as base liquor batches to be diluted shortly before use.
  • Acidic additives include inorganic mineral acids and non-surfactant organic acids with 1 to 8 carbon atoms, e.g.
  • Amidosulfonic acid urea compounds of orthophosphoric acid, boric acid, oxalic acid, lactic acid, glycolic acid, citric acid, tartaric acid, benzoic acid, phthalic acid, gluconic acid, formic acid, acetic acid and propionic acid as well as benzene-, toluene- or xylene sulfonic acid, sulfoacetic acid or acidic acid or acidic acid or acidic acid acids.
  • Glycolic acid and citric acid are preferred acids because of their easy access and non-toxicity.
  • the polyhydroxyalkyl polyamines according to the invention can also be used in tumble aids. If you add a flexible sheet, for example made of nonwoven fabric or foam, which contains a suitable amount of the new compounds, to a batch of freshly washed damp laundry in the tumbler, the laundry is given a pleasant feel and excellent absorbency.
  • the fabrics can optionally contain auxiliaries and additives, such as contain other textile softening agents, emulsifiers, fragrances, preservatives, solvents, dyes, pigments or other substances customary in such agents.
  • the new compounds according to the invention can also have a softening effect in detergents and washing aids.
  • mild detergents containing about 2 to 15 percent by weight of these active ingredients clean and care for the laundry at the same time, giving them pleasant wearing properties.
  • Example 1 describes the preparation of a new compound according to the invention from 1,2-C 14 -epoxyalkane and dipropylenetriamine.
  • the main product solidified at room temperature to a semi-solid mass, which at 60 ° C turned into a clear melt.
  • the absorbency of the treated textiles was determined using the rising height method (DIN 53924).
  • so-called "Krefeld test fabric” which had previously been washed three times with a commercial heavy-duty detergent, was mixed with the new compounds in a concentration of 0.3 g per liter at a liquor ratio of 1:10 for 5 minutes in a launderometer with the addition of 10 Steel balls shaken per container.
  • Adhesive liquid was then largely removed by centrifuging (30 seconds) in a terry towel. The sample lobes were then air-conditioned for 24 hours at 23 ° C and 60 to 70 S relative humidity.
  • test results show that the new compounds according to the invention, with good softening performance, bring about a much better absorbency of the textiles treated therewith than a commercially known active ingredient.
  • compositions of concentrated fabric softening agents which are used either in this form in a correspondingly lower dosage or after prior dilution with water to, for example, 10 times the volume for post-washing in the washing cycle of commercial washing machines, household washing machines or in separate fleets.
  • a laundry softener in diluted form has the following composition, for example:
  • Impregnated with the active ingredient from Example 1 a viscose nonwoven fabric with low absorbency such that about 40 to 45 g of active ingredient are contained on the nonwoven per m 2 , and this impregnated nonwoven (about 3 50 cm 2 ) is added to a laundry item in the tumbler , the active ingredient is transferred to the laundry during the drying process and brings about a noticeable improvement in the softness of the items of laundry treated in this way.
  • a fabric softener that has a softening and excrusting effect has the following composition:
  • a mild detergent of the specified composition has excellent washing power and at the same time gives the washed textiles a pleasant feel with very good absorbency.

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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)
  • Detergent Compositions (AREA)
EP19810104719 1980-06-26 1981-06-19 Utilisation de polyhydroxyalcoylpolyamines pour l'adoucissement du tissu Withdrawn EP0043046A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803023947 DE3023947A1 (de) 1980-06-26 1980-06-26 Neue polyhydroxyalkylpolyamine, verfahren zu ihrer herstellung und ihre verwendung als textilweichmacher
DE3023947 1980-06-26

Publications (1)

Publication Number Publication Date
EP0043046A1 true EP0043046A1 (fr) 1982-01-06

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EP19810104719 Withdrawn EP0043046A1 (fr) 1980-06-26 1981-06-19 Utilisation de polyhydroxyalcoylpolyamines pour l'adoucissement du tissu

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EP (1) EP0043046A1 (fr)
JP (1) JPS5732253A (fr)
BR (1) BR8104025A (fr)
DE (1) DE3023947A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000015746A1 (fr) * 1998-09-15 2000-03-23 The Procter & Gamble Company Compositions de lavage et d'entretien des tissus comprenant des polyamines cycliques ou lineaires de faible poids moleculaire
WO2022140518A1 (fr) * 2020-12-23 2022-06-30 Ecolab Usa Inc. Adoucissants non cationiques et procédés d'utilisation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009001289A (ja) * 2007-06-19 2009-01-08 Kobe Bio Robotix Kk 蓋を有する容器および蓋着脱システム

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3956502A (en) * 1974-09-04 1976-05-11 Nalco Chemical Company Polyamine alcohols as microbiocides
FR2310342A1 (fr) * 1975-05-07 1976-12-03 Henkel & Cie Gmbh Melanges d'aminoalcanols, leur preparation et leur utilisation, notamment comme agents anticorrosion dans des carburants, des huiles ou des lubrifiants
US4049557A (en) * 1972-07-17 1977-09-20 Colgate-Palmolive Company Fabric conditioning compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049557A (en) * 1972-07-17 1977-09-20 Colgate-Palmolive Company Fabric conditioning compositions
US3956502A (en) * 1974-09-04 1976-05-11 Nalco Chemical Company Polyamine alcohols as microbiocides
FR2310342A1 (fr) * 1975-05-07 1976-12-03 Henkel & Cie Gmbh Melanges d'aminoalcanols, leur preparation et leur utilisation, notamment comme agents anticorrosion dans des carburants, des huiles ou des lubrifiants

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000015746A1 (fr) * 1998-09-15 2000-03-23 The Procter & Gamble Company Compositions de lavage et d'entretien des tissus comprenant des polyamines cycliques ou lineaires de faible poids moleculaire
US6525013B1 (en) 1998-09-15 2003-02-25 The Procter & Gamble Company Fabric care and laundry compositions comprising low molecular weight linear or cyclic polyamines
WO2022140518A1 (fr) * 2020-12-23 2022-06-30 Ecolab Usa Inc. Adoucissants non cationiques et procédés d'utilisation
US20220204889A1 (en) * 2020-12-23 2022-06-30 Ecolab Usa Inc. Non-cationic softeners and methods of use
US12600924B2 (en) * 2020-12-23 2026-04-14 Ecolab Usa Inc. Non-cationic softeners and methods of use

Also Published As

Publication number Publication date
BR8104025A (pt) 1982-03-16
JPS5732253A (en) 1982-02-20
DE3023947A1 (de) 1982-01-21

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Inventor name: HACHMANN, KLAUS, DR.

Inventor name: JAEGER, HANS-ULRICH, DR.

Inventor name: RUTZEN, HORST, DR.

Inventor name: PUCHTA, ROLF, DR.

Inventor name: NIKOLAUS, PETER, DR.

Inventor name: BISCHOFF, MARTIN, DR.