WO2001023394A1 - Organosilicon compounds with amido groups - Google Patents

Organosilicon compounds with amido groups Download PDF

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Publication number
WO2001023394A1
WO2001023394A1 PCT/EP2000/009492 EP0009492W WO0123394A1 WO 2001023394 A1 WO2001023394 A1 WO 2001023394A1 EP 0009492 W EP0009492 W EP 0009492W WO 0123394 A1 WO0123394 A1 WO 0123394A1
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Prior art keywords
radical
organosilicon compounds
formula
different
compounds according
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PCT/EP2000/009492
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German (de)
French (fr)
Inventor
Amit Kumar Paul
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Wacker-Chemie Gmbh
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Publication of WO2001023394A1 publication Critical patent/WO2001023394A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • 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
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
    • 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

  • the invention relates to organosilicon compounds containing amido groups, their preparation and their use.
  • Amino silicone emulsions or cationic plasticizers or mixtures thereof are usually used in the softening treatment of textiles and garments using the pull-out or padding process.
  • plasticizers are not only not readily biodegradable, but also have some undesirable effects on the textile after treatment, as discussed below:
  • the cationic plasticizer has a plasticizing effect, but is not permanently anchored to the textile.
  • these cationic plasticizers are inherently basic, which leads to the yellowing of the textile.
  • a conventional aminosilicone emulsion gives a good softening effect - and is permanently anchored to the fabric, but causes the fabric to yellow.
  • Mixtures of aminosilicone emulsion and cationic plasticizer show a good to medium plasticizing effect, but the high alkalinity of such mixtures also causes the textile to yellow.
  • mixtures of cationic plasticizers and conventional aminosilicone emulsions are anchored less well on the textile due to the cationic content.
  • the object was to provide organosilicon compounds which are suitable as plasticizers for textiles, give the textiles a soft feel, have good adhesion to the textiles, give the textiles good protection against ozone fading and do not cause yellowing of the textiles.
  • Another object was to provide organosilicon compounds which can be in both liquid and solid form, which are easily emulsifiable and which can form (micro) emulsions and which are biodegradable and environmentally friendly. The object is achieved by the invention.
  • the invention relates to organido silicon compounds of the general formula containing amido groups
  • R can be identical or different and denotes a monovalent hydrocarbon radical
  • Rl can be the same or different and hydrogen atom, one
  • Y can be the same or different and a radical of the formula
  • R 3 can be identical or different and is a hydrogen atom or an alkyl radical
  • R 4 is a divalent hydrocarbon radical
  • A is a radical R 3 or a radical F of the formula
  • R 2 may be the same or different and a monovalent saturated or unsaturated
  • Hydrocarbon radical having at least 15 carbon atoms, preferably of a fatty acid, z is 0 or an integer from 1 to 10, preferably 0 or 1, 2,
  • 3 is a is 0, 1, 2 or 3
  • c is 0, 1 or 2
  • d is 0, 1, 2 or 3, with the proviso that the sum of a, c and d in the units of the formula (I) is less than or equal to 3 and contains at least one radical Y with at least one radical F per molecule.
  • the invention further relates to a method for
  • R 5 may be the same or different and is a hydrogen atom or an alkyl radical, with the proviso that a hydrogen atom is bonded to at least one nitrogen atom in the radical X, b is 0, 1 or 2, with the proviso that the sum of a, b and d in the units of the formula (II) is less than or equal to 3 and at least one radical X is contained per molecule, with fatty acids (2), which have at least 16 carbon atoms, or glycerides of these fatty acids are reacted.
  • the radical R is preferably monovalent hydrocarbon radicals having 1 to 18 carbon atoms.
  • radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. -Butyl-, n-pentyl-, iso-pentyl-, neo-pentyl-, tert.
  • Pentyl radical hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radical, such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals , such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, octadecyl radicals, such as the n-octadecyl radical; Alkenyl radicals, such as the vinyl and allyl radicals, cycloalkyl radicals, such as cyclopentyl, cyclohexyl,
  • the radical R is preferably an alkyl radical with 1 to 4 carbon atoms. Examples of alkyl radicals R are
  • alkoxyalkyl radicals are the methoxyethyl and the ethoxyethyl radical.
  • the radical R 2 is preferably a monovalent saturated or unsaturated hydrocarbon radical with 15 to 27 carbon atoms, preferably 15 to 23 carbon atoms, particularly preferably 15 to 19 carbon atoms.
  • alkyl radicals R also apply in full to alkyl radicals R 3 and R 5 .
  • the radical R 4 is preferably a divalent one
  • radicals R 4 Hydrocarbon radical with 1 to 12 carbon atoms per radical.
  • radicals R 4 are the methylene, ethylene, propylene, butylene, cyclohexylene, octadecylene, phenylene and butenylene radical, where, in particular because of the easy accessibility, the ethylene and the n-propylene radical are preferred.
  • radicals X are examples of radicals X.
  • H 2 N (CH 2 ) 3 - H 2 N (CH 2 ) 2 NH (CH 2 ) 3 - are preferred.
  • radicals Y are therefore
  • organosilicon compounds according to the invention are preferably organopolysiloxanes.
  • the organosilicon compounds according to the invention preferably have a viscosity of 50 mPa's at 25 ° C to 100,000 mPas at 60 ° C, preferably 50 mPa 's at 25 ° C to 10,000 mPas at 60 ° C.
  • the organosilicon compounds according to the invention preferably have a molecular weight (M n ) of 500 to 1,000,000 g / mol, preferably 500 to 100,000 g / mol.
  • the organosilicon compounds according to the invention preferably have an amine number of 0.01 to 4.0 mequiv / g, preferably 0.1 to 2.0 mequiv / g.
  • the organosilicon compounds according to the invention can be in liquid form or in solid form, for example in waxy form.
  • R and X have the meaning given above, g is 0, 1 or 2, n is 0 or an integer from 1 to 1000, m is 0 or an integer from 1 to 100, with the proviso that at least one X is contained per molecule and the n-units (SiR2 ⁇ ) and the m-units (SiRXO) can be distributed as desired in the molecule.
  • Organopolysiloxanes of the general formula are therefore preferred as the organosilicon compound according to the invention
  • R and Y have the meaning given above, g is 0, 1 or 2, n is 0 or an integer from 1 to 1000, p is 0 or an integer from 1 to 100, with the proviso that at least one Radical Y is contained with at least one radical F per molecule and the n-units (SiR2 ⁇ ) and the p-units (SiRYO) can be distributed as desired in the molecule.
  • the organosilicon compounds of the formula (I) according to the invention can also contain amino groups, ie contain units of the formula (II), and the organopolysiloxanes of the formula (IV) can also contain SiRXO units, if not all of the amino groups X in the Organopolysiloxanes of the formula (III) were converted into amido groups Y, for example because the reaction with fatty acids (2) was substoichiometric or the reaction was not complete.
  • the organosilicon compounds used in the inventive method (1) have a viscosity of preferably 10 to 100,000 mPa 's at 25 ° C, preferably 50 to 10,000 mPa-s at 25 ° C.
  • Organosilicon compounds (1) are preferably produced by equilibration of organopolysiloxanes selected from the group consisting of linear, terminal
  • Organopolysiloxanes containing triorganosiloxy groups linear organopolysiloxanes containing terminal hydroxyl groups, cyclic organopolysiloxanes and copolymers of diorganosiloxane and monoorganosiloxane units with aminosilanes, such as ⁇ -aminopropylmethyldimethoxysilane or
  • Aminoethylaminopropylmethyldimethoxysilane in the presence of catalysts that promote equilibration, preferably basic catalysts such as alkali metal hydroxides, e.g. Sodium or potassium hydroxide, or trimethylammonium hydroxide.
  • basic catalysts such as alkali metal hydroxides, e.g. Sodium or potassium hydroxide, or trimethylammonium hydroxide.
  • preferred fatty acids (2) are preferably those having 16 to 28 carbon atoms
  • Glycerides of these fatty acids are used.
  • fatty acid One type of fatty acid or two or more types of fatty acids can be used.
  • the glycerides can be used.
  • Glycerol esters of mixtures of different fatty acids are Glycerol esters of mixtures of different fatty acids.
  • fatty acids examples include palmitic acid (C ⁇ 6 ), stearic acid
  • Vegetable oils such as safflower oil, sesame oil, soybean oil, corn oil, sunflower seed oil, olive oil, palm oil, coconut oil and castor oil can also be used.
  • the organosilicon compounds according to the invention are in solid form, e.g. as waxes, preferably to obtain saturated fatty acids, such as stearic acid, or glycerides, such as glycerol monostearate, and in order to obtain the organosilicon compounds according to the invention in liquid form, preferably unsaturated fatty acids, preferably polyunsaturated fatty acids, such as linoleic acid or linolenic acid, or the above-mentioned vegetable oils span.-
  • the fatty acids (2) or glycerol esters of these fatty acids are used in such amounts that the acid group in the fatty acid (2) to N-bonded hydrogen in the rest X of the organosilicon compound (1) in a molar ratio of preferably 0.1 : 1 to 1.2: 1, preferably 0.5: 1 to 1.0: 1.
  • the process according to the invention is carried out at a temperature of preferably 120 ° C. to 180 ° C., preferably 130 ° C. to 150 ° C., and preferably at the pressure of the surrounding atmosphere, that is to say at 1020 hPa (abs.). However, it can also be carried out at lower pressures, such as 3 to 500 hPa, or higher pressures.
  • Organic solvent can optionally be used in the process according to the invention.
  • organic solvents are toluene, xylene, n-hexane and cyclohexane.
  • the water formed in the process according to the invention can be removed, preferably by azeotropic distillation, whereby it can be carried out in the presence of a water removing agent such as dicyclohexylcarbodiimide.
  • the organosilicon compounds according to the invention can be emulsified and are then in the form of (micro) emulsions.
  • the organosilicon compounds according to the invention are mixed with emulsifiers, such as neutral or ionic emulsifiers, and water and then emulsified.
  • emulsifiers such as neutral or ionic emulsifiers
  • water and then emulsified.
  • emulsifiers such as neutral or ionic emulsifiers
  • the preparation of emulsions is known to the person skilled in the art.
  • Mixing and emulsification can be carried out in conventional mixing devices suitable for the production of emulsions, such as high-speed stator-rotor stirring devices according to Prof. P. Willems, as are known under the registered trademark "Ultra-Turrax".
  • organosilicon compounds according to the invention have the advantage that they are biodegradable and are environmentally friendly.
  • the invention further relates to a method for
  • the organosilicon compounds according to the invention can be used, preferably in liquid form, as plasticizers for textiles, the textiles being impregnated with the organosilicon compounds according to the invention.
  • the organosilicon compounds according to the invention have the advantage that they have a soft handle effect on the treated textiles, have good anchoring on the textiles and impart ozone fastness and yellowing resistance to the textile materials.
  • all organic fibers in the form of threads, yarns, nonwovens, mats, strands, woven, knitted or knitted textiles which could previously also be impregnated with organosilicon compounds can be impregnated.
  • fibers that can be impregnated are those made of keratin, in particular wool, mixed polymers of vinyl acetate, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose, viscose and mixtures of at least two such fibers.
  • the fibers can be of natural or synthetic origin.
  • the textiles can be in the form of fabric or pieces of clothing or parts of clothing.
  • the application to the fibers to be impregnated can be carried out in any suitable and well-known manner for the impregnation of fibers, e.g. B. by dipping, brushing, pouring, spraying, including spraying from aerosol packaging, rolling, padding or printing.
  • organosilicon compounds according to the invention can also be used as lubricants for yarn or thread finishing.
  • Organosilicon compounds preferably in solid form, e.g. in the form of a wax, as a polish or polishing agent for ceramic surfaces and lacquers.
  • organosilicon compounds according to the invention can also be used in cosmetics.
  • organosilicon compounds according to the invention can also be used in hair care products.
  • organosilicon compounds according to the invention can also be used in liquids for reprography.
  • the inside temperature of the reactor was kept for 30 minutes. After the nitrogen purge had been switched off, a vacuum was applied at 150 ° C., 510 g of volatile components being obtained. The reactor contents were cooled to 135 ° C. Then 800 g of corn oil were introduced into the reactor and flushed with nitrogen. The reaction was continued under vacuum for 12 hours. 4,650 g of light brown, clear polymer with a viscosity of 10,000 cps (25 ° C.) and a volatile fraction of 1.4% were obtained.
  • Si 29 NMR spectroscopy confirmed the desired structure of the polymer.
  • the amine number of the polymer was determined to be 0.3 mmol / g.
  • the final polymer obtained is a liquid when unsaturated fatty acids are used and a wax when saturated fatty acids are used.
  • Examples 5 to 12 The polymers of Examples 1 to 4 above and a conventional aminosilicone polymer having an amine number of 0.57 and a viscosity of 1,300 cps at 25 ° C. (identified as Example 5), as explained in more detail under Table II, Emulsion produced.
  • Example 5 a conventional aminosilicone polymer having an amine number of 0.57 and a viscosity of 1,300 cps at 25 ° C.
  • Example 6 was the emulsion of Example 5, again using the same emulsifiers.
  • Example 11 is a mixture of Example 5 and cationic plasticizer.
  • Example 12 is exclusively a cationic plasticizer.
  • the new organosilicon polymer plasticizer (Examples 6 to 9) provides excellent soft feel over conventional aminosilicone or cationic plasticizer or a mixture thereof.
  • the new biodegradable silicone polymer according to the invention has been tested for biodegradability of the polymer compared to conventional aminosilicone polymers.
  • Fig.l shows the oxidation property when treated with 2% H 2 0 2 :

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Abstract

The invention relates to novel organosilicon compounds with amido groups, of general formula (I), wherein R can be the same or different and means a monovalent carbohydrate radical, R<1> can be the same or different and means a hydrogen atom, an alkyl radical or an alkoxyalkyl radical, Y can be the same or different and means a radical of formula -(R<4>-NA-)zR<4>-NR<3>A, R<3> being the same or different and being a hydrogen atom or an alkyl radical, R<4> being a divalent hydrocarbon radical, A being a radical R<3> or a radical F of formula -C(=O)R<2>, R<2> being the same or different and being a monovalent saturated or unsaturated hydrocarbon radical with at least 16 carbon atoms, preferably of a fatty acid, z being 0 or a whole number from 1 to 10, a being 0, 1, 2 or 3, c being 0, 2 or 3 and d being 0, 1, 2, or 3, on the condition that the sum of a, c and d in the units of formula (I) is less than or equal to 3 and at least one radical Y with at least one radical F is contained per molecule.

Description

Amidogruppen aufweisende Organosiliciumverbindungen Organosilicon compounds containing amido groups
Die Erfindung betrifft Amidogruppen aufweisende Organosiliciumverbindungen, deren Herstellung und deren Verwendung.The invention relates to organosilicon compounds containing amido groups, their preparation and their use.
Üblicherweise setzt man bei der weichmachenden Behandlung von Textilien und Kleidungsstücken nach dem Auszieh- oder Foulardierverfahren Aminosilicon- emulsionen oder kationische Weichmacher oder Mischungen davon ein. Derartige Weichmacher sind aber biologisch nicht nur nicht leicht abbaubar, sondern haben nach der Behandlung auch einige unerwünschte Auswirkungen auf den textilen Stoff, wie im folgenden diskutiert:Amino silicone emulsions or cationic plasticizers or mixtures thereof are usually used in the softening treatment of textiles and garments using the pull-out or padding process. Such plasticizers are not only not readily biodegradable, but also have some undesirable effects on the textile after treatment, as discussed below:
(i) Der kationische Weichmacher hat zwar eine weichmachende Wirkung, ist aber nicht permanent auf dem Textil verankert. Zudem sind diese kationischen Weichmacher von Haus aus basisch, was zur Vergilbung des Textils führt.(i) The cationic plasticizer has a plasticizing effect, but is not permanently anchored to the textile. In addition, these cationic plasticizers are inherently basic, which leads to the yellowing of the textile.
(ii) Eine herkömmliche Aminosiliconemulsion ergibt zwar eine gute weichmachende Wirkung - und ist permanent auf dem Stoff verankert, bewirkt aber ein Vergilben des textilen Stoffes. (iii) Mischungen aus Aminosiliconemulsion und kationischem Weichmacher zeigen zwar eine gute bis mittlere weichmachende Wirkung, die hohe Alkalinität solcher Mischungen bewirkt aber ebenfalls ein Vergilben des Textils. Zudem sind Mischungen aus kationischem Weichmacher und herkömmlicher Aminosiliconemulsion aufgrund des kationischen Anteils entsprechend weniger gut auf dem Textil verankert. In US-A 4,104,296 (Union Carbide Corporation, ausgegeben am 1. August 1978) und US-A 3,440,261 (Dow Corning Corporation, ausgegeben am 22. April 1969) sind Amidogruppen aufweisende Organosiliciumverbindungen beschrieben .(ii) A conventional aminosilicone emulsion gives a good softening effect - and is permanently anchored to the fabric, but causes the fabric to yellow. (iii) Mixtures of aminosilicone emulsion and cationic plasticizer show a good to medium plasticizing effect, but the high alkalinity of such mixtures also causes the textile to yellow. In addition, mixtures of cationic plasticizers and conventional aminosilicone emulsions are anchored less well on the textile due to the cationic content. US 4,104,296 (Union Carbide Corporation, issued August 1, 1978) and US 3,440,261 (Dow Corning Corporation, issued April 22, 1969) describe organosilicon compounds containing amido groups.
Es bestand die Aufgabe Organosiliciumverbindungen bereitzustellen, die als Weichmacher für Textilien geeignet sind, den Textilien einen weichen Griff verleihen, eine gute Haftung auf den Textilen aufweisen, den Textilien einen guten Schutz gegen Ozonfading verleihen und keine Vergilbung der Textilien bewirken. Es bestand weiterhin die Aufgabe, Organosiliciumverbindungen bereitzustellen, die sowohl in flüssiger als auch in fester Form vorliegen können, die leicht emulgierbar sind und (Micro) emulsionen bilden können und die biologisch abbaubar und umweltfreundlich sind. Die Aufgabe wird durch die Erfindung gelöst.The object was to provide organosilicon compounds which are suitable as plasticizers for textiles, give the textiles a soft feel, have good adhesion to the textiles, give the textiles good protection against ozone fading and do not cause yellowing of the textiles. Another object was to provide organosilicon compounds which can be in both liquid and solid form, which are easily emulsifiable and which can form (micro) emulsions and which are biodegradable and environmentally friendly. The object is achieved by the invention.
Gegenstand der Erfindung sind Amidogruppen aufweisende Organosiliciumverbindungen der allgemeinen FormelThe invention relates to organido silicon compounds of the general formula containing amido groups
RaYc(OR1)dSi04-(a+c+d) (I)R a Y c (OR 1 ) d Si0 4 - (a + c + d) (I)
worin R gleich oder verschieden sein kann und einen einwertigen Kohlenwasserstoffrest bedeutet,where R can be identical or different and denotes a monovalent hydrocarbon radical,
Rl gleich oder verschieden sein kann und Wasserstoffatom, einenRl can be the same or different and hydrogen atom, one
Alkylrest oder einen Alkoxyalkylrest bedeutet,Means alkyl radical or an alkoxyalkyl radical,
Y gleich oder verschieden sein kann und einen Rest der FormelY can be the same or different and a radical of the formula
-(R4-NA-)ZR4-NR3A,- (R 4 -NA-) Z R 4 -NR 3 A,
bedeutet, wobei R3 gleich oder verschieden sein kann und ein Wasserstoffatom oder ein Alkylrest ist, R4 ein zweiwertiger Kohlenwasserstoffrest ist, A ein Rest R3 oder ein Rest F der Formelmeans, where R 3 can be identical or different and is a hydrogen atom or an alkyl radical, R 4 is a divalent hydrocarbon radical, A is a radical R 3 or a radical F of the formula
-C(=0)R"-C (= 0) R "
ist, wobei R2 gleich oder verschieden sein kann und ein einwertiger gesättigter oder ungesättigteris, where R 2 may be the same or different and a monovalent saturated or unsaturated
Kohlenwasserstoffrest mit mindestens 15 Kohlenstoffatomen, vorzugsweise von einer Fettsäure ist, z 0 oder eine ganze Zahl von 1 bis 10, bevorzugt 0 oder 1, 2,Hydrocarbon radical having at least 15 carbon atoms, preferably of a fatty acid, z is 0 or an integer from 1 to 10, preferably 0 or 1, 2,
3 ist, a 0, 1, 2 oder 3, c 0, 1 oder 2 und d 0, 1, 2 oder 3 ist, mit der Maßgabe, daß die Summe aus a, c und d in den Einheiten der Formel (I) kleiner oder gleich 3 ist und pro Molekül mindestens ein Rest Y mit mindestens einem Rest F enthalten ist.3 is a is 0, 1, 2 or 3, c is 0, 1 or 2 and d is 0, 1, 2 or 3, with the proviso that the sum of a, c and d in the units of the formula (I) is less than or equal to 3 and contains at least one radical Y with at least one radical F per molecule.
Gegenstand der Erfindung ist weiterhin ein Verfahren zurThe invention further relates to a method for
Herstellung der erfindungsgemäßen Amidogruppen aufweisenden Organosiliciumverbindungen, wobeiPreparation of the organosilicon compounds containing amido groups according to the invention, wherein
Aminogruppen aufweisende Organosiliciumverbindungen (1) der allgemeinen FormelOrganosilicon compounds (1) having amino groups of the general formula
RaXb (OR1) dSiθ4_(a±b±d) dl) R a X b ( OR 1) d Siθ4_ (a ± b ± d) dl )
wobei R, R1, a und d die oben dafür angegebene Bedeutung haben, X ein Rest der Formelwhere R, R 1 , a and d have the meaning given above, X is a radical of the formula
-(R4-NR5-)ZR4-NR5 2,- (R 4 -NR 5 -) Z R 4 -NR 5 2 ,
ist, wobei R4 und z die oben dafür angegebene Bedeutung haben, R5 gleich oder verschieden sein kann und ein Wasserstoffatom oder einen Alkylrest bedeutet, mit der Maßgabe, dass an mindestens einem Stickstoffatom im Rest X ein Wasserstoffatom gebunden ist, b 0, 1 oder 2 ist, mit der Maßgabe, daß die Summe aus a, b und d in den Einheiten der Formel (II) kleiner oder gleich 3 ist und pro Molekül mindestens ein Rest X enthalten ist, mit Fettsäuren (2), die mindestens 16 Kohlenstoffatome aufweisen, oder Glyceride dieser Fettsäuren umgesetzt werden.where R 4 and z have the meaning given above, R 5 may be the same or different and is a hydrogen atom or an alkyl radical, with the proviso that a hydrogen atom is bonded to at least one nitrogen atom in the radical X, b is 0, 1 or 2, with the proviso that the sum of a, b and d in the units of the formula (II) is less than or equal to 3 and at least one radical X is contained per molecule, with fatty acids (2), which have at least 16 carbon atoms, or glycerides of these fatty acids are reacted.
Beim Rest R handelt es sich vorzugsweise um einwertige Kohlenwasserstoffreste mit 1 bis 18 Kohlenstoffatom (en) .The radical R is preferably monovalent hydrocarbon radicals having 1 to 18 carbon atoms.
Beispiel für Reste R sind Alkylreste, wie der Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, tert . -Butyl-, n- Pentyl-, iso-Pentyl-, neo-Pentyl-, tert . -Pentylrest, Hexylreste, wie der n-Hexylrest, Heptylreste, wie der n- Heptylrest, Octylreste, wie der n-Octylrest und iso-Octylrest, wie der 2, 2, 4-Trimethylpentylrest, Nonylreste, wie der n- Nonylrest, Decylreste, wie der n-Decylrest, Dodecylreste, wie der n-Dodecylrest, Octadecylreste, wie der n-Octadecylrest; Alkenylreste, wie der Vinyl- und der Allylrest, Cycloalkylreste, wie Cyclopentyl-, Cyclohexyl-,Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. -Butyl-, n-pentyl-, iso-pentyl-, neo-pentyl-, tert. Pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radical, such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals , such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, octadecyl radicals, such as the n-octadecyl radical; Alkenyl radicals, such as the vinyl and allyl radicals, cycloalkyl radicals, such as cyclopentyl, cyclohexyl,
Cycloheptylreste und Methylcyclohexylreste, Arylreste, wie der Phenyl-, Naphthyl-, Anthryl- und Phenanthrylrest; Alkarylreste, wie o-, m-, p-Tolylreste, Xylylreste und Ethylphenylreste; Aralkylreste, wie der Benzylrest, der α- und der ß- Phenylethylrest, wobei der Methylrest, Ethylrest, n-Propylrest, Iso-Propylrest und n-Butylrest bevorzugt sind und der Methylrest besonders bevorzugt ist.Cycloheptyl residues and methylcyclohexyl residues, aryl residues, such as the phenyl, naphthyl, anthryl and phenanthryl residue; Alkaryl groups such as o-, m-, p-tolyl groups, xylyl groups and ethylphenyl groups; Aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical, the methyl radical, ethyl radical, n-propyl radical, isopropyl radical and n-butyl radical being preferred and the methyl radical being particularly preferred.
Beim Rest R handelt es sich vorzugsweise um Alkylreste mit 1 bis 4 Kohlenstoffatom(en) . Bespiele für Alkylreste R sind derThe radical R is preferably an alkyl radical with 1 to 4 carbon atoms. Examples of alkyl radicals R are
Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl- und tert . -Butylrest, wobei der Methyl- und Ethylrest bevorzugt sind.Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert. -Butyl radical, with the methyl and ethyl radical being preferred.
Beispiele für Alkoxyalkylreste sind der Methoxyethyl- und der Ethoxyethylrest .Examples of alkoxyalkyl radicals are the methoxyethyl and the ethoxyethyl radical.
Beim Rest R2 handelt es sich vorzugsweise um einen einwertigen gesättigten oder ungesättigten Kohlenwasserstoffrest mit 15 bis 27 Kohlenstoffatomen, bevorzugt 15 bis 23 Kohlenstoffatomen, besonders bevorzugt 15 bis 19 Kohlenstoffatomen.The radical R 2 is preferably a monovalent saturated or unsaturated hydrocarbon radical with 15 to 27 carbon atoms, preferably 15 to 23 carbon atoms, particularly preferably 15 to 19 carbon atoms.
Beispiele für Alkylreste R gelten im vollen Umfang auch für Alkylreste R3 und R5.Examples of alkyl radicals R also apply in full to alkyl radicals R 3 and R 5 .
Der Rest R4 ist vorzugsweise ein zweiwertigerThe radical R 4 is preferably a divalent one
Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatom (en) je Rest. Beispiele für Reste R4 sind der Methylen-, Ethylen-, Propylen-, Butylen-, Cyclohexylen-, Octadecylen-, Phenylen- und Butenylenrest, wobei, insbesondere wegen der leichten Zugänglichkeit, der Ethylen- und der n-Propylenrest bevorzugt sind.Hydrocarbon radical with 1 to 12 carbon atoms per radical. Examples of radicals R 4 are the methylene, ethylene, propylene, butylene, cyclohexylene, octadecylene, phenylene and butenylene radical, where, in particular because of the easy accessibility, the ethylene and the n-propylene radical are preferred.
Beispiele für Reste X sindExamples of radicals X are
H2N(CH2)3-H 2 N (CH 2 ) 3 -
H2N(CH2)2NH(CH2)3-H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -
H2N (CH2) 2NHC (CH3) 2CH2- (H3C)2N(CH2)2NH(CH2)3-H 2 N (CH 2 ) 2 NHC (CH 3 ) 2 CH 2 - (H 3 C) 2 N (CH 2 ) 2 NH (CH 2 ) 3 -
H2N(CH2)2-H 2 N (CH 2 ) 2 -
H3CNH(CH2)3-H 3 CNH (CH 2 ) 3 -
H2N(CH2)4-H 2 N (CH 2 ) 4 -
H2N(CH2)5- H(NHCH2CH2)3-H 2 N (CH 2 ) 5 - H (NHCH 2 CH 2 ) 3 -
C4H9NH (CH2) 2NH (CH2) 2-and cyclo-C6HnNH(CH2)3-, wobei die ResteC 4 H 9 NH (CH 2 ) 2 NH (CH 2 ) 2 -and cyclo-C 6 HnNH (CH 2 ) 3 -, with the residues
H2N(CH2)3- H2N(CH2)2NH(CH2)3- bevorzugt sind.H 2 N (CH 2 ) 3 - H 2 N (CH 2 ) 2 NH (CH 2 ) 3 - are preferred.
Beispiele für Reste Y sind daherExamples of radicals Y are therefore
ANH(CH2)3-ANH (CH 2 ) 3 -
ANH(CH2)2NH(CH2)3- ANH(CH2)2NA(CH2)3-ANH (CH 2 ) 2 NH (CH 2 ) 3 - ANH (CH 2 ) 2 NA (CH 2 ) 3 -
ANH (CH2) 2NHC (CH3) 2CH2-ANH (CH 2 ) 2 NHC (CH 3 ) 2 CH 2 -
ANH (CH2) 2NAC (CH3) 2CH2- (H3C)2N(CH2)2NA(CH2)3- ANH(CH2)2-ANH (CH 2 ) 2 NAC (CH 3 ) 2 CH 2 - (H 3 C) 2 N (CH 2 ) 2 NA (CH 2 ) 3 - ANH (CH 2 ) 2 -
H3CNA(CH2)3-H 3 CNA (CH 2 ) 3 -
ANH(CH2)4-ANH (CH 2 ) 4 -
ANH(CH2)5-ANH (CH 2 ) 5 -
ANHCH2CH2NHCH2CH2NHCH2CH2- ANHCH2CH2NACH2CH2NHCH2CH2-ANHCH 2 CH 2 NHCH 2 CH 2 NHCH 2 CH 2 - ANHCH 2 CH 2 AFTER 2 CH 2 NHCH 2 CH 2 -
ANHCH2CH2NACH2CH2NACH2CH2-ANHCH 2 CH 2 AFTER 2 CH 2 AFTER 2 CH 2 -
C4H9NA(CH2)2NA(CH2)2- and cyclo-C6HnNA(CH2)3-, wobei die Reste ANH(CH2)3-C 4 H 9 NA (CH 2 ) 2 NA (CH 2 ) 2 - and cyclo-C 6 HnNA (CH 2 ) 3 -, with the residues ANH (CH 2 ) 3 -
ANH(CH2)2NH(CH2)3-ANH (CH 2 ) 2 NH (CH 2 ) 3 -
ANH(CH2)2NA(CH2)3- bevorzugt sind, worin A ein Rest der Formel -C(=0)R2 (wobei R2 die oben dafür angegebene Bedeutung hat) ist.ANH (CH 2 ) 2 NA (CH 2 ) 3 - are preferred, in which A is a radical of the formula -C (= 0) R 2 (where R 2 has the meaning given above).
Die erfindungsgemäßen Organosiliciumverbindungen sind vorzugsweise Organopolysiloxane .The organosilicon compounds according to the invention are preferably organopolysiloxanes.
Die erfindungsgemäßen Organosiliciumverbindungen haben vorzugsweise eine Viskosität von 50 mPa's bei 25°C bis 100.000 mPas bei 60°C, bevorzugt 50 mPa's bei 25°C bis 10000 mPas bei 60°C.The organosilicon compounds according to the invention preferably have a viscosity of 50 mPa's at 25 ° C to 100,000 mPas at 60 ° C, preferably 50 mPa 's at 25 ° C to 10,000 mPas at 60 ° C.
Die erfindungsgemäßen Organosiliciumverbindungen haben vorzugsweise ein Molekulargewicht (Mn) von 500 bis 1.000.000 g/mol, bevorzugt 500 bis 100000 g/mol .The organosilicon compounds according to the invention preferably have a molecular weight (M n ) of 500 to 1,000,000 g / mol, preferably 500 to 100,000 g / mol.
Die erfindungsgemäßen Organosiliciumverbindungen weisen vorzugsweise eine Aminzahl von 0,01 bis 4,0 mequiv/g, bevorzugt 0,1 bis 2,0 mequiv/g auf. Die erfindungsgemäßen Organosiliciumverbindungen können in flüssiger Form oder in fester Form, z.B. in wachsartiger Form, vorliegen.The organosilicon compounds according to the invention preferably have an amine number of 0.01 to 4.0 mequiv / g, preferably 0.1 to 2.0 mequiv / g. The organosilicon compounds according to the invention can be in liquid form or in solid form, for example in waxy form.
Bevorzugt werden in dem erfindungsgemäßen Verfahren als Aminogruppen aufweisende Organosiliciumverbindungen (1) Organopolysiloxane der allgemeinen FormelIn the process according to the invention, preference is given to organosilicon compounds (1) having amino groups and organopolysiloxanes of the general formula
XgR3_gSiO(SiR20)n(SiRXO)mSiR3_gXg (III),X g R3_ g SiO (SiR 2 0) n (SiRXO) m SiR3_ g X g (III),
wobei R und X die oben dafür angegebene Bedeutung haben, g 0, 1 oder 2 ist, n 0 oder eine ganze Zahl von 1 bis 1000 ist, m 0 oder eine ganze Zahl von 1 bis 100 ist, mit der Maßgabe, daß mindestens ein Rest X je Molekül enthalten ist und die n-Einheiten (SiR2θ) und die m-Einheiten (SiRXO) beliebig im Molekül verteilt sein können, eingesetzt.wherein R and X have the meaning given above, g is 0, 1 or 2, n is 0 or an integer from 1 to 1000, m is 0 or an integer from 1 to 100, with the proviso that at least one X is contained per molecule and the n-units (SiR2θ) and the m-units (SiRXO) can be distributed as desired in the molecule.
Bevorzugt als erfindungsgemäße Organosiliciumverbindung sind daher Organopolysiloxane der allgemeinen FormelOrganopolysiloxanes of the general formula are therefore preferred as the organosilicon compound according to the invention
YgR3_gSiO(SiR20)n(SiRYO)pSiR3_gYg (IV) ,Y g R3_ g SiO (SiR 2 0) n (SiRYO) pSiR 3 _ g Y g (IV),
wobei R und Y die oben dafür angegebene Bedeutung haben, g 0, 1 oder 2 ist, n 0 oder eine ganze Zahl von 1 bis 1000 ist, p 0 oder eine ganze Zahl von 1 bis 100 ist, mit der Maßgabe, daß mindestens ein Rest Y mit mindestens einem Rest F je Molekül enthalten ist und die n-Einheiten (SiR2θ) und die p-Einheiten (SiRYO) beliebig im Molekül verteilt sein können.wherein R and Y have the meaning given above, g is 0, 1 or 2, n is 0 or an integer from 1 to 1000, p is 0 or an integer from 1 to 100, with the proviso that at least one Radical Y is contained with at least one radical F per molecule and the n-units (SiR2θ) and the p-units (SiRYO) can be distributed as desired in the molecule.
Die erfindungsgemäßen Organosiliciumverbindungen der Formel (I) können neben den Amidogruppen noch Aminogruppen enthalten, d.h. Einheiten der Formel (II) enthalten, und die Organopolysiloxane der Formel (IV) können noch SiRXO- Einheiten enthalten, wenn nicht alle Aminogruppen X in den Organopolysiloxanen der Formel (III) in Amidogruppen Y umgesetzt wurden, beispielsweise weil die Umsetzung mit Fettsäuren (2) unterstöchiometrisch erfolgte oder die Umsetzung nicht vollständig war.In addition to the amido groups, the organosilicon compounds of the formula (I) according to the invention can also contain amino groups, ie contain units of the formula (II), and the organopolysiloxanes of the formula (IV) can also contain SiRXO units, if not all of the amino groups X in the Organopolysiloxanes of the formula (III) were converted into amido groups Y, for example because the reaction with fatty acids (2) was substoichiometric or the reaction was not complete.
Die bei dem erfindungsgemäßen Verfahren eingesetzten Organosiliciumverbindungen (1) haben eine Viskosität von vorzugsweise 10 bis 100 000 mPa's bei 25°C, bevorzugt 50 bis 10000 mPa-s bei 25°C.The organosilicon compounds used in the inventive method (1) have a viscosity of preferably 10 to 100,000 mPa 's at 25 ° C, preferably 50 to 10,000 mPa-s at 25 ° C.
Die Herstellung der eingesetzten Organosiliciumverbindungen (1) ist dem Fachmann bekannt. Die eingesetztenThe preparation of the organosilicon compounds (1) used is known to the person skilled in the art. The used
Organosiliciumverbindungen (1) werden vorzugsweise hergestellt durch Equilibrierung von Organopolysiloxanen ausgewählt aus der Gruppe bestehend aus linearen, endständigeOrganosilicon compounds (1) are preferably produced by equilibration of organopolysiloxanes selected from the group consisting of linear, terminal
Triorganosiloxygruppen aufweisenden Organopolysiloxanen, linearen, endständige Hydroxylgruppen aufweisenden Organopolysiloxanen, cyclischen Organopolysiloxanen und Mischpolymerisaten aus Diorganosiloxan- und Monoorganosiloxaneinheiten mit Aminosilanen, wie γ- Aminopropylmethyldimethoxysilan oderOrganopolysiloxanes containing triorganosiloxy groups, linear organopolysiloxanes containing terminal hydroxyl groups, cyclic organopolysiloxanes and copolymers of diorganosiloxane and monoorganosiloxane units with aminosilanes, such as γ-aminopropylmethyldimethoxysilane or
Aminoethylaminopropylmethyldimethoxysilan, in Gegenwart von Katalysatoren, die die Equilibrierung fördern, bevorzugt basische Katalysatoren, wie Alkalimetallhydroxide, z.B. Natrium- oder Kaliumhydroxid, oder Trimethylammoniumhydroxid.Aminoethylaminopropylmethyldimethoxysilane, in the presence of catalysts that promote equilibration, preferably basic catalysts such as alkali metal hydroxides, e.g. Sodium or potassium hydroxide, or trimethylammonium hydroxide.
Bei dem erfindungsgemäßen Verfahren werden als Fettsäuren (2) vorzugsweise solche mit 16 bis 28 Kohlenstoffatomen, bevorzugtIn the process according to the invention, preferred fatty acids (2) are preferably those having 16 to 28 carbon atoms
16 bis 24 Kohlenstoffatomen, besonders bevorzugt 16 bis 20 Kohlenstoffatomen, d.h. vorzugsweise solche der Formel R2COOH, wobei R2 die oben dafür angegebene Bedeutung hat, eingesetzt.16 to 24 carbon atoms, particularly preferably 16 to 20 carbon atoms, ie preferably those of the formula R 2 COOH, where R 2 has the meaning given above.
Es können gesättigte oder ungesättigte Fettsäuren oderIt can be saturated or unsaturated or
Glyceride dieser Fettsäuren eingesetzt werden.Glycerides of these fatty acids are used.
Es kann eine Art von Fettsäure oder zwei oder mehr Arten von Fettsäuren eingesetzt werden. Die Glyceride könnenOne type of fatty acid or two or more types of fatty acids can be used. The glycerides can
Glycerinester von Mischungen verschiedener Fettsäuren sein.Glycerol esters of mixtures of different fatty acids.
Beispiele für Fettsäuren sind Palmitinsäure (Cι6) , StearinsäureExamples of fatty acids are palmitic acid (Cι 6 ), stearic acid
(Cis) , Ölsäure (Ci8) , Linolsäure (Cι8) , Linolensäure (Cι8) Hexacosansäure (C26) und Glyceride dieser Fettsäuren, beispielsweise Glycerolmonostearat .(Cis), oleic acid (C i8 ), linoleic acid (Cι 8 ), linolenic acid (Cι 8 ) Hexacosanoic acid (C 26 ) and glycerides of these fatty acids, for example glycerol monostearate.
Weiterhin können pflanzliche Öle, wie Safloröl, Sesamöl, Sojabohnenöl, Maisöl, Sonnenblumenkernöl, Olivenöl, Palmöl, Kokosöl und Ricinusöl, eingesetzt werden.Vegetable oils such as safflower oil, sesame oil, soybean oil, corn oil, sunflower seed oil, olive oil, palm oil, coconut oil and castor oil can also be used.
Abhängig vom Molekulargewicht und der Anzahl der Aminogruppen X in den eingesetzten Organosiliciumverbindungen (1) werden um die erfindungsgemäßen Organosiliciumverbindungen in fester Form, z.B. als Wachse, zu erhalten vorzugsweise gesättigte Fettsäuren, wie Stearinsäure, oder Glyceride, wie Glycerolmonostearat, eingesetzt, und um die erfindungsgemäßen Organosiliciumverbindungen in flüssiger Form zu erhalten vorzugsweise ungesättigte Fettsäuren, bevorzugt mehrfach ungesättigte Fettsäuren, wie Linolsäure oder Linolensäure, oder die oben genannten planzlichen Öle eingesetzt.-Depending on the molecular weight and the number of amino groups X in the organosilicon compounds (1) used, the organosilicon compounds according to the invention are in solid form, e.g. as waxes, preferably to obtain saturated fatty acids, such as stearic acid, or glycerides, such as glycerol monostearate, and in order to obtain the organosilicon compounds according to the invention in liquid form, preferably unsaturated fatty acids, preferably polyunsaturated fatty acids, such as linoleic acid or linolenic acid, or the above-mentioned vegetable oils eingesetzt.-
In dem erfindungsgemäßen Verfahren werden die Fettsäuren (2) bzw. Glycerinester dieser Fettsäuren in solchen Mengen eingesetzt, dass die Säuregruppe in der Fettsäure (2) zu N- gebundenem Wasserstoff im Rest X der Organosiliciumverbindung (1) im molaren Verhältnis von vorzugsweise 0,1 : 1 bis 1,2 : 1, bevorzugt 0,5 : 1 bis 1,0 : 1, vorliegt.In the process according to the invention, the fatty acids (2) or glycerol esters of these fatty acids are used in such amounts that the acid group in the fatty acid (2) to N-bonded hydrogen in the rest X of the organosilicon compound (1) in a molar ratio of preferably 0.1 : 1 to 1.2: 1, preferably 0.5: 1 to 1.0: 1.
Das erfindungsgemäße Verfahren wird bei einer Temperatur von vorzugsweise 120°C bis 180°C, bevorzugt 130°C bis 150°C, und vorzugsweise beim Druck der umgebenden Atmosphäre, also bei 1020 hPa (abs.), durchgeführt. Es kann aber auch bei niedrigeren Drücken, wie 3 bis 500 hPa, oder höheren Drücken durchgeführt werden.The process according to the invention is carried out at a temperature of preferably 120 ° C. to 180 ° C., preferably 130 ° C. to 150 ° C., and preferably at the pressure of the surrounding atmosphere, that is to say at 1020 hPa (abs.). However, it can also be carried out at lower pressures, such as 3 to 500 hPa, or higher pressures.
Bei dem erfindungsgemäßen Verfahren kann gegebenenfalls organisches Lösungsmittel mitverwendet werden. Beispiele für organische Lösungsmittel sind Toluol, Xylol, n-Hexan und Cyclohexan.Organic solvent can optionally be used in the process according to the invention. Examples of organic solvents are toluene, xylene, n-hexane and cyclohexane.
Das bei dem erfindungsgemäßen Verfahren gebildete Wasser kann entfernt werden, vorzugsweise durch azeotrope Destillation, wobei sie in Gegenwart eines Wasser entfernenden Mittels, wie Dicyclohexylcarbodiimid, durchgeführt werden kann.The water formed in the process according to the invention can be removed, preferably by azeotropic distillation, whereby it can be carried out in the presence of a water removing agent such as dicyclohexylcarbodiimide.
Die erfindungsgemäßen Organosiliciumverbindungen können emulgiert werden und liegen dann in Form von (Micro) Emulsionen vor. Zur Herstellung der Emulsionen werden die erfindungsgemäßen Organosiliciumverbindungen mit Emulgatoren, wie neutralen oder ionischen Emulgatoren, und Wasser vermischt und anschließend emulgiert. Die Herstellung von Emulsionen ist dem Fachmann bekannt. Das Vermischen und Emulgieren kann in üblichen, zur Herstellung von Emulsionen geeigneten Mischgeräten, wie schnelllaufenden Stator-Rotor-Rührgeräten nach Prof. P. Willems, wie sie unter dem registrierten Warenzeichen "Ultra-Turrax" bekannt sind, erfolgen.The organosilicon compounds according to the invention can be emulsified and are then in the form of (micro) emulsions. To prepare the emulsions, the organosilicon compounds according to the invention are mixed with emulsifiers, such as neutral or ionic emulsifiers, and water and then emulsified. The preparation of emulsions is known to the person skilled in the art. Mixing and emulsification can be carried out in conventional mixing devices suitable for the production of emulsions, such as high-speed stator-rotor stirring devices according to Prof. P. Willems, as are known under the registered trademark "Ultra-Turrax".
Die erfindungsgemäßen Organosiliciumverbindungen haben den Vorteil, dass sie biologisch abbaubar sind und umweltfreundlich sind.The organosilicon compounds according to the invention have the advantage that they are biodegradable and are environmentally friendly.
Gegenstand der Erfindung ist weiterhin ein Verfahren zurThe invention further relates to a method for
Imprägnierung von organischen Fasern mit den erfindungsgemäßen Organosiliciumverbindungen .Impregnation of organic fibers with the organosilicon compounds according to the invention.
Die erfindungsgemäßen Organosiliciumverbindungen können, vorzugsweise in flüssiger Form, als Weichmacher für Textilien, eingesetzt werden, wobei die Textilien mit den erfindungsgemäßen Organosiliciumverbindungen imprägniert werden. Die erfindungsgemäßen Organosiliciumverbindungen haben den Vorteil, dass sie bei den behandelten Textilien einen Weichgriffeffekt bewirken, eine gute Verankerung auf den Textilien aufweisen und den textilen Stoffen Ozonechtheit und Vergilbungsbeständigkeit verleihen.The organosilicon compounds according to the invention can be used, preferably in liquid form, as plasticizers for textiles, the textiles being impregnated with the organosilicon compounds according to the invention. The organosilicon compounds according to the invention have the advantage that they have a soft handle effect on the treated textiles, have good anchoring on the textiles and impart ozone fastness and yellowing resistance to the textile materials.
Nach dem erfindungsgemäßen Verfahren zur Imprägnierung von organischen Fasern können alle organischen Fasern in Form von Fäden, Garnen, Vliesen, Matten, Strängen, gewebten, gewirkten oder gestrickten Textilien imprägniert werden, die auch bisher mit Organosiliciumverbindungen imprägniert werden konnten. Beispiele für Fasern, die imprägniert werden können, sind solche aus Keratin, insbesondere Wolle, Mischpolymere von Vinylacetat, Baumwolle, Rayon, Hanf, natürliche Seide, Polypropylen, Polyethylen, Polyester, Polyurethan, Polyamid, Cellulose, Viskose und Gemische aus mindestens zwei solcher Fasern. Wie aus der vorstehenden Aufzählung ersichtlich, können die Fasern natürlicher oder synthetischer Herkunft sein. Die Textilien können in Form von Stoffbahnen oder Kleidungsstücken bzw. Teilen von Kleidungsstücken vorliegen.According to the process according to the invention for impregnating organic fibers, all organic fibers in the form of threads, yarns, nonwovens, mats, strands, woven, knitted or knitted textiles which could previously also be impregnated with organosilicon compounds can be impregnated. Examples of fibers that can be impregnated are those made of keratin, in particular wool, mixed polymers of vinyl acetate, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose, viscose and mixtures of at least two such fibers. As can be seen from the above list, the fibers can be of natural or synthetic origin. The textiles can be in the form of fabric or pieces of clothing or parts of clothing.
Das Auftragen auf die zu imprägnierenden Fasern kann in beliebiger für die Imprägnierung von Fasern geeigneter und vielfach bekannter Weise erfolgen, z. B. durch Tauchen, Streichen, Gießen, Sprühen, einschließlich Sprühen aus Aerosolverpackung, Aufwalzen, Klotzen oder Drucken.The application to the fibers to be impregnated can be carried out in any suitable and well-known manner for the impregnation of fibers, e.g. B. by dipping, brushing, pouring, spraying, including spraying from aerosol packaging, rolling, padding or printing.
Die erfindungsgemäßen Organosiliciumverbindungen können weiterhin als Gleitmittel für die Garn- oder Fadenausrüstung verwendet werden.The organosilicon compounds according to the invention can also be used as lubricants for yarn or thread finishing.
Weiterhin können die erfindungsgemäßenFurthermore, the invention
Organosiliciumverbindungen, vorzugsweise in fester Form, z.B. in Form eines Wachses, als Politur oder Poliermittel für keramische Oberflächen und Lacke verwendet werden.Organosilicon compounds, preferably in solid form, e.g. in the form of a wax, as a polish or polishing agent for ceramic surfaces and lacquers.
Die erfindungsgemäßen Organosiliciumverbindungen können weiterhin in der Kosmetik verwendet werden.The organosilicon compounds according to the invention can also be used in cosmetics.
Die erfindungsgemäßen Organosiliciumverbindungen können weiterhin in Haarpflegemitteln verwendet werden.The organosilicon compounds according to the invention can also be used in hair care products.
Die erfindungsgemäßen Organosiliciumverbindungen können weiterhin in Flüssigkeiten für die Reprografie verwendet werden.The organosilicon compounds according to the invention can also be used in liquids for reprography.
Die Aufgaben/Vorteile der vorliegenden Erfindung und die Mittel zu ihrer Ausführung werden im folgenden anhand nicht einschränkender Ausführungsbeispiele näher erläutert. BeispieleThe objects / advantages of the present invention and the means for carrying it out are explained in more detail below on the basis of non-restrictive exemplary embodiments. Examples
Beispiel 1example 1
Im Reaktor wurden 4.000 g eines mit Silanolgruppen gestopperten Polydimethylsiloxans einer Viskosität von 80 cps (25°C), 272 g γ-Aminoethylaminopropylmethyl- dimethoxysilan, 100 g eines mit Trimethylsiloxy gestopperten Siloxans einer Viskosität von 10 cps (25°C) und 50 g Tetramethylammoniumsiliconat als Katalysator vorgelegt. In der Reaktion wurde mit einer Stickstoffspülung begonnen. Der Reaktor wurde auf etwa 110 °C erhitzt und etwa 4 h lang bei dieser Temperatur gehalten. Nach etwa 4 h Reaktion wurde die Innentemperatur des Reaktors auf 150°C eingestellt. Die Innentemperatur des Reaktors wurde 30 min lang gehalten. Nach Abstellen der Stickstoffspülung wurde bei 150°C ein Vakuum angelegt, wobei 510 g flüchtige Anteile erhalten wurden. Der Reaktorinhalt wurde auf 135 °C abgekühlt. Anschließend wurden 800 g Maisöl in den Reaktor eingegeben und mit Stickstoff gespült. Die Umsetzung wurde 12 Stunden lang unter Vakuum weitergeführt. Erhalten wurden 4.650 g hellbraunes, klares Polymer mit einer Viskosität von 10.000 Cps (25°C) und einem flüchtigen Anteil von 1,4%.4,000 g of a polydimethylsiloxane stopped with silanol groups and having a viscosity of 80 cps (25 ° C.), 272 g of γ-aminoethylaminopropylmethyldimethoxysilane, 100 g of a siloxane stopped with trimethylsiloxy and having a viscosity of 10 cps (25 ° C.) and 50 g of tetramethylammonium silicon submitted as a catalyst. A nitrogen purge was started in the reaction. The reactor was heated to about 110 ° C and held at that temperature for about 4 hours. After about 4 hours of reaction, the inside temperature of the reactor was adjusted to 150 ° C. The inside temperature of the reactor was kept for 30 minutes. After the nitrogen purge had been switched off, a vacuum was applied at 150 ° C., 510 g of volatile components being obtained. The reactor contents were cooled to 135 ° C. Then 800 g of corn oil were introduced into the reactor and flushed with nitrogen. The reaction was continued under vacuum for 12 hours. 4,650 g of light brown, clear polymer with a viscosity of 10,000 cps (25 ° C.) and a volatile fraction of 1.4% were obtained.
Die Si29-NMR-Spektroskopie bestätigte den erwünschten Aufbau des Polymers. Die Aminzahl des Polymers wurde zu 0,3 mmol/g bestimmt.Si 29 NMR spectroscopy confirmed the desired structure of the polymer. The amine number of the polymer was determined to be 0.3 mmol / g.
Beispiele 2 bis 4:Examples 2 to 4:
Analog Beispiel 1 wurden weitere Beispiele (2, 3 & 4) mit verschiedenen Fettsäure/Glykosid Verhältnissen durchgeführt. Die Ergebnisse sind in der Tabelle I zusammengefaßt . Tabelle IAnalogously to Example 1, further examples (2, 3 & 4) were carried out with different fatty acid / glycoside ratios. The results are summarized in Table I. Table I
Figure imgf000014_0001
Figure imgf000014_0001
Aus der obigen Tabelle I ist es ersichtlich, daß es sich bei dem endgültig erhaltenen Polymer bei Einsatz von ungesättigten Fettsäuren um eine Flüssigkeit, bei Einsatz gesättigter Fettsäure um ein Wachs handelt.It can be seen from Table I above that the final polymer obtained is a liquid when unsaturated fatty acids are used and a wax when saturated fatty acids are used.
Beispiele 5 bis 12 : Aus den Polymeren der obigen Beispiele 1 bis 4 und aus einem herkömmlichen Aminosiliconpolymer einer Aminzahl von 0,57 und einer Viskosität von 1.300 cps bei 25°C (gekennzeichnet als Beispiel 5) wird, wie unter Tabelle II näher erläutert, Emulsion hergestellt. Die in Tabelle II angegebenen Emulsionen (d. h.Examples 5 to 12: The polymers of Examples 1 to 4 above and a conventional aminosilicone polymer having an amine number of 0.57 and a viscosity of 1,300 cps at 25 ° C. (identified as Example 5), as explained in more detail under Table II, Emulsion produced. The emulsions listed in Table II (i.e.
Beispiele 6 bis 9) wurden sämtlich mit den gleichen Emulgatoren hergestellt und unterscheiden sich nur hinsichtlich des biologisch abbaubaren Organosiliciumpolymers. Beispiel 10 ist die Emulsion von Beispiel 5, wiederum unter Einsatz gleicher Emulgatoren. Bei Beispiel 11 handelt es sich um eine Mischung aus Beispiel 5 und kationischem Weichmacher. Bei Beispiel 12 handelt es sich ausschließlich um einen kationischen Weichmacher.Examples 6 to 9) were all produced with the same emulsifiers and differ only in terms of their biodegradability Organosilicon. Example 10 is the emulsion of Example 5, again using the same emulsifiers. Example 11 is a mixture of Example 5 and cationic plasticizer. Example 12 is exclusively a cationic plasticizer.
Tabelle IITable II
Figure imgf000015_0001
Figure imgf000015_0001
Das Weichgriffverhalten der verschiedenen, gemäß den Beispielen 6 bis 12 erhaltenen Emulsionen wurde wie folgt beurteilt.The soft grip behavior of the various emulsions obtained according to Examples 6 to 12 was assessed as follows.
Beispiel 13:Example 13:
Drei verschiedene Typen Weißtextil, nämlich 100%iges Polyester, Mischung aus 60% Viskose/40% Polyester sowie 100% Baumwolle wurden mit diesen sieben Beispielen foulardiert, wobei die Flotte konstant bei einem Festgehalt von 4% gehalten und mit einer Flottenaufnahme von 1 % appliziert wurde. Danach wurden die Textilien 10 min lang bei 160 °C konditioniert . Die so behandelten Textilien wurden zur Beurteilung des Weichgriffs einem Prüf-Team aus vier Personen vorgelegt, denen die Zuordnung Behandlungsmittel/Behandlungssubstrat nicht bekannt war.Three different types of white textile, namely 100% polyester, a mixture of 60% viscose / 40% polyester and 100% cotton were padded with these seven examples, the liquor being kept constant at a solids content of 4% and applied with a liquor absorption of 1% has been. The textiles were then conditioned at 160 ° C. for 10 minutes. The textiles treated in this way were used to assess the soft hand Test team of four people presented to whom the assignment of treatment agent / treatment substrate was not known.
Die Prüfer erteilten die in der folgenden Tabelle III angegebenen Noten gemäß ihrer persönlichen Einschätzung des Weichgriffes.The examiners gave the grades given in Table III below according to their personal assessment of the softness.
Tabelle IIITable III
Figure imgf000016_0001
Figure imgf000016_0001
Aus der Tabelle III ist ersichtlich, daß der neue Organosiliciumpolymerweichmacher (Beispiele 6 bis 9) gegenüber herkömmlichem Aminosilicon oder kationischem Weichmacher oder deren Mischung einen ausgezeichneten Weichgriff verleiht.It can be seen from Table III that the new organosilicon polymer plasticizer (Examples 6 to 9) provides excellent soft feel over conventional aminosilicone or cationic plasticizer or a mixture thereof.
Beispiel 14 :Example 14:
Das neue biologisch abbaubare Siliconpolymer gemäß der Erfindung wurde einer Prüfung der biologischen Abbaubarkeit des Polymers im Vergleich zu herkömmlichen Aminosiliconpolymeren unterzogen.The new biodegradable silicone polymer according to the invention has been tested for biodegradability of the polymer compared to conventional aminosilicone polymers.
Zur Belegung der besseren biologischen Abbaubarkeit in Abwasserströmen wurden drei Beispiele 1, 4 & 5 untersucht. Von diesen Beispielen wurden drei wäßrige Lösungen mit einer solchen Konzentration hergestellt, daß der chemische Sauerstoffbedarf COD (Chemical Oxygen Demand) anfänglich bei 5.000 lag. Dann wurden zur Simulierung einer typischen Abwasserbehandlung jeweils 2% Wasserstoffperoxid zugesetzt. Bei einer Temperatur von 32 °C wurden in regelmäßigen Zeitabständen Proben entnommen und die COD-Restwerte bestimmt. Die erhaltenen Werte sind in der beigefügten Graphik dargestellt.Three examples 1, 4 & 5 were examined to demonstrate the better biodegradability in wastewater streams. From these examples, three aqueous solutions were prepared at a concentration such that the COD (Chemical Oxygen Demand) was initially 5,000. Then 2% hydrogen peroxide was added to simulate a typical wastewater treatment. Samples were taken at regular intervals at a temperature of 32 ° C removed and the residual COD values determined. The values obtained are shown in the attached graph.
Aus Fig.l ist ersichtlich, daß der COD bei den Beispielen 1 und 4 bereits am zweiten Tag erheblich zurückgegangen ist, während das Beispiel 5 unter den gleichen Bedingungen bei 2000 blieb.From Fig. 1 it can be seen that the COD in Examples 1 and 4 already decreased significantly on the second day, while Example 5 remained at 2000 under the same conditions.
Das zeigt deutlich die niedrigen COD-Gehalte der erfindungsgemäßen Polymere, was die schnelle biologische Abbaubarkeit und so die Umweltfreundlichkeit des Polymers belegt.This clearly shows the low COD contents of the polymers according to the invention, which demonstrates the rapid biodegradability and thus the environmental friendliness of the polymer.
Fig.l zeigt die Oxidationseigenschaft bei Behandlung mit 2% H202 : Fig.l shows the oxidation property when treated with 2% H 2 0 2 :
Figure imgf000017_0001
Figure imgf000017_0001
X = COD (Chemical Oxygen Demand) Beispiel 1 t = Behandlungsdauer in Tagen Beispiel 4 Beispiel 5 X = COD (Chemical Oxygen Demand) Example 1 t = treatment duration in days Example 4 Example 5

Claims

Patentansprücheclaims
1. Amidogruppen aufweisende Organosiliciumverbindungen der allgemeinen Formel1. Organosilicon compounds having amido groups of the general formula
RaYc (OR1) dSi04-(a+c+d) (IIR a Y c ( OR 1) d Si0 4 - (a + c + d) (II
worin R gleich oder verschieden sein kann und einen einwertigen Kohlenwasserstoffrest bedeutet, R gleich oder verschieden sein kann und Wasserstoffatom, einen Alkylrest oder einen Alkoxyalkylrest bedeutet, Y gleich oder verschieden sein kann und einen Rest der Formelwherein R can be identical or different and represents a monovalent hydrocarbon radical, R can be identical or different and represents hydrogen atom, an alkyl radical or an alkoxyalkyl radical, Y can be identical or different and a radical of the formula
-(R4-NA-)ZR4-NR3A,- (R 4 -NA-) Z R 4 -NR 3 A,
bedeutet, wobei R3 gleich oder verschieden sein kann und ein Wasserstoffatom oder ein Alkylrest ist, R4 ein zweiwertiger Kohlenwasserstoffrest ist, A ein Rest R3 oder ein Rest F der Formelmeans, where R 3 may be the same or different and is a hydrogen atom or an alkyl radical, R 4 is a divalent hydrocarbon radical, A is a radical R 3 or a radical F of the formula
-C(=0)R2 -C (= 0) R 2
ist, wobei R2 gleich oder verschieden sein kann und ein einwertiger gesättigter oder ungesättigteris, where R 2 may be the same or different and a monovalent saturated or unsaturated
Kohlenwasserstoffrest mit mindestens 15 Kohlenstoffatomen ist, z 0 oder eine ganze Zahl von 1 bis 10 ist, a 0, 1, 2 oder 3, c 0, 1 oder 2 und d 0, 1, 2 oder 3 ist, mit der Maßgabe, daß die Summe aus a, c und d in denIs hydrocarbon radical having at least 15 carbon atoms, z is 0 or an integer from 1 to 10, a is 0, 1, 2 or 3, c is 0, 1 or 2 and d is 0, 1, 2 or 3, with the proviso that the sum of a, c and d in the
Einheiten der Formel (I) kleiner oder gleich 3 ist und proUnits of formula (I) is less than or equal to 3 and per
Molekül mindestens ein Rest Y mit mindestens einem Rest F enthalten ist. Molecule contains at least one radical Y with at least one radical F.
2. Organosiliciumverbindungen nach Anspruch 1, dadurch gekennzeichnet, dass es Organopolysiloxane der allgemeinen2. Organosilicon compounds according to claim 1, characterized in that there are organopolysiloxanes of the general
Formelformula
YgR3_gSiO(SiR20)n(SiRYO)pSiR3_gYg (IV) ,Y g R3_ g SiO (SiR 2 0) n (SiRYO) pSiR 3 _ g Y g (IV),
wobei R und Y die in Anspruch 1 dafür angegebene Bedeutung haben, g 0, 1 oder 2 ist, n 0 oder eine ganze Zahl von 1 bis 1000 ist, p 0 oder eine ganze Zahl von 1 bis 100 ist, mit der Maßgabe, daß mindestens ein Rest Y mit mindestens einem Rest F je Molekül enthalten ist und die n-Einheiten (SiR20) und die p-Einheiten (SiRYO) beliebig im Molekül verteilt sein können, sind.wherein R and Y have the meaning given in claim 1, g is 0, 1 or 2, n is 0 or an integer from 1 to 1000, p is 0 or an integer from 1 to 100, with the proviso that at least one radical Y is present with at least one radical F per molecule and the n units (SiR 2 O) and the p units (SiRYO) can be distributed as desired in the molecule.
3. Organosiliciumverbindungen nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass Y ein Rest der Formel3. Organosilicon compounds according to claim 1 or 2, characterized in that Y is a radical of the formula
R2C(=0)NH-(CH2)3- oderR 2 C (= 0) NH- (CH 2 ) 3 - or
R2C(=0)NH-(CH2)2-NH-(CH2)3- oderR 2 C (= 0) NH- (CH 2 ) 2 -NH- (CH 2 ) 3 - or
R2C (=0) NH- (CH2) 2-NC (=0) R2- (CH2) 3- ist, wobei R2 die in Anspruch 1 angegebene Bedeutung hat.R 2 is C (= 0) NH- (CH 2 ) 2 -NC (= 0) R 2 - (CH 2 ) 3 -, where R 2 has the meaning given in claim 1.
4. Verfahren zur Herstellung der Amidogruppen aufweisenden Organosiliciumverbindungen nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, dass4. A process for the preparation of the organosilicon compounds containing amido groups according to claim 1, 2 or 3, characterized in that
Aminogruppen aufweisende Organosiliciumverbindungen (1) der allgemeinen FormelOrganosilicon compounds (1) having amino groups of the general formula
RaXb(OR1)dSi04-(a+b+d) (II)R a X b (OR 1 ) d Si0 4 - (a + b + d ) (II)
wobei R, R1, a und d die oben dafür angegebene Bedeutung haben, X ein Rest der Formelwhere R, R 1 , a and d have the meaning given above, X is a radical of the formula
-(R-NR5-)ZR-NR5 2,- (R-NR 5 -) Z R-NR 5 2 ,
ist, wobei R4 und z die im Anspruch 1 dafür angegebeneis, wherein R 4 and z that specified in claim 1 therefor
Bedeutung haben,Have meaning
R5 gleich oder verschieden sein kann und ein Wasserstoffatom oder einen Alkylrest bedeutet, mit der Maßgabe, dass an mindestens einem Stickstoffatom im Rest X einR 5 can be the same or different and represents a hydrogen atom or an alkyl radical, with the proviso that at least one nitrogen atom in the radical X is a
Wasserstoffatom gebunden ist, b 0, 1 oder 2 ist, mit der Maßgabe, dass die Summe aus a, b und d in denHydrogen atom is bound, b is 0, 1 or 2, with the proviso that the sum of a, b and d in the
Einheiten der Formel (II) kleiner oder gleich 3 ist und pro Molekül mindestens ein Rest X enthalten ist, mit Fettsäuren (2), die mindestens 16 Kohlenstoffatome aufweisen, oder Glyceride dieser Fettsäuren umgesetzt werden.Units of the formula (II) is less than or equal to 3 and each molecule contains at least one radical X, with fatty acids (2) which have at least 16 carbon atoms, or glycerides of these fatty acids.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass als Aminogruppen aufweisende Organosiliciumverbindungen (1) Organopolysiloxane der allgemeinen Formel5. The method according to claim 4, characterized in that as amino groups having organosilicon compounds (1) organopolysiloxanes of the general formula
XgR3_gSiO(SiR20)n(SiRXO)raSiR3_gXg (III),X g R3_ g SiO (SiR 2 0) n (SiRXO) ra SiR 3 _ g X g (III),
wobei R und X die in Anspruch 4 angegebene Bedeutung haben, g 0, 1 oder 2 ist, n 0 oder eine ganze Zahl von 1 bis 1000 ist, m 0 oder eine ganze Zahl von 1 bis 100 ist, mit der Maßgabe, daß mindestens ein Rest X je Molekül enthalten ist und die n-Einheiten (SiR20) und die m-wherein R and X have the meaning given in claim 4, g is 0, 1 or 2, n is 0 or an integer from 1 to 1000, m is 0 or an integer from 1 to 100, with the proviso that at least one X is contained per molecule and the n-units (SiR 2 0) and the m-
Einheiten (SiRXO) beliebig im Molekül verteilt sein können, eingesetzt werden. Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, dass X ein Rest der FormelUnits (SiRXO) can be distributed anywhere in the molecule. A method according to claim 4 or 5, characterized in that X is a radical of the formula
H2N(CH2)3- oderH 2 N (CH 2 ) 3 - or
H2N(CH2)2NH(CH2)3- ist .H 2 N (CH 2 ) 2 NH (CH 2 ) 3 -.
7. Verfahren zur Imprägnierung von organischen Fasern mit den Organosiliciumverbindungen nach Anspruch 1, 2 oder 3.7. A method for impregnating organic fibers with the organosilicon compounds according to claim 1, 2 or 3.
8. Verwendung der Organosiliciumverbindungen nach Anspruch 1, 2 oder 3, als Gleitmittel für die Garn- oder Fadenausrüstung.8. Use of the organosilicon compounds according to claim 1, 2 or 3, as a lubricant for the yarn or thread finishing.
9. Verwendung der Organosiliciumverbindungen nach Anspruch 1, 2 oder 3, als Poliermittel für keramische Oberflächen und Lacke.9. Use of the organosilicon compounds according to claim 1, 2 or 3, as a polishing agent for ceramic surfaces and paints.
10. Verwendung der Organosiliciumverbindungen nach Anspruch 1, 2 oder 3, in der Kosmetik.10. Use of the organosilicon compounds according to claim 1, 2 or 3, in cosmetics.
11. Verwendung der Organosiliciumverbindungen nach Anspruch 1, 2 oder 3, in Haarpflegemitteln.11. Use of the organosilicon compounds according to claim 1, 2 or 3, in hair care products.
12. Verwendung der Organosiliciumverbindungen nach Anspruch 1, 2 oder 3, in Flüssigkeiten für die Reprografie. 12. Use of the organosilicon compounds according to claim 1, 2 or 3, in liquids for reprography.
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WO2012041733A1 (en) * 2010-09-28 2012-04-05 Wacker Chemie Ag Fully acylated amino-functional organopolysiloxanes
WO2017182061A1 (en) 2016-04-19 2017-10-26 Wacker Chemie Ag Amino-organopolysiloxane and preparation method thereof
WO2021111714A1 (en) * 2019-12-05 2021-06-10 信越化学工業株式会社 Organopolysiloxane and fiber treating agent using same
WO2022140522A1 (en) 2020-12-23 2022-06-30 Ecolab Usa Inc. Laundry sour softener with extra stability and additional benefits of laundry fire mitigation and sunscreen removal
WO2022140505A1 (en) 2020-12-23 2022-06-30 Ecolab Usa Inc. Soil removal on cotton via treatment in the rinse step for enhanced cleaning in the subsequent wash
WO2023122196A1 (en) 2021-12-22 2023-06-29 Ecolab Usa Inc. Compositions comprising multiple charged cationic compounds for soil release

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WO2012041733A1 (en) * 2010-09-28 2012-04-05 Wacker Chemie Ag Fully acylated amino-functional organopolysiloxanes
CN103282410A (en) * 2010-09-28 2013-09-04 瓦克化学股份公司 Fully acylated amino-unctional organopolysiloxanes
JP2013543530A (en) * 2010-09-28 2013-12-05 ワッカー ケミー アクチエンゲゼルシャフト Fully acylated amino-functional organopolysiloxane
CN103282410B (en) * 2010-09-28 2015-06-03 瓦克化学股份公司 Fully acylated amino-unctional organopolysiloxanes
WO2017182061A1 (en) 2016-04-19 2017-10-26 Wacker Chemie Ag Amino-organopolysiloxane and preparation method thereof
US10954342B2 (en) 2016-04-19 2021-03-23 Wacker Chemie Ag Amino-organopolysiloxanes and preparation method therefor
WO2021111714A1 (en) * 2019-12-05 2021-06-10 信越化学工業株式会社 Organopolysiloxane and fiber treating agent using same
JP2021088670A (en) * 2019-12-05 2021-06-10 信越化学工業株式会社 Organopolysiloxane and fiber treating agent using the same
WO2022140522A1 (en) 2020-12-23 2022-06-30 Ecolab Usa Inc. Laundry sour softener with extra stability and additional benefits of laundry fire mitigation and sunscreen removal
WO2022140505A1 (en) 2020-12-23 2022-06-30 Ecolab Usa Inc. Soil removal on cotton via treatment in the rinse step for enhanced cleaning in the subsequent wash
WO2023122196A1 (en) 2021-12-22 2023-06-29 Ecolab Usa Inc. Compositions comprising multiple charged cationic compounds for soil release

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