EP1268614A1 - Emulsions polymeres aqueuses stables, leur preparation et leur utilisation - Google Patents

Emulsions polymeres aqueuses stables, leur preparation et leur utilisation

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Publication number
EP1268614A1
EP1268614A1 EP01931548A EP01931548A EP1268614A1 EP 1268614 A1 EP1268614 A1 EP 1268614A1 EP 01931548 A EP01931548 A EP 01931548A EP 01931548 A EP01931548 A EP 01931548A EP 1268614 A1 EP1268614 A1 EP 1268614A1
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EP
European Patent Office
Prior art keywords
general formula
component
fatty acid
alkyl
polymer emulsions
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.)
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Application number
EP01931548A
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German (de)
English (en)
Inventor
Günther GLAS
Toni Simenc
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BASF SE
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BASF SE
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Publication of EP1268614A1 publication Critical patent/EP1268614A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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
    • D06M13/10—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 oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/419—Amides having nitrogen atoms of amide groups substituted by hydroxyalkyl or by etherified or esterified hydroxyalkyl 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • 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
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
    • 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
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
    • 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 present invention relates to aqueous polymer emulsions which contain polyolefin or paraffin oxides and amino-polyorganosiloxanes and emulsifiers and optionally nitrogen-based esters, processes for the advantageous preparation of the polymer emulsions according to the invention and their use as auxiliaries in textile finishing, in particular as plasticizers, as smoothing agents and for Improving sewability.
  • DE-A-196 26 317 discloses condensation products of alcohols containing amino groups and of polyols with fatty acids, which can be used to reduce yellowing when storing colored textiles and as a plasticizer for low-yellowing high-quality finishing of textiles.
  • DE-A-33 43 575 discloses a process for the preparation of stable emulsions from a) terminal diorganopolysiloxanes containing Si-bonded OH groups, b) polyorganosiloxanes which have at least two substituents containing -NH or -NH groups, c) polyorganosiloxanes which have at least two hydroxyl, alkoxy or acyloxy groups bonded to Si directly or via a polyether chain and a condensation catalyst.
  • the emulsions are intended for permanent, chemical cleaning-stable improvement of the grip and elasticity of textile materials.
  • Paraffin and polyolefin oxidates are described which are caused by air oxidation of paraffins or polyolefms, in particular for example polyethylene, at temperatures above 100 ° C.
  • paraffins or polyolefms in particular for example polyethylene
  • These products are emulsifiable on account of their carboxyl and ester group contents and have been used in a wide variety of applications.
  • the emulsions can be used, for example, to improve the tear resistance, the dirt repellency and for water repellency.
  • the aids known from the prior art have each been used for relatively narrow areas of responsibility. They are not suitable to adequately meet the need for textile auxiliaries with the broadest possible performance profile. This shows that it is very difficult to satisfactorily meet the sometimes contradicting requirements for such aids.
  • the present invention thus relates to stable aqueous polymer emulsions comprising components A to C, water and, if appropriate, further auxiliaries and additives, component A being
  • R 1 for hydrogen or lower alkyl and R 2 for hydrogen, -COOH, or another functional group containing oxygen and
  • R 2 furthermore represents a short- or medium-chain alkyl or alkenyl group, or cyclohexyl group, which can also be substituted by -COOH or another functional group containing oxygen, or R 1 and R 2 together represent oxygen, and r represents a number from 30 to 200,
  • R 3 is the same or different lower alkyl or lower alkoxy groups
  • R 4 is hydroxy or a radical R 3
  • Z is an aminoalkyl radical
  • s is a number from ⁇ 50 to ⁇ 300 and t is a number from 1 to 4
  • nonionic emulsifiers consisting of mixtures of alkoxylated higher alkanols are used as component C.
  • the emulsions according to the invention expediently also contain components D and E in order to optimize the application properties and the production process and to further improve the emulsion stability, component D being condensation products of fatty acids of the general formula III
  • R 5 is a medium- to long-chain alkyl or alkenyl radical, with 5 to 150 mol% per mole of fatty acid amino alcohols of the general formula IV
  • a 1 and A 2 denote lower alkylene groups
  • R 6 , R 7 and R 8 are identical or different and each represent hydrogen, lower alkyl or a group -A ⁇ OH or -A 2 -OH and n is an integer from 1 to 5, and with 5 to 200 mol- % per mole of fatty acid polyols of the general formula V
  • R 9 denotes hydrogen, lower alkyl, another hydroxy-lower alkyl group
  • R 10 denotes hydrogen, lower alkyl, or a further hydroxy-lower alkyl group, and as component E at least partially quaternized condensation products of fatty acids of the general formula VI
  • R, ⁇ is a medium- to long-chain alkyl or alkenyl radical, with 0.35 to 2.0 moles per mole of fatty acid, tertiary amino alcohols of the general formula VII
  • a 3 , A 4 and A 5 denote lower alkylene groups, quaternized with quaternizing agents of the formula XR, in which X is a radical which can be split off as an anion and R 12 is a lower alkyl radical.
  • the emulsions may contain other suitable additives which are customary for the respective field of application, such as, for example, fungicides, insecticides, color brighteners, foam suppressants and the like. Are preferred as component A.
  • R 1 is hydrogen or C ⁇ - to C 4 - alkyl
  • R 2 represents hydrogen, -COOH, -CHO, -OH, lower alkylcarbonyloxy (-O-CO-R 13 ) or lower alkoxycarbonyl (-COOR 14 ), where R 13 and R 14 are alkyl radicals, preferably with 1 to 4, in particular 1 to 2 carbon atoms are and
  • R 2 also represents a - to C 6 - alkyl or alkenyl group, or cyclohexyl group, which can also be substituted by -COOH, -CHO, -OH, lower alkylcarbonyloxy (-O-CO-R 13 ) or lower alkoxycarbonyl (-COOR 14 ) can, wherein R 13 and R 14 are alkyl radicals, preferably having 1 to 4, in particular 1 to 2, carbon atoms, it being possible for COOH and - OH groups which represent R or are present in substituents R to form intermolecular or intramolecular esters with one another , or
  • R and R together represent oxygen, r represents a number from 30 to 200, preferably from 40 to 100, and the polyolefin oxidate has an acid number from 10 to 60, preferably from 15 to 30, mg KOH / g according to DIN 53402.
  • component D is preferred as component D.
  • R 5 denotes a C 9 to C 21 alkyl or alkenyl radical, with 5 to 150 mol% per mole of fatty acid amino alcohols of the general formula IV
  • a 1 and A 2 denote C 2 to C 4 alkylene groups
  • R, R and R are the same or different and each is hydrogen, Ci to C - alkyl or a group
  • n is an integer from 1 to 5, and with 5 to 200 mol% per mole of fatty acid polyols of the general formula V.
  • Y represents a chemical bond or a group -CR 9 R 10 -
  • R 9 denotes hydrogen, C 1 -C 4 -alkyl, a further hydroxyalkyl group having 1 to 4 C atoms and
  • R 10 is hydrogen, Ci to C - alkyl, or a further hydroxyalkyl group with 1 to 4 carbon atoms.
  • Preferred as component E are at least partially quaternized condensation products of fatty acids of the general formula VI
  • R 11 is a C - to C j - alkyl or alkenyl radical, with 0.35 to 2 mol, preferably 0.5 to 2 mol, per mol of fatty acid tertiary amino alcohols of the general formula VII
  • A, A and AC denote 2 to C alkylene groups, preferably ethylene groups, quaternized with quaternizing agents of the formula XR 12 , in which X is a radical which can be split off as an anion and R 12 is a lower alkyl radical having 1 to 4 C atoms.
  • the alkylene groups A 1 and A 2 contained in a compound of the formula IV can be the same or different. The same applies to those in a connection of the formula VII contained alkylene groups A 3 , A 4 and A 5 .
  • Compounds of the formula II preferably have two identical alkylene groups A and A, compounds of the formula VII three identical alkylene groups A 3 , A 4 and A 5 .
  • the free bonds of the alkylene groups can be on adjacent C atoms or, in the case of chain lengths over 2, on non-adjacent C atoms.
  • a butylene group can also have the structure of a 2-methyl-propane-diyl group.
  • the polymer emulsions according to the invention can contain individual substances or several substances from each of component groups A to E.
  • the materials used to manufacture components A to E are technical products, such as native fatty acids and amines, the composition of which corresponds on average to the formulas given above, but whose building blocks differ within the definitions given for them.
  • Preferred polymer emulsions according to the invention comprise components A to E, water and optionally further auxiliaries and additives. Conveniently, they contain
  • component A 1 to 15% by weight, in particular 2 to 10% by weight, component A,
  • the performance properties of the polymer emulsions according to the invention naturally also depend essentially on the structure of the components and thus also on the structure of the starting materials used, on the molar ratios used in the preparation and, as explained further below, on the reaction conditions during the preparation from.
  • polyolefin oxidates contained as component A in the polymer emulsions according to the invention represent functionalized polyolefins which can be illustrated by the general formula I given above.
  • the polyolefin oxidates are known substances which are produced by known processes by air oxidation of natural paraffins or synthetic polyolefms. In this oxidation, chain cleavage and / or hydrogen cleavage generally occurs and oxygen, predominantly in the form of COOH groups and OH groups, is introduced into the alkane chains.
  • the carboxyl and hydroxyl groups also react to a certain extent with one another to form intermolecular and intramolecular ester groups which, if desired, can be transesterified with short to medium chain length alkanols.
  • other complicated side reactions such as isomerization, and to a lesser extent the formation of aldehyde and keto functions take place.
  • R preferably represents hydrogen, R preferably represents -COOH and ester groups.
  • Amino-functional polyorganosiloxanes of the general formula II given above are used as component B, in which R 3 is the same or different alkyl or alkoxy groups having 1 to 4 carbon atoms,
  • R 4 is hydroxy or a radical R 3
  • Z is an aminoalkyl radical n is a number from ⁇ 50 to ⁇ 300 and m is a number from 1 to 4.
  • R 3 is preferably methyl, ethyl, methoxy or ethoxy, in particular R 3 represents a methyl group.
  • R 4 is preferably hydroxy or methyl.
  • n is preferably chosen so that the polyorganosiloxane of the formula II, if R 4 is methyl, has a viscosity - measured according to Brookfield - of 150 to 400 mPa.s, preferably 180 to 300 mPa.s, and if R is hydroxyl or alkoxy stands, has a viscosity of 2000 to 10000 mPa.s, preferably 3000 to 8000 mPa.s, measured at 25 ° C.
  • the alkylene group of the aminoalkyl radical representing Z represents a bridge member L between the silicon atom and the amino group.
  • the alkylene bridge L has 1 to 10 C atoms, preferably 1 to 5 C atoms; it can be linear or branched and the carbon chain can be interrupted by a hetero link, for example -O-, -S- or -NR 15 -, the R 15 of the -NR 15 group representing hydrogen or C ⁇ - or C 2 - Alkyl, preferably hydrogen.
  • bridge members L are -CH 2 -, -C 2 H -, -CH (CH 3 ) CH 2 -, - (CH 2 ) 3 -, - (CH 2 ) 6 -, -CH 2 CH (CH 3 ) CH 2 -, - (CH 2 ) 10 -, -CH 2 CH 2 SCH 2 CH 2 -, -CH 2 CH 2 OCH 2 CH2-, -OCH2CH2-, -O (CH 2 ) 3 -, or -CH2CH2NHCH2CH 2 -.
  • the amino group of the aminoalkyl radical representing Z corresponds to the formula - NR 16 R 17 , where R 16 and R 17 independently of one another are hydrogen or C 1 -C 4 -alkyl radicals.
  • R 16 and R 17 independently of one another are hydrogen or C 1 -C 4 -alkyl radicals.
  • preferred aminoalkyl radicals are -C 3 H 6 -NH 2 , -C 3 H 6 -NH-C 2 H -NH2, -CH 2 -N (CH 3 ) 2 , - (CH 2 ) 5 -NH 2 .
  • m is chosen so that the polyorganosiloxane has an amine number of 0.1 to 0.4. (The amine number is the number of ml In HC1 required to neutralize 1 g of the substance to be tested.)
  • Polyorganosiloxanes of the formula XI which are suitable as component D for the polymer emulsions according to the invention, are manufactured and traded on an industrial scale by several companies.
  • the alkylene oxide units contained in these components have 2 to 4, preferably 2 or 3, in particular 2, carbon atoms.
  • component D are condensation products of fatty acids of the formula III in which R 5 is branched and above all linear Cn to C 19 alkyl or alkenyl and in particular C 13 to C 1 alkyl or alkenyl.
  • the grouping R 5 -CO- of the fatty acids of the formula III is derived, for example, from lauric acid, myristic acid, elaidic acid, linoleic acid, linolenic acid or
  • fatty acids are used, in many cases they can be mixtures of homologues and / or mixtures of saturated and unsaturated carbon atoms of the same number.
  • tallow fatty acid and coconut fatty acid are therefore both the mixtures of the fatty acids present in the natural fats in the mixing ratios present in the fats and also individual fractions or individuals which can be isolated therefrom.
  • the mixtures of the fatty acids present in the natural fats in the mixing ratios present in the fats are preferred.
  • Alkylene groups A 1 and A 2 in the amino alcohols of the formula II are, for example, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 1,3-
  • condensation products D which use an amino alcohol of the general formula IVa
  • R 6 , R 7 and R 8 are the same or different and each represent hydrogen, methyl or ethyl and m represents the numbers 2 or 3, are obtained.
  • amino alcohol of the formula IVa is N- ( ⁇ -aminoethyl) ethanolamine.
  • the amino alcohols of the formulas IV and IVa can - in particular if technical qualities are used - certain proportions of mono-, di- or trialkanolamines of the formula [HO-A 1 (or A 2 )] X -NH (3-X ), where x means the numbers 1, 2 or 3. These proportions should be below 20% by weight, preferably below 10% by weight.
  • condensation products D which, using a polyol of the general formula Va,
  • R 9 is a hydroxyl group or a hydroxymethyl group
  • R 10 signifies hydrogen, methyl, ethyl or hydroxymethyl, can be obtained.
  • the fatty acids of the formula III are heated with the amino alcohols IV and the polyols V in the molar ratios indicated above in the presence of an acid catalyst, preferably in the presence of catalytic amounts of phosphorous acid and / or hypophosphorous acid.
  • the condensation is expediently carried out at temperatures of 150 to 170.degree.
  • condensation can also be carried out in the presence of a solvent or diluent.
  • a solvent or diluent for example, it is advantageous to use an entrainer which forms an aceotrope with water, which considerably facilitates the removal of the water from the reaction mixture, and to work under a protective gas such as, for example, nitrogen.
  • Fatty acids of the formula III are preferably condensed with the amino alcohols of the formula IV and the polyols of the formula V in such a ratio that the condensation products D are fatty acid alkanolamine esters of the general formula VIII
  • components D are preferred, the fatty acid alkanolamine esters of the general formula Villa
  • Condensation products of fatty acids of the formula III with 40 to 70 mol% per mole of fatty acid amino alcohols of the formula IV and 30 to 120 mol% per mole of fatty acid polyols of the formula V are therefore particularly suitable as components D.
  • Preferred components of the polymer emulsions according to the invention are in particular those components D which contain 0 to 50 mol% per mole of fatty acid alkanolamine ester alkanolamines of the formula IV, preferably of the formula IVa, and 0 to 100 mol% per mole of fatty acid polyol ester polyols of the formula V, preferably of the formula Va.
  • the amino esters contained in component D can be present in the polymer emulsions according to the invention in free form or in the form of their salts, preferably as formates or acetates.
  • Preferred components E of the polymer emulsions according to the invention are at least partially quaternized condensation products of fatty acids of the general formula VI given above with 0.5 to 2.0 mol, in particular 0.85 to 1.5 mol, of tertiary amino alcohols of the general formula VII per mol of fatty acid.
  • the condensation products E are quaternized with quaternizing agents of the formula XR 12 , in which R 12 is a lower alkyl radical having 1 to 4 carbon atoms and anionically removable radical X is usually a halogen atom, the methosulfate or sulfate group or a sulfonate group, preferably the methosulfate group.
  • the partially quaternized condensation products consist of a mixture of compounds of the formulas X and XI,
  • R 18 is a radical of the formula -CO-R 11 , X represents one of the abovementioned anions and p represents 0, 1, 2 or 3.
  • the proportions of the components contained in said mixture depend on the one hand on the molar ratio in which fatty acids of the formula VI have been condensed with amines of the formula VII and on the molar ratio in which the esterified amines of the formula X have been reacted with the quartering agent , on the other hand according to the reaction conditions under which the condensation has been carried out.
  • the composition can therefore be varied as desired by the person skilled in the art within the definition limits specified above in the formulas by suitable selection of the molar ratios and the reaction conditions.
  • Mixtures in which, on average, one or two of the OH groups of the amine of the formula VII are esterified with the fatty acid the person skilled in the art will choose a molar ratio of fatty acid to amine of 1: 1 or 1: 2.
  • Such a statistical mixture usually contains compounds of the formula X in which p has values of 0, 1, 2 and 3.
  • the proportions of these mixture components are very different, the highest proportion usually being the compound, the composition of which most closely approximates the statistical composition agent.
  • the scatter of the proportions depends on the one hand on the natural reactivities of the reactants, but can within certain limits be routinely controlled by the person skilled in the art through the choice of the reaction conditions, in particular the condensation temperature and the reaction time.
  • the polymer emulsions according to the invention have an optimal combination of various performance properties. To the best of our knowledge, products with such an advantageous property profile are not yet on the market.
  • the polymer emulsions according to the invention give the treated textiles a very pleasant, soft, somewhat smooth, silk-like handle.
  • the stability of the polymer emulsions according to the invention is excellent.
  • the size of the emulsified droplets is in the semimicro range, i.e. they have an average diameter of 15 to 20 nm, with the result that the aqueous dilutions of the polymer emulsions are transparent, almost like real aqueous solutions.
  • the polymer emulsions according to the invention have very good storage stability. They remain unchanged even after one month at 60 ° C.
  • the polymer emulsions according to the invention are stable in all pH ranges, even in the strongly acidic one. They can therefore also be used in the moisture crosslinking process, which works in the strongly acidic pH range.
  • the polymer emulsions according to the invention are extremely stable even in the presence of electrolyte additives; they thus show a so-called "masked non-ionic character". This results in the further considerable application-technical advantage that they are compatible with all additives which are also used in the finishing of textile materials.
  • the polymer emulsions according to the invention are free from yellowing, i.e. they do not yellow on the white goods at the condensation temperatures of up to 180 ° C that are common in high finishing.
  • Another advantage is that they can be produced in a low-foaming embodiment, so that they can also be used for exhaust processes in apparatus with high circulation currents, e.g. are suitable in JET apparatus.
  • the polymer emulsions according to the invention are not only extremely stable themselves, but also that they largely prevent the deposition of condensation products from the resin precondensates used as high-quality agents on the rollers and tub walls of the machines used. They can therefore be used with particular advantage as aids in the finishing of textile materials.
  • the present invention therefore also relates to the use of the polymer emulsions according to the invention alone or in combination with other additives and in particular with high-quality finishing agents for textile treatment.
  • Textile materials in the sense of this description are fiber materials made of natural or synthetic fibers, which in principle can exist in all processing states. However, for reasons of expediency, flat textile materials and ready-made goods are preferably treated using the polymer emulsions according to the invention.
  • the preparation of the polymer emulsions according to the invention can in principle be carried out by a person skilled in the art in a manner known per se using conventional mixing devices. Since the components A to E contained in the polymer emulsions according to the invention have a different ionogenicity and consistency, it has proven to be advantageous to mix the components in a specific sequence and within certain temperature ranges in order to achieve optimal "product harmony".
  • components B and D can also be used in the form of prefabricated emulsions. This measure considerably simplifies the production of polymer emulsions according to the invention.
  • components D1, D2 and E used in the exemplary embodiments are produced as follows: Production of component Dl
  • the molar ratio of fatty acid: aminoethanolamine: trimethylolpropane is 1.9: 1: 1.5.
  • the amount of catalyst is 0.3% by weight, based on the amount of fatty acid used.
  • the flask is flushed with nitrogen, and as soon as the air is displaced, the clear, yellowish reactant mixture is heated to 160 ° C. while maintaining a slow stream of nitrogen, and stirring is continued for 4.5 hours at this temperature. During this time, the water formed during the reaction is continuously removed (distilled off).
  • the acid number (measured potentiometrically) has a value of 19 mg KOH / g, which corresponds to a degree of conversion of approx. 92% (based on fatty acid).
  • the liquid waxy reaction product obtained is cooled to 80 to 90 ° C. and neutralized by adding 26 g of acetic acid.
  • the molar ratio of fatty acid: aminoethanolamine: trimethylolpropane is 1.9: 1: 1.
  • the amount of catalyst is 0.3% by weight, based on the amount of fatty acid used.
  • the flask is flushed with nitrogen, and as soon as the air is displaced, the clear, yellowish reactant mixture is heated to 160 ° C. while maintaining a slow stream of nitrogen, and stirring is continued for 4.5 hours at this temperature. During this time, the water formed during the reaction is continuously removed (distilled off).
  • the acid number (measured potentiometrically) has a value of 20 mg KOH / g, which corresponds to a degree of conversion of approx. 90% (based on fatty acid).
  • the liquid waxy reaction product obtained is cooled to 80 to 90 ° C. and neutralized by adding 26 g of acetic acid.
  • the molar ratio of fatty acid: triethanolamine is 1: 1.02.
  • the amount of catalyst is about 0.3% by weight, based on the amount of fatty acid used.
  • the flask is flushed with nitrogen, and as soon as the air has been displaced, the clear, yellowish reactant mixture is heated to 160 ° C. while maintaining a slow nitrogen stream, and stirring is continued for 5 hours at this temperature. During this time, the water formed during the reaction is continuously removed.
  • the acid number (measured potentiometrically) has a value of 20 mg KOH / g, which corresponds to a degree of conversion of approx. 90% (based on fatty acid).
  • the liquid waxy reaction product obtained is cooled to 70 to 80 ° C. and 14.54 g of dimethyl sulfate are added dropwise at this temperature in the course of about 30 minutes. The mixture is left to stir for a further hour at 80 ° C. and then cooled to room temperature.
  • component A is a polyethylene wax oxidized with air (eg commercial product ® LUWACHS OA 2), which has the following parameters: Molar mass: 3000 g / mol, dropping point according to Ubbelohde: 107 to 113 ° C, melting point according to DIN 51007: 99 to 108 ° C density: 0.96 g / cm3, acid number: 20 to 25 mg KOH / g.
  • a polyethylene wax oxidized with air eg commercial product ® LUWACHS OA 2
  • Molar mass 3000 g / mol
  • dropping point according to Ubbelohde 107 to 113 ° C
  • melting point according to DIN 51007 99 to 108 ° C density: 0.96 g / cm3
  • acid number 20 to 25 mg KOH / g.
  • Dimethyl-polysiloxane which has an OH group bonded to silicon in the terminal assemblies, with a viscosity measured at
  • Composition of the melts SI to S5 in parts by weight (parts by weight) of the components are provided.
  • aqueous solutions L1 to L5 of components Dl, D2 and E and optionally a defoamer are prepared with the compositions shown in Table 2.
  • the specified amounts of the components and, if appropriate, a defoamer are stirred into the stated amount of water in succession at 98 ° C. and stirring is continued until complete homogenization.
  • composition of the aqueous solutions L1 to L5 in parts by weight (parts by weight) of the components.
  • each of the emulsions SL1 to SL3 thus produced 10 parts by weight. (containing 3 parts by weight of solid substance), 20 parts by weight (containing 6 parts by weight of solid substance) of the above-mentioned emulsion of component B are stirred into emulsion SL4.
  • the SL5 emulsion does not contain any component B.
  • the emulsions SL1 to SL4 remained homogeneous after storage.
  • the emulsion SL5 was separated after a storage period of 6 hours.
  • the shear stability was tested with the emulsions SL1 to SL4 according to the invention.
  • the SL5 emulsion was not subjected to this test because of the poor storage stability.
  • composition in g / 1 of the test fleets for testing for shear stability Composition in g / 1 of the test fleets for testing for shear stability.
  • test liquors VI to V5 were first stirred at 3000 rpm for 10 minutes and then tested as follows:
  • the foulard has 2 horizontally mounted rollers with a diameter of 9 cm and a length of 15 cm.
  • the drive takes place electrically via a continuously variable transmission.
  • the roller pressure is adjusted via a lever arm of 35 cm in length, which in the end is loaded with a lead weight of approx. 12 kg.
  • the hardness of the paddle rollers is 72 ° Shore for the drive roller and 84 ° Shore for the pressure roller.
  • An endless cotton fabric 12 cm wide and 56 cm long is run at a speed of approx. 12 m / min for 30 minutes through the fleet into the crushing unit from below. Then the roll covering that may have been formed is assessed visually, with the grade 1 meaning no roll covering, the grade 5 indicating a strong roll covering.
  • test liquor V6 (without the addition of a polymer emulsion according to the invention) does not produce any roll coating (grade 1)
  • test liquors VI to V3 (containing the emulsions SL1, SL2 and SL3) do not result in any roll covering.
  • the roller surface remains smooth and clean (grade 1).
  • the liquor V4 (containing the emulsion SL4) gives a visually barely perceptible (grade 1-2) and the liquor V5 (containing only component D) a clearly recognizable roller coating (grade 2-3).
  • a mixed fabric polyester / cotton 50/50 with a basis weight of approx. 90 g / m 2 is impregnated with the test liquors VI to V6 and on the foulard to a liquor absorption of approx. 70% by weight, based on the weight of the dry fabric , squeezed.
  • the moist tissue is then dried at 110 ° C. and condensed at 140 ° C. for 4 minutes. Result:
  • tissue samples treated with the fleets VI, V2, V3 and V5 show no differences in the handle; they feel equally soft, with a characteristic silicone-specific smoothness.
  • the goods equipped with the fleet V4 correspond in terms of softness to the fabric samples equipped with the fleets VI to V3 and V5, but they are slightly better than those in terms of smoothness.
  • the fabric equipped with the V6 fleet on the other hand, feels hard and rough.
  • a knitted cotton fabric was equipped as described in the inspection of the fabric handle.
  • the finished material was sewn on an industrial sewing machine with a needle system 5620 SES, thread no. 120, at a speed of 4500 rpm and 6 stitches per cm.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des émulsions polymères aqueuses stables comprenant les composants A à C, de l'eau et éventuellement d'autres auxiliaires et additifs. Le composant C est formé par des produits d'oxydation de polyoléfine qui contiennent en particulier des groupes carboxyle et ester. Des polyorganosiloxanes à fonctions amine constituent le composant D, et des émulsifiants non ioniques le composant E. De préférence, ces émulsions polymères contiennent en outre des produits de condensation d'acides gras comportant 5 à 150 % en moles d'amino-alcools par mole d'acide gras et 5 à 200 % en mole de polyols (composant D) par mole d'acide gras, ainsi que des produits de condensation, au moins partiellement quaternisés, d'acides gras comportant 0,35 à 3,5 moles d'amino-alcools tertiaires par mole d'acide gras, quaternisés avec des agents de quaternisation de formule X-R14, dans laquelle X représente un reste séparable sous forme d'anion, et R14 un reste alkyle inférieur. L'invention concerne un procédé pour préparer de manière avantageuse lesdites émulsions polymères, ainsi que leur utilisation en tant qu'auxiliaire dans l'ennoblissement des textiles, notamment comme assouplissant, comme agent lissant et pour améliorer le comportement à la couture.
EP01931548A 2000-03-27 2001-03-26 Emulsions polymeres aqueuses stables, leur preparation et leur utilisation Withdrawn EP1268614A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10015174A DE10015174A1 (de) 2000-03-27 2000-03-27 Stabile wäßrige Polymeremulsionen, ihre Herstellung und Verwendung
DE10015174 2000-03-27
PCT/EP2001/003406 WO2001072874A1 (fr) 2000-03-27 2001-03-26 Emulsions polymeres aqueuses stables, leur preparation et leur utilisation

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EP1268614A1 true EP1268614A1 (fr) 2003-01-02

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US (1) US20040024112A1 (fr)
EP (1) EP1268614A1 (fr)
CN (1) CN1420902A (fr)
AU (1) AU2001258297A1 (fr)
DE (1) DE10015174A1 (fr)
WO (1) WO2001072874A1 (fr)

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DE602006004429D1 (de) * 2005-02-02 2009-02-05 Wacker Chemie Ag Herstellung einer stabilen kleinteiligen organopolysiloxanemulsion
CN101633781B (zh) * 2008-07-22 2012-11-14 道康宁（上海）有限公司 乳液组合物,使纤维结构柔软的方法,以及含纤维基材
US8293002B2 (en) * 2009-04-29 2012-10-23 Angus Chemical Company Tertiary aminoalcohols as low VOC additives for paints and coatings
CN103003335B (zh) * 2010-07-21 2015-08-19 道康宁公司 氨基官能有机硅的乳液

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DE3343575A1 (de) * 1983-12-01 1985-10-03 Wacker-Chemie GmbH, 8000 München Verfahren zur herstellung von waessrigen emulsionen
DE4026029A1 (de) * 1989-09-07 1992-02-20 Sandoz Ag Waessrige aminopolysiloxanmikroemulsionen, deren herstellung und verwendung
US5310772A (en) * 1990-09-07 1994-05-10 Alliedsignal Inc. Coemulsification of oxidized polyethylene homopolymers and amino functional silicone fluids
CN1058274C (zh) * 1990-09-07 2000-11-08 联合信号股份有限公司 水性共乳化液及其制备方法和用途
CH685392A5 (de) * 1992-09-26 1995-06-30 Sandoz Ag Wässrige Wachs- und Silicon-Dispersionen und Verfahren zu deren Herstellung.
DE4329244A1 (de) * 1993-08-31 1995-03-02 Sandoz Ag Wässrige Wachs- und Silicon-Dispersionen, deren Herstellung und Verwendung
DE19626317A1 (de) * 1996-07-01 1998-01-08 Basf Ag Kondensationsprodukte von Fettsäuren mit Aminoalkoholen und Polyolen und ihre Verwendung als Textilhilfsmittel

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Title
See references of WO0172874A1 *

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US20040024112A1 (en) 2004-02-05
DE10015174A1 (de) 2001-10-04
WO2001072874A1 (fr) 2001-10-04
AU2001258297A1 (en) 2001-10-08
CN1420902A (zh) 2003-05-28

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