DE4435404A1 - Process for the preparation of stabilized aqueous polyolefin wax dispersions - Google Patents
Process for the preparation of stabilized aqueous polyolefin wax dispersionsInfo
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- DE4435404A1 DE4435404A1 DE4435404A DE4435404A DE4435404A1 DE 4435404 A1 DE4435404 A1 DE 4435404A1 DE 4435404 A DE4435404 A DE 4435404A DE 4435404 A DE4435404 A DE 4435404A DE 4435404 A1 DE4435404 A1 DE 4435404A1
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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
- C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/003—Organic compounds containing only carbon and hydrogen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—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
- D06M13/165—Ethers
- D06M13/17—Polyoxyalkyleneglycol ethers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—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 sulfur or phosphorus
- D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—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 sulfur or phosphorus
- D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
- D06M13/295—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing polyglycol moieties; containing neopentyl moieties
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
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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
- 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
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung stabili sierter wäßriger Polyolefinwachs-Dispersionen, bei dem man wäßrige Dispersionen aus einem Polyolefinwachs und einem sau ren tensidischen Dispergiermittel bei erhöhter Temperatur und gegebenenfalls erhöhtem Druck neutralisiert.The invention relates to a method for producing stabili based aqueous polyolefin wax dispersions, in which one aqueous dispersions of a polyolefin wax and a sau ren surfactant dispersant at elevated temperature and if necessary neutralized increased pressure.
Polymere auf Basis Ethylen und/oder Propylen mit einer mitt leren Molmasse im Bereich von 500 bis 20 000 weisen einen wachsartigen Charakter auf. Wäßrige Dispersionen dieser Po lyolefinwachse werden daher seit langem als Ersatz für na türliche Wachsemulsionen eingesetzt und dienen beispielsweise zur Versiegelung von harten Oberflächen, zur textilen Ausrü stung oder als Entschäumer.Polymers based on ethylene and / or propylene with an average leren molecular weight in the range of 500 to 20,000 have a waxy character. Aqueous dispersions of this bottom Lyolefin waxes have therefore long been a substitute for na Door wax emulsions used and serve for example for sealing hard surfaces, for textile finishing or as a defoamer.
Ein Problem bei der Herstellung dieser Polyolefinwachsdis persionen besteht darin, feinteilige Dispersionen zu erzie len, die über einen möglichst langen Zeitraum stabil sind und nicht sedimentieren. Eine Möglichkeit, die Dispergierbarkeit der Polyolefine zu verbessern, besteht in einer oxidativen Oberflächenbehandlung der Polymere. Hierbei werden Methyl- zu Carboxylgruppen oxidiert und die Polarität der Wachse erhöht. Üblicherweise werden die Polyolefine jedoch in die wäßrige Lösung eines tensidischen Dispergiermittels, vorzugsweise eines Alkylphosphates, eingerührt und über den Schmelzpunkt erhitzt. Die auf diesem Wege zugänglichen Dispersionen sind zwar hinreichend feinteilig, weisen jedoch eine nicht immer zufriedenstellende Lagerstabilität auf.A problem in the manufacture of these polyolefin wax disks persions consists of educating finely divided dispersions len that are stable for as long as possible and do not sediment. One way of dispersibility To improve the polyolefins is an oxidative Surface treatment of the polymers. Here, methyl- Carboxyl groups oxidized and the polarity of the waxes increased. Usually, however, the polyolefins are in the aqueous Solution of a surfactant dispersant, preferably of an alkyl phosphate, stirred in and above the melting point heated. The dispersions accessible in this way are Although sufficiently fine-grained, they do not always have one satisfactory storage stability.
Die Aufgabe der Erfindung hat somit darin bestanden, ein verbessertes Verfahren zur Herstellung von feinteiligen wäß rigen Polyolefinwachs-Dispersionen mit verbesserter Lager stabilität zur Verfügung zu stellen.The object of the invention was therefore a improved process for the production of finely divided aq rige Polyolefinwachs-Dispersions with improved storage to provide stability.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung stabilisierter wäßriger Polyolefinwachs-Dispersionen, bei dem manThe invention relates to a method for producing stabilized aqueous polyolefin wax dispersions in which one
- (a) eine wäßrige Lösung aus einem sauren tensidischen Dis pergiermittel und feinverteiltem Polyolefinwachs her stellt und(a) an aqueous solution of an acidic surfactant dis Pergiermittel and finely divided polyolefin wax represents and
- (b) die Dispersion anschließend durch Zugabe von Alkalihy droxiden oberhalb des Schmelzpunktes des Wachses neutra lisiert.(b) the dispersion is then added by adding alkali metal droxides above the melting point of the wax neutra lized.
Nachdem bekannt war, Polyolefinwachs-Dispersionen durch die Verwendung von Tensiden und insbesondere neutralisierten Alkylphosphaten zu stabilisieren, wurde überraschenderweise festgestellt, daß besonders feinteilige Dispersionen verbes serter Stabilität resultieren, wenn man Tenside in saurer Form, vorzugsweise saure Alkylphosphate, und Polyolefinwachse gegebenenfalls unter Druck einer gemeinsamen Neutralisation unterwirft.After it was known by the polyolefin wax dispersions Use of surfactants and especially neutralized Stabilizing alkyl phosphates has surprisingly been found that particularly fine dispersions verbes Serter stability result when surfactants in acid Form, preferably acidic alkyl phosphates, and polyolefin waxes possibly under pressure of a common neutralization submits.
Als Dispergiermittel kommen grundsätzlich anionische Tenside in ihrer sauren, d. h. nicht neutralisierten Form in Betracht. Typische Beispiele sind Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersulfonate, α-Methylestersulfonate, Sulfofettsäuren, Alkylsulfate, Fett alkoholethersulfate, Glycerinethersulfate, Hydroxymischether sulfate, Monoglycerid(ether)sulfate, Fettsäureamid(ether)sul fate, Mono- und Dialkylsulfosuccinate, Mono- und Dialkylsul fosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbon säuren, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäu retauride, Acyllactylate, Alkyloligoglucosidsulfate und Pro teinfettsäurekondensate (insbesondere pflanzliche Produkte auf Sojabasis). Sofern die anionischen Tenside Polyglycol etherketten enthalten, können sie eine konventionelle, vor zugsweise jedoch eine eingeengte Homologenverteilung aufwei sen. Vorzugsweise handelt es sich bei den Dispergiermitteln um Alkyl- bzw. Alkyletherphosphate in der sauren Form. Anionic surfactants are generally used as dispersants in their acidic, d. H. not neutralized form into consideration. Typical examples are alkylbenzenesulfonates, alkanesulfonates, Olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fat alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ethers sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sul fate, mono- and dialkylsulfosuccinates, mono- and dialkylsul fosuccinamate, sulfotriglycerides, amide soaps, ether carbon acids, fatty acid isethionates, fatty acid sarcosinates, fatty acid retaurides, acyl lactylates, alkyl oligoglucoside sulfates and Pro fatty acid condensates (especially vegetable products based on soy). If the anionic surfactants polyglycol Containing ether chains, they can be a conventional one but preferably a narrow homolog distribution sen. The dispersants are preferably to alkyl or alkyl ether phosphates in the acidic form.
Alkylphosphate und Alkyletherphosphate stellen bekannte anio nische Tenside dar, die üblicherweise durch Umsetzung von gegebenenfalls ethoxylierten Fettalkoholen mit Phosphorpent oxid hergestellt werden. In Abhängigkeit des Einsatzverhält nisses der Komponenten werden dabei technische Gemische er halten, die überwiegend Mono- und Dialkylester, neben Tri estern, Phosphorsäure und nicht umgesetzter Alkoholkomponente enthalten. Übersichten zu diesem Thema sind beispielsweise von R. S. Cooper sowie G. Imokawa in J. Am. Oil. Chem. Soc. 41, 337 (1964) bzw. 55, 839 (1978), H. Distler in Tenside Detergents 12, 263 (1975) und O′Lennick in Soap, Cosm., Chem. Spec. 7, 26 (1986) erschienen.Alkyl phosphates and alkyl ether phosphates are known anio African surfactants, which are usually by the implementation of optionally ethoxylated fatty alcohols with phosphorus pent oxide are produced. Depending on the application Technical components are then used in the components hold the predominantly mono and dialkyl esters, in addition to tri esters, phosphoric acid and unreacted alcohol component contain. Overviews on this topic are, for example by R. S. Cooper and G. Imokawa in J. Am. Oil. Chem. Soc. 41, 337 (1964) and 55, 839 (1978), H. Distler in Tenside Detergents 12, 263 (1975) and O'Lennick in Soap, Cosm., Chem. Spec. 7, 26 (1986) appeared.
Alkyl(ether)phosphate, die im Sinne der Erfindung in Betracht kommen, folgen der Formel (I),Alkyl (ether) phosphates which are considered in the context of the invention come, follow the formula (I),
in der R¹ für einen linearen oder verzweigten Alkylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder eine Gruppe R¹(OCH₂CH₂)n und n für 0 oder Zahlen von 1 bis 10 steht.in which R¹ is a linear or branched alkyl radical having 6 to 22 carbon atoms, R² is hydrogen or a group R¹ (OCH₂CH₂) n and n is 0 or numbers from 1 to 10.
Typische Beispiele sind Mono- und/oder Dialkylester auf Basis von Addukten von 1 bis 10, vorzugsweise 2 bis 8 Mol Ethylen oxid an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylal kohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Iso stearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylal kohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylal kohol sowie deren technische Mischungen, die z. B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen′schen Oxo synthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen.Typical examples are mono- and / or dialkyl esters based on adducts of 1 to 10, preferably 2 to 8, moles of ethylene oxide on capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, Caprinal alcohol, lauryl alcohol, isotridecyl alcohol, myristylal alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, iso stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinylal alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucylal alcohol and their technical mixtures, the z. B. at the High pressure hydrogenation of technical methyl esters based of fats and oils or aldehydes from Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
Besonders bevorzugt ist der Einsatz von Alkylphosphaten bzw. Alkyletherphosphaten mit einem Veresterungsgrad im Bereich von 1 bis 2,5 und vorzugsweise 1,3 bis 2,1 auf Basis von 2- Ethylhexanol oder C12/14- bzw. C12/18-Kokosfettalkohol, Talg fettalkohol sowie von deren Anlagerungsprodukten mit 1 bis 5 Mol Ethylenoxid.The use of alkyl phosphates or alkyl ether phosphates with a degree of esterification in the range from 1 to 2.5 and preferably 1.3 to 2.1 based on 2-ethylhexanol or C 12/14 or C 12/18 coconut fatty alcohol is particularly preferred , Tallow fatty alcohol and their adducts with 1 to 5 moles of ethylene oxide.
Unter Polyolefinwachsen sind überwiegend lineare Polyolefine mit wachsartigem Charakter zu verstehen. Technische Bedeutung haben Polypropylen- und insbesondere Polyethylenwachse, bei denen es sich um Produkte mit relativ niedrigen Molmassen im Bereich von 500 bis 20 000 handelt. Die Herstellung der Poly olefinwachse erfolgt in der Regel durch direkte Hoch- oder Niederdruckpolymerisation der Monomere oder durch gezielte Depolymerisation von Produkten höherer Molmassen. Modifizier te Polyolefinwachse können durch Copolymerisation von Ethylen mit geeigneten anderen Monomeren wie beispielsweise Vinylace tat oder Acrylsäure hergestellt werden. Schließlich ist es möglich, die Dispergierbarkeit von Polyolefinen durch oxida tive Oberflächenbehandlung zu verbessern. Übersichten zu die sem Thema finden sich beispielsweise in Ullmann′s Enzyklopä die der technischen Chemie (4. Aufl.), 24, 36 sowie Enzcycl. Polym. Sci. Engng. 17, 792f.Linear polyolefins are predominantly among polyolefin waxes to understand with a waxy character. Technical meaning have polypropylene and especially polyethylene waxes which are products with relatively low molecular weights in Range from 500 to 20,000. The production of the poly olefin waxes are usually done by direct up or down Low pressure polymerization of the monomers or by targeted Depolymerization of products with higher molecular weights. Modify Polyolefin waxes can be obtained by copolymerizing ethylene with suitable other monomers such as Vinylace tat or acrylic acid can be produced. After all it is possible, the dispersibility of polyolefins by oxida tive surface treatment to improve. Overviews of the his subject can be found, for example, in Ullmann’s Encyclopaedia those of technical chemistry (4th ed.), 24, 36 and Enzcycl. Polym. Sci. Narrow 17, 792f.
Im Sinne des erfindungsgemäßen Verfahrens ist der Einsatz von high-density Polyethylenwachs mit einem mittleren Molekular gewicht im Bereich von 500 bis 10 000 und insbesondere 2000 bis 5000 bevorzugt. Der Anteil des sauren Dispergiermittels kann 1 bis 40 und vorzugsweise 5 bis 25 Gew.-% - bezogen auf das Polyolefinwachs - betragen. Die wäßrigen Dispersionen weisen in der Regel einen Feststoffgehalt von 1 bis 40 und vorzugsweise 2 bis 25 Gew.-% auf.The use of high-density polyethylene wax with a medium molecular weight weight in the range of 500 to 10,000 and in particular 2000 up to 5000 preferred. The proportion of the acidic dispersant can 1 to 40 and preferably 5 to 25 wt .-% - based on the polyolefin wax - amount. The aqueous dispersions usually have a solids content of 1 to 40 and preferably 2 to 25% by weight.
Die Neutralisation der sauren Dispergiermittel erfolgt vor zugsweise unter Zugabe von wäßrigen Alkalihydroxidlösungen. Typische Beispiele sind wäßrige 5- bis 25gew.-%ige Lösungen von Natrium- und vorzugsweise Kaliumhydroxid.The acidic dispersants are neutralized before preferably with the addition of aqueous alkali hydroxide solutions. Typical examples are aqueous 5 to 25% by weight solutions of sodium and preferably potassium hydroxide.
Die gemeinsame Neutralisation von saurem Dispergiermittel und Polyolefinwachs findet oberhalb des Schmelzpunktes des Wach ses, vorzugsweise bei Temperaturen im Bereich von 120 bis 180 und insbesondere 150 bis 160°C statt. Der Druck kann 1 bis 10 bar betragen. Vorzugsweise erfolgt die Neutralisation der Dispersion unter einem autogenen Druck von 2 bis 6 bar. An schließend wird die Dispersion auf Raumtemperatur abgekühlt.The joint neutralization of acidic dispersant and Polyolefin wax takes place above the melting point of the wax ses, preferably at temperatures in the range of 120 to 180 and in particular 150 to 160 ° C instead. The pressure can be 1 to 10 bar. The neutralization preferably takes place Dispersion under an autogenous pressure of 2 to 6 bar. On finally the dispersion is cooled to room temperature.
In einer bevorzugten Ausführungsform der Erfindung wird die Neutralisation in Gegenwart eines Co-Dispergators durchge führt. Hierfür kommen in erster Linie nichtionische Tenside der Formel (II) in Betracht,In a preferred embodiment of the invention, the Neutralization in the presence of a co-dispersant leads. Primarily non-ionic surfactants are used for this of formula (II) into consideration
R³O(CH₂CH₂O)mH (II)R³O (CH₂CH₂O) m H (II)
in der R³ für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen oder einen Nonylphenylrest und m für Zahlen von 1 bis 20 steht.in the R³ for an alkyl and / or alkenyl radical with 6 to 22nd Carbon atoms or a nonylphenyl radical and m for numbers from 1 to 20.
Typische Beispiele sind Anlagerungsprodukte von durchschnitt lich 1 bis 20 und vorzugsweise 7 bis 15 Mol Ethylenoxid an Fettalkohole mit 12 bis 18 Kohlenstoffatome oder Nonylphenol wie beispielsweise C12/14-Kokosfettalkohol-9EO-Addukt, C12/18-Kokosfettalkohol-7EO-Addukt, C16/18-Talgalkohol-14EO- Addukt oder Nonylphenol-10EO-Addukt.Typical examples are addition products of on average 1 to 20 and preferably 7 to 15 moles of ethylene oxide onto fatty alcohols with 12 to 18 carbon atoms or nonylphenol such as, for example, C 12/14 coconut fatty alcohol 9EO adduct, C 12/18 coconut fatty alcohol 7EO adduct, C 16/18 tallow alcohol-14EO adduct or nonylphenol-10EO adduct.
Die nach dem erfindungsgemäßen Verfahren erhältlichen wäßri gen Polyolefinwachs-Dispersionen zeichnen sich durch eine besonders feine Verteilung der Teilchen sowie eine verbesser te Lagerstabilität aus und eignen sich beispielsweise zum Beschichten von festen Oberflächen und textilen Flächenge bilden, wie etwa Fasern, Garnen und Textilien, sowie als Entschäumer.The obtainable by the process according to the invention polyolefin wax dispersions are characterized by a particularly fine distribution of the particles and an improvement te storage stability and are suitable for Coating of solid surfaces and textile surfaces form, such as fibers, yarns and textiles, as well as Defoamer.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken.The following examples are intended to be the subject of the invention explain in more detail without restricting it.
- A1) Polyethylenwachs, Festpunkt: 127°C, mittlere Molmasse: 5000A1) polyethylene wax, fixed point: 127 ° C, average molecular weight: 5000
- B1) Stearylphosphat, Veresterungsgrad 1,5B1) Stearyl phosphate, degree of esterification 1.5
- B2) Stearylphosphat-Natriumsalz, Veresterungsgrad 1,5B2) Stearyl phosphate sodium salt, degree of esterification 1.5
- B3) Dodecylbenzolsulfonat-KaliumsalzB3) Dodecylbenzenesulfonate potassium salt
- C1) C12/18-Kokosfettalkohol-9EO-Addukt, FORYL® 100, Henkel KGaAC1) C 12/18 coconut fatty alcohol 9EO adduct, FORYL® 100, Henkel KGaA
In 500 ml einer 5gew.-%igen Lösung des sauren Dispergiermit tels B1 wurden 155 g Polyethylenwachs A1 eingerührt. Der Feststoffgehalt der resultierenden Dispersion betrug ca. 27 Gew.-%, der Anteil des Dispergiermittels - bezogen auf das Wachs - 16 Gew.-%. Die Dispersion wurde mit 25gew.-%iger Kaliumhydroxidlösung neutralisiert und danach 30 min auf 150°C erhitzt. Anschließend ließ man auf Raumtemperatur ab kühlen. Die Dispersion wurde 3 Wochen bei 20°C gelagert und Feinteiligkeit bzw. Stabilität optisch beurteilt. Hierbei bedeuten:In 500 ml of a 5% by weight solution of the acidic dispersant 155 g of polyethylene wax A1 were stirred in using B1. Of the The solids content of the resulting dispersion was approximately 27 % By weight, the proportion of the dispersant - based on the Wax - 16% by weight. The dispersion was 25 wt .-% Potassium hydroxide solution neutralized and then 30 min 150 ° C heated. The mixture was then let down to room temperature cool. The dispersion was stored at 20 ° C. for 3 weeks and Fine grading or stability assessed optically. Here mean:
Feinteiligkeit:
+++ = beinahe klare Dispersion
++ = leicht milchige Dispersion
+ = milchig-trübe DispersionFine division:
+++ = almost clear dispersion
++ = slightly milky dispersion
+ = milky cloudy dispersion
Stabilität:
+++ = kein Bodensatz
++ = sehr geringer Bodensatz
+ = geringer Bodensatz
- = deutlicher Bodensatz.Stability:
+++ = no sediment
++ = very low sediment
+ = low sediment
- = significant sediment.
Die Ergebnisse sind in Tabelle 1 zusammengefaßt.The results are summarized in Table 1.
Beispiel 1 wurde wiederholt, die Neutralisation jedoch in ei nem Autoklaven durchgeführt, wobei sich bei 150°C ein autoge ner Druck von 6 bar einstellte. Die Ergebnisse sind in Tabel le 1 zusammengefaßt.Example 1 was repeated, but the neutralization in egg nem autoclave performed, with an autogenous at 150 ° C. set a pressure of 6 bar. The results are in table le 1 summarized.
Beispiel 1 wurde wiederholt, jedoch die Neutralisation in Gegenwart von 5 Gew.-% - bezogen auf die Dispersion - des Co- Dispergators C1 durchgeführt. Die Ergebnisse sind in Tabelle 1 zusammengefaßt. Example 1 was repeated, but the neutralization in Presence of 5% by weight, based on the dispersion, of the co- Dispergators C1 performed. The results are in the table 1 summarized.
Beispiel 2 wurde wiederholt, jedoch die Neutralisation in Gegenwart von 5 Gew.-% - bezogen auf die Dispersion - des Co- Dispergators C1 durchgeführt. Die Ergebnisse sind in Tabelle 1 zusammengefaßt.Example 2 was repeated, but the neutralization in Presence of 5% by weight, based on the dispersion, of the co- Dispergators C1 performed. The results are in the table 1 summarized.
Beispiel 1 wurde unter Einsatz des neutralisierten Disper giermittels B2 wiederholt und auf eine nachträgliche Neutra lisation verzichtet. Die Ergebnisse sind in Tabelle 1 zusam mengefaßt.Example 1 was made using the neutralized Disper greed B2 repeated and on a subsequent neutra lization waived. The results are summarized in Table 1 quantified.
Beispiel 1 wurde unter Einsatz des neutralisierten Disper giermittels B3 wiederholt und auf eine nachträgliche Neutra lisation verzichtet. Die Ergebnisse sind in Tabelle 1 zusam mengefaßt. Example 1 was made using the neutralized Disper greed B3 repeated and to a subsequent neutra lization waived. The results are summarized in Table 1 quantified.
Claims (8)
- (a) eine wäßrige Lösung aus einem sauren tensidischen Dispergiermittel und feinverteiltem Polyolefin wachs herstellt und
- (b) die Dispersion anschließend durch Zugabe von Alka lihydroxiden oberhalb des Schmelzpunktes des Wachses neutralisiert.
- (a) produces an aqueous solution of an acidic surfactant dispersant and finely divided polyolefin wax and
- (b) the dispersion is then neutralized by adding alkali hydroxides above the melting point of the wax.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4435404A DE4435404A1 (en) | 1994-10-04 | 1994-10-04 | Process for the preparation of stabilized aqueous polyolefin wax dispersions |
PCT/EP1995/003796 WO1996010599A1 (en) | 1994-10-04 | 1995-09-25 | Process for producing stabilised aqueous polyolefine wax dispersions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4435404A DE4435404A1 (en) | 1994-10-04 | 1994-10-04 | Process for the preparation of stabilized aqueous polyolefin wax dispersions |
Publications (1)
Publication Number | Publication Date |
---|---|
DE4435404A1 true DE4435404A1 (en) | 1996-04-11 |
Family
ID=6529898
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE4435404A Withdrawn DE4435404A1 (en) | 1994-10-04 | 1994-10-04 | Process for the preparation of stabilized aqueous polyolefin wax dispersions |
Country Status (2)
Country | Link |
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DE (1) | DE4435404A1 (en) |
WO (1) | WO1996010599A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2784110A1 (en) * | 1998-10-06 | 2000-04-07 | Atochem Elf Sa | PROCESS FOR THE POLYMERIZATION OF OLEFINS IN THE PRESENCE OF WATER |
FR2790978A1 (en) * | 1999-03-19 | 2000-09-22 | Atochem Elf Sa | PROCESS FOR POLYMERIZING OLEFINS IN THE PRESENCE OF NICKEL COMPLEXES AND CORRESPONDING CATALYTIC SYSTEM |
EP1510620A3 (en) * | 2003-08-07 | 2006-01-04 | Takemoto Yushi Kabushiki Kaisha | Low concentration aqueous solution of an agent for processing synthetic fibers, method of producing same and method of processing synthetic fibers |
EP3010873A4 (en) * | 2013-06-18 | 2017-02-22 | EURENCO Bofors AB | Phlegmatisation of an explosive in an aqueous suspension |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US8679726B2 (en) | 2012-05-29 | 2014-03-25 | Eastman Kodak Company | Negative-working lithographic printing plate precursors |
US9063423B2 (en) | 2013-02-28 | 2015-06-23 | Eastman Kodak Company | Lithographic printing plate precursors and use |
US9201302B2 (en) | 2013-10-03 | 2015-12-01 | Eastman Kodak Company | Negative-working lithographic printing plate precursor |
US11633948B2 (en) | 2020-01-22 | 2023-04-25 | Eastman Kodak Company | Method for making lithographic printing plates |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3745135A (en) * | 1970-08-17 | 1973-07-10 | Du Pont | Polymerized ethylenically unsaturated fatty acids as emulsifiers for aqueous dispersions |
US4129507A (en) * | 1978-01-18 | 1978-12-12 | Allied Chemical Corporation | Spin finish for polyamide yarn |
US4357185A (en) * | 1981-05-20 | 1982-11-02 | The United States Of America As Represented By The Secretary Of The Navy | Process for coating crystalline explosives with polyethylene wax |
US5007961A (en) * | 1988-05-24 | 1991-04-16 | Eastman Kodak Company | Aqueous additive systems, methods and polymeric particles |
US4767646A (en) * | 1985-10-24 | 1988-08-30 | Allied Corporation | Wet abrasion resistant yarn and cordage |
-
1994
- 1994-10-04 DE DE4435404A patent/DE4435404A1/en not_active Withdrawn
-
1995
- 1995-09-25 WO PCT/EP1995/003796 patent/WO1996010599A1/en active Application Filing
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2784110A1 (en) * | 1998-10-06 | 2000-04-07 | Atochem Elf Sa | PROCESS FOR THE POLYMERIZATION OF OLEFINS IN THE PRESENCE OF WATER |
WO2000020464A1 (en) * | 1998-10-06 | 2000-04-13 | Atofina | Method for polymerising olefins in the presence of water |
US6737483B1 (en) | 1998-10-06 | 2004-05-18 | Atanas Tomov | Method for polymerising olefins in the presence of water |
FR2790978A1 (en) * | 1999-03-19 | 2000-09-22 | Atochem Elf Sa | PROCESS FOR POLYMERIZING OLEFINS IN THE PRESENCE OF NICKEL COMPLEXES AND CORRESPONDING CATALYTIC SYSTEM |
EP1510620A3 (en) * | 2003-08-07 | 2006-01-04 | Takemoto Yushi Kabushiki Kaisha | Low concentration aqueous solution of an agent for processing synthetic fibers, method of producing same and method of processing synthetic fibers |
EP3010873A4 (en) * | 2013-06-18 | 2017-02-22 | EURENCO Bofors AB | Phlegmatisation of an explosive in an aqueous suspension |
Also Published As
Publication number | Publication date |
---|---|
WO1996010599A1 (en) | 1996-04-11 |
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