WO1992014763A1 - Process for producing an aqueous, autoxidatively drying emulsion polymer, preferably used as binder for lacquers - Google Patents

Process for producing an aqueous, autoxidatively drying emulsion polymer, preferably used as binder for lacquers Download PDF

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Publication number
WO1992014763A1
WO1992014763A1 PCT/DE1992/000107 DE9200107W WO9214763A1 WO 1992014763 A1 WO1992014763 A1 WO 1992014763A1 DE 9200107 W DE9200107 W DE 9200107W WO 9214763 A1 WO9214763 A1 WO 9214763A1
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WIPO (PCT)
Prior art keywords
acid
polymer
solution polymer
solution
mass
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PCT/DE1992/000107
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German (de)
French (fr)
Inventor
Karl-Heinz Weinert
Siegfried Müller
Hans-Joachim Lorkowski
Doris Zekai
Klaus Tauer
Original Assignee
Lankwitzer Lackfabrik Gmbh. & Co. Kg
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Publication of WO1992014763A1 publication Critical patent/WO1992014763A1/en

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Classifications

    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of acids or salts

Definitions

  • the invention relates to a process for producing an aqueous, autoxidatively drying emulsion polymer, preferably as a binder for lacquers, in which "a solution polymer containing carboxyl groups is first prepared by polymerizing an addition product from unsaturated fatty acids and unsaturated monomers, and then an emulsion polymerization of unsaturated monomers is carried out together with this solution polymer.
  • binder dispersions disclosed in US Pat. No. 4,122,052 show poor results in terms of gloss and toughness. Furthermore, these polymers contain too much organic solvents. as well as ammonia or amine, so that when used as a coating material they still represent strong environmental hazards.
  • the emulsifier is a maleic acid adduct of an alkyd resin. Disadvantages of such systems are the deepening of the color of the products caused by the formation of maleic acid adduct and the inadequate compatibility between the emulsifier and the polymer formed with the vinyl monomers.
  • the object of the invention is to carry out the process mentioned at the outset in such a way that better products are obtained in comparison with the known solutions.
  • This object is achieved by a process for producing an aqueous, autoxidatively drying emulsion polymer
  • an unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid and maleic anhydride, alone or in combination, where
  • the solution polymer has an acid number between 20 and 160 and a number average molecular weight M ,, of 1,500 to 80,000 and the unsaturated fatty acid (s) form 15-60% by mass of the solution polymer,
  • the solution polymer fulfills two functions:
  • the two functions of the solution polymer are influenced by the degree of neutralization of the carboxyl groups:
  • the solubility of the solution polymer is reduced, so that it can only act insufficiently as a dispersion stabilizer. If the degree of neutralization is too high, the solubility increases such that not only is the dynamic equilibrium of the distribution of the solution polymer between the interior of the solution and the phase boundary regions monomer / water or polymer / water shifted in favor of the interior of the solution, but also at the same time due to the increased degree of dissociation of the carboxyl group, the polymer molecules expand. The latter behavior can even increase the viscosity to such an extent that conventional emulsion polymerization is prevented or unsuitable cream-like products are formed.
  • the dispersed polymer particles surprisingly have a core-shell morphology, the unsaturated fatty acids introduced via the solution polymer being enriched in the shell region.
  • the polymer particles penetrate and bond mainly with their shell areas. These determine the properties of the overall film.
  • This morphology requires a degree of neutralization that is neither 0 nor 1. With one between these Accordingly, the two degrees of neutralization have particularly good properties.
  • the lacquers which are produced according to the teaching according to the invention are more weather-resistant, storage-stable, light-resistant, shear-stable, glossy and harder than the lacquers which are produced by the known processes.
  • the binders according to the invention contain less amines or ammonia.
  • the binders according to the invention are notable for high water, in particular salt water and solvent resistance.
  • the conversion to the addition product from unsaturated fatty acids and unsaturated monomers, preferably glycidyl methacrylate, is usually carried out at a temperature of 120 to 190 ° C., preferably at a temperature of 150 ° C., and with the catalyst tetraethylammonium bromide in a time of 1 to 6 hours, preferably 2 hours.
  • the acid number of the mixture drops below 3% of the initial value after the reaction.
  • the solution polymer is preferably synthesized by free-radical polymerization of the addition product with unsaturated carboxylic acids, preferably with methacrylic acid in cyclohexanone or butoxyethanol at 90 ° to 150 ° C., preferably at 120 ° C. in butoxyethanol, with the aid of azo initiators.
  • the content of carboxylic acid must not be too high, but also not too low. A minimum value must be reached in order for the solution polymer to be sufficiently water-soluble, and a maximum value must not be exceeded so that the finished coating remains sufficiently hydrophobic.
  • the proportion of methacrylic acid in the solution polymer is preferably 20% by mass.
  • the emulsion polymerization is carried out at temperatures from 60 ° to 80 ° C., preferably 70 ° C.
  • the monomers are reacted under nitrogen without first removing any inhibitor that may be present.
  • Ammonium peroxodisulfate is preferably used as the water-soluble radical initiator.
  • the use of an external emulsifier can be dispensed with, since its function is essentially carried out by the solution polymer.
  • the anionic emulsifier sodium alkyl sulfate is preferably used.
  • external emulsifiers are those which are incorporated in the course of the emulsion polymerization.
  • Monosodium sulfopropyl monododecyl maleate is preferably used.
  • tetraethylammonium bromide 0.25 g are dissolved in 131.5 g of glycidyl methacrylate (GMA), which contains 0.005% by mass of hydroquinone monoethyl ether, and then mixed with 250 g of soybean oil fatty acid. The mixture is melted under nitrogen in an ampoule and heated in an oil bath at 155 ° C. for 90 minutes. The conversion of the carboxyl groups is checked by gas chromatography by determining the acid number or that of the GMA. The monomer (1.1) obtained has an acid number below 3% of the initial value.
  • GMA glycidyl methacrylate
  • the product (1.3) is mixed with 4.4 g of sodium dodecyl sulfate, 68 g of methyl methacrylate and 250 g of n-butyl methacrylate, and an emulsion is prepared under vigorous stirring under nitrogen. After heating to 70 ° C., 0.86 g of ammonium peroxodisulfate, dissolved in 20 ml of water, are added to the emulsion and the reaction is ended after 7 hours.
  • the polymer particles have an average size of 220 nm.
  • Example 2 The polymer dispersions are prepared analogously to that of Example 1, except that instead of the 52.2 g of methacrylic acid in stage 1.2, 80.7 g of methacrylic acid and Example 3 67.5 g of acrylic acid are used in Example 2. Because of the increase in the acid content, the proportion of ammonia solution is increased from 9.3 to 13.4 ml in the neutralization stage.
  • the particle sizes reach an average value of 70 nm, in example 3 this is 280 nm.
  • the polymer dispersion is prepared analogously to that of Example 2, only 68 g of styrene are used instead of 68 g of methyl methacrylate in stage 1.4.
  • the particle sizes have an average value of 230 nm.
  • the polymer dispersion is prepared analogously to that of Example 4, except that 67.5 g of acrylic acid are used instead of methacrylic acid in stage 1.2 and 13.4 ml of ammonia solution in stage 1.3.
  • the particle sizes have an average value of 310 nm.
  • the polymer dispersion is prepared analogously to that of Example 2, except that the emulsifier instead of the 4.4 g Na dodecyl sulfate used the same amount of monosodium sulfopropyl monododecyl maleate.
  • the particle sizes have an average value of 85 nm.
  • emulsion polymers according to the invention can also be used in other cases and not only for lacquers, for example for floor care products.

Abstract

A process is disclosed for producing an aqueous, autoxidatively drying emulsion polymer, preferably used as binder for lacquers. A carboxyl group-containing solution polymer is first produced by polymerizing an addition product from unsaturated fatty acids and unsaturated monomers with another substance, and then an emulsion polymerization of unsaturated monomers is carried out with this solution polymer. According to the invention, the degree of neutralization of the solution polymer is set before the emulsion polymerization by admixture of a base, in particular amines or ammonia, especially aqueous ammonia, at 0.4 to 0.9, in particular 0.7. Coatings produced with such a lacquer are characterized by remarkable properties.

Description

VERFAHREN ZUR HERSTELLUNG EINES WASSRIGEN, AUTOXIDATIV TROCKNENDEN EMULSIQNSPOLYMERISΛTES VORZUGSWEISE ALS BINDEMITTEL FÜR LACKEMETHOD FOR PRODUCING AN AQUEOUS, AUTOXIDATIVELY DRYING EMULSIQNSPOLYMERISΛTES PREFERABLY AS A BINDING AGENT FOR VARNISHES
Die Erfindung bezieht sich auf ein Verfahren zum Her¬ stellen eines wässrigen, autoxidativ trocknenden Emul¬ sionspolymerisats vorzugsweise als Bindemittel für Lak- ke, bei dem "zunächst ein carboxylgruppenhaltiges Lö¬ sungspolymerisat durch Polymerisation eines Additions¬ produktes aus ungesättigten Fettsäuren und ungesättigten Monomeren hergestellt und dann gemeinsam mit diesem Lö¬ sungspolymerisat eine Emulsionspolymerisation ungesät¬ tigter Monomerer durchgeführt wird.The invention relates to a process for producing an aqueous, autoxidatively drying emulsion polymer, preferably as a binder for lacquers, in which "a solution polymer containing carboxyl groups is first prepared by polymerizing an addition product from unsaturated fatty acids and unsaturated monomers, and then an emulsion polymerization of unsaturated monomers is carried out together with this solution polymer.
Aus der US-Patentschrift 3 880 793 und der DE-AS 2 513 516 ist es bekannt, Dispersionen mit Hilfe von maleini- sierte Polybutadien als Emulgator zu synthetisieren. Diese Systeme zeigen wegen ihres hohen Doppelbindungsge¬ haltes und des dadurch begünstigten photochemischen Ab¬ baus keine gute Witterungsbeständigkeit.It is known from US Pat. No. 3,880,793 and DE-AS 2,513,516 to synthesize dispersions using maleated polybutadiene as an emulsifier. Because of their high double bond content and the photochemical degradation favored thereby, these systems do not show good weather resistance.
In der Schrift zum US-Patent 4 073 -758 werden als E ul- gatoren Produkte eingesetzt, deren technologischer Syn¬ theseaufwand relativ hoch liegt. Der Emulgator wird im Ergebnis einer Lösungspolymerisation von ungesättigten Monomeren, die die OH- und Epoxy-Substituenten tragen, und einer anschließenden energieaufwendigen polymerana¬ logen Umsetzung z.B. mit Ölfettsäure sowie Maleinsäu¬ reanhydrid hergestellt. Solche Produkte tendieren dazu, im Verlaufe dieser Prozedur dunkelfarbig zu werden.In the document relating to US Pat. No. 4,073-758, products are used as emulators whose technological outlay is relatively high. The emulsifier is the result of a solution polymerization of unsaturated monomers which carry the OH and epoxy substituents and a subsequent energy-intensive polymer-analogous reaction, e.g. made with oleic acid and maleic anhydride. Such products tend to turn dark in color during this procedure.
Die in der Schrift zum US-Patent 4 122 052 offenbarten Bindemitteldispersionen zeigen hinsichtlich des Glanzes und der Zähigkeit ungünstige Resultate. Des weiteren enthalten diese Polymere zu viel organische Lösungsmit- tel sowie Ammoniak oder A ine, so daß sie in der Anwen¬ dung als Beschichtungsmasse noch starke Umweltgef hrdün¬ gen darstellen.The binder dispersions disclosed in US Pat. No. 4,122,052 show poor results in terms of gloss and toughness. Furthermore, these polymers contain too much organic solvents. as well as ammonia or amine, so that when used as a coating material they still represent strong environmental hazards.
In den Polymerdispersionen, bekannt aus dem JP 52-102 390 A, ist der Emulgator ein Maleinsäureaddukt eines Alkydharzes. Nachteilig sind an derartigen Systemen die durch die Maleinsäureadduktbildung verursachte Farbver¬ tiefung der Produkte sowie eine ungenügende Verträglich¬ keit zwischen dem Emulgator und dem mit den Vinylmonome- ren entstandenen Polymeren.In the polymer dispersions, known from JP 52-102 390 A, the emulsifier is a maleic acid adduct of an alkyd resin. Disadvantages of such systems are the deepening of the color of the products caused by the formation of maleic acid adduct and the inadequate compatibility between the emulsifier and the polymer formed with the vinyl monomers.
Die in dem EP 0 305 795 A2 beschriebenen dispergierten Polymere enthalten neben Caboxylgruppen erhebliche An¬ teile weiterer hydrophiler Gruppierungen infolge der Verwendung von Polyolen bzw. Polyethylenglykolen. Da¬ durch bleibt die Wasserbeständigkeit von Filmen noch unzureichend.The dispersed polymers described in EP 0 305 795 A2 contain, in addition to caboxyl groups, considerable proportions of further hydrophilic groups due to the use of polyols or polyethylene glycols. As a result, the water resistance of films still remains inadequate.
Bei den genannten Verfahren, bis auf das letzte, werden die als Emulgator wirkenden carboxylgruppenhaltigen, relativ kurzkettigen Polymere mit einem Neutralisations¬ grad von 1 bis nahezu 1 eingesetzt.In the processes mentioned, with the exception of the last, the relatively short-chain polymers containing carboxyl groups and acting as emulsifiers are used with a degree of neutralization of 1 to almost 1.
Der Erfindung liegt die Aufgabe zugrunde, das eingangs erwähnte Verfahren derart durchzuführen, daß im Ver¬ gleich zu den bekannten Lösungen bessere Produkte erhal¬ ten werden.The object of the invention is to carry out the process mentioned at the outset in such a way that better products are obtained in comparison with the known solutions.
Diese Aufgabe wird gelöst durch ein Verfahren zur Her¬ stellung eines wässrigen, autoxidativ trocknenden Emul¬ sionspolymerisates durchThis object is achieved by a process for producing an aqueous, autoxidatively drying emulsion polymer
a) übliche Lösungspolymerisation aa) eines Monomeren, welches durch Addition einer unge¬ sättigten Fettsäure an Glycidylacrylat bzw. -metha- crylat entsteht, mita) usual solution polymerization a a ) of a monomer which is formed by adding an unsaturated fatty acid to glycidyl acrylate or methacrylate
ab) einer ungesättigten Carbonsäure ausgewählt aus der Gruppe Acrylsäure, Methacrylsäure, Crotonsäure, Fu- marsäure, Itaconsäure sowie Maleinsäureanhydrid al¬ lein oder in Kombination, wobeia b ) an unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid and maleic anhydride, alone or in combination, where
ac) das Lösungspolymerisat eine Säurezahl zwischen 20 und 160 und ein Zahlenmittel der Molmasse M,, von 1 500 bis 80 000 aufweist und die ungesättigte (n) Fettsäure (n) 15 - 60 Masse-% des Lösungspolymerisates bilden,a c ) the solution polymer has an acid number between 20 and 160 and a number average molecular weight M ,, of 1,500 to 80,000 and the unsaturated fatty acid (s) form 15-60% by mass of the solution polymer,
b) Teilneutralisation des Lösungspolymerisates durch Zugabe von Aminen oder Ammoniak auf einen Neutralisa¬ tionsgrad zwischen 0,4 und 0,9 undb) Partial neutralization of the solution polymer by adding amines or ammonia to a degree of neutralization between 0.4 and 0.9 and
c) übliche Emulsionspolymerisationen des teilneutrali¬ sierten Lösungspolymerisates mit mindestens einem Monomeren aus der Gruppe Styren, c -Methylstyrol, p-Methylstyrol und Methylmethacrylat kombiniert mit mindestens einem aus der Gruppe Methyl-, Ethyl-, Butyl-, 2-Ethylhexylacrylat bzw. Butyl- und 2-Ethylhexylmethacrylat, wobei das Lösungspolymerisat 15 bis 35 Masse-% bezogen auf den Feststoffanteil im Emulsionspolymerisat bildet.c) customary emulsion polymerizations of the partially neutralized solution polymer with at least one monomer from the group styrene, c-methylstyrene, p-methylstyrene and methyl methacrylate combined with at least one from the group methyl, ethyl, butyl, 2-ethylhexyl acrylate or butyl and 2-ethylhexyl methacrylate, the solution polymer forming 15 to 35% by mass, based on the solids content in the emulsion polymer.
Diesem Vorschlag liegt folgende Überlegung zugrunde:This proposal is based on the following consideration:
Das Lösungspolymerisat erfüllt zwei Funktionen:The solution polymer fulfills two functions:
Einerseits wirkt es als Dispersionsstabilisator bei der Herstellung der Polymerdispersion infolge der Hydrophi- lie seiner Carboxylgruppen und andererseits als autoxi- dable Komponente in Beschichtungen wegen seiner als Ester gebundenen ungesättigten Fettsäuren. Diese Fett¬ säuren bestimmen wesentlich die Eigenschaften der Be¬ schichtung, wie z.B. die Härte und die Wasseraufnahme der fertigen Beschichtung.On the one hand it acts as a dispersion stabilizer in the production of the polymer dispersion due to the hydrophilicity of its carboxyl groups and on the other hand as an autoxidizable component in coatings because of its as Ester bound unsaturated fatty acids. These fatty acids essentially determine the properties of the coating, such as the hardness and water absorption of the finished coating.
Die beiden Funktionen des Lösungspolymerisats werden durch den Neutralisationsgrad der Carboxylgruppen beein¬ flußt:The two functions of the solution polymer are influenced by the degree of neutralization of the carboxyl groups:
Bei einem zu geringen Neutralisationsgrad verringert sich die Löslichkeit des Lösungspolymerisats, so daß es nur unzureichend als Dispersionsstabilisator wirken kann. Bei einem zu hohen Neutralisationsgrad vergrößert sich die Löslichkeit derart, daß nicht nur das dynami¬ sche Gleichgewicht der Verteilung des Lösungspolymeri¬ sats zwischen dem Lösungsinnern und den Phasengrenzbe- reichen Monomer/Wasser bzw. Polymer/Wasser zugunsten des Lόsungsinneren verschoben ist, sondern zugleich auch durch den gestiegenen Dissoziationsgrad der Carboxyl- gruppe eine Aufweitung der Polymermoleküle erfolg . Letzteres Verhalten kann die Viskosität sogar so weit erhöhen, daß eine übliche Emulsionspolymerisation ver¬ hindert wird bzw. sich ungeeignete cremeartige Produkte bilden.If the degree of neutralization is too low, the solubility of the solution polymer is reduced, so that it can only act insufficiently as a dispersion stabilizer. If the degree of neutralization is too high, the solubility increases such that not only is the dynamic equilibrium of the distribution of the solution polymer between the interior of the solution and the phase boundary regions monomer / water or polymer / water shifted in favor of the interior of the solution, but also at the same time due to the increased degree of dissociation of the carboxyl group, the polymer molecules expand. The latter behavior can even increase the viscosity to such an extent that conventional emulsion polymerization is prevented or unsuitable cream-like products are formed.
Weiterhin ist folgendes zu bedenken: Die dispergierten Polymerteilchen weisen dabei überraschenderweise eine Kern-Schale-Morphologie auf, wobei im Schalenbereich die über das Lösungspolymerisat eingebrachten ungesättigten Fettsäuren angereichert sind. Bei der Filmbildung der Beschichtungsmassen durchdringen und verbinden sich die Polymerteilchen hauptsächlich mit ihren Schalenberei¬ chen. Diese bedingen die Eigenschaften des Gesamtfilms. Diese Morphologie setzt einen Neutralisationsgrad vor¬ aus, der weder 0 noch 1 ist. Bei einem zwischen diesen beiden Grenzwerten liegenden Neutralisationsgrad hat man demgemäß besonders gute Eigenschaften.The following should also be considered: The dispersed polymer particles surprisingly have a core-shell morphology, the unsaturated fatty acids introduced via the solution polymer being enriched in the shell region. During the film formation of the coating compositions, the polymer particles penetrate and bond mainly with their shell areas. These determine the properties of the overall film. This morphology requires a degree of neutralization that is neither 0 nor 1. With one between these Accordingly, the two degrees of neutralization have particularly good properties.
Im Endeffekt sind die Lacke, die nach der erfindungsge¬ mäßen Lehre hergestellt werden, witterungsbeständiger, lagerungsbeständiger, lichtbeständiger, scherstabiler, glänzender und härter als die Lacke, die nach den be¬ kannten Verfahren hergestellt werden. Außerdem enthalten die erfindungsgemäßen Bindemittel weniger Amine oder Ammoniak. Weiterhin zeichnen sich die erfindungsgemäßen Bindemittel durch eine hohe Wasser-, insbesondere Salzwasser-, und Lösungsmittelbeständigkeit aus.In the end, the lacquers which are produced according to the teaching according to the invention are more weather-resistant, storage-stable, light-resistant, shear-stable, glossy and harder than the lacquers which are produced by the known processes. In addition, the binders according to the invention contain less amines or ammonia. Furthermore, the binders according to the invention are notable for high water, in particular salt water and solvent resistance.
Die Umsetzung zum Additionsprödukt aus ungesättigten Fettsäuren und ungesättigten Monomeren, vorzugsweise Glycidylmethacrylat, wird üblicherweise bei einer Tempe¬ ratur von 120 bis 190°C, vorzugsweise bei einer Tempera¬ tur von 150°C, und mit dem Katalysator Tetraethylammoni- umbromid in einer Zeit von 1 bis 6 Stunden, vorzugsweise 2 Stunden, vorgenommen. Die Säurezahl des Gemisches sinkt nach der Reaktion unter 3% des Ausgangswertes.The conversion to the addition product from unsaturated fatty acids and unsaturated monomers, preferably glycidyl methacrylate, is usually carried out at a temperature of 120 to 190 ° C., preferably at a temperature of 150 ° C., and with the catalyst tetraethylammonium bromide in a time of 1 to 6 hours, preferably 2 hours. The acid number of the mixture drops below 3% of the initial value after the reaction.
Das Lösungspolymerisat wird vorzugsweise durch radikali¬ sche Polymerisation des Additionsproduktes mit ungesät¬ tigten Carbonsäuren, vorzugsweise mit Methacrylsäure in Cyclohexanon oder Butoxyethanol bei 90° bis 150°C, vor¬ zugsweise bei 120°C in Butoxyethanol, unter Zuhilfenahme von Azoinitiatoren synthedisiert. Der Gehalt an Carbon¬ säure darf nicht zu hoch, aber auch nicht zu niedrig liegen. Ein Mindestwert muß erreicht werden, um auf eine ausreichende Wasserlöslichkeit des Lösungspolymerisats zu kommen, und ein Maximalwert darf nicht überschritten werden, damit die fertige Beschichtung ausreichend hy¬ drophob bleibt. Der Anteil von Methacrylsäure im Lö¬ sungspolymerisat beträgt vorzugsweise 20 Masse-%. Die Emulsionspolymerisation wird bei Temperaturen von 60° bis 80°C, vorzugsweise 70°C, durchgeführt. Die Mono- ere werden unter Stickstoff umgesetzt, ohne vorher ei¬ nen eventuell vorhandenen Inhibitor zu entfernen. Als wasserlöslicher Radikalinitiator kommt vorzugsweise Am- moniumperoxodisulfat- zum Einsatz.The solution polymer is preferably synthesized by free-radical polymerization of the addition product with unsaturated carboxylic acids, preferably with methacrylic acid in cyclohexanone or butoxyethanol at 90 ° to 150 ° C., preferably at 120 ° C. in butoxyethanol, with the aid of azo initiators. The content of carboxylic acid must not be too high, but also not too low. A minimum value must be reached in order for the solution polymer to be sufficiently water-soluble, and a maximum value must not be exceeded so that the finished coating remains sufficiently hydrophobic. The proportion of methacrylic acid in the solution polymer is preferably 20% by mass. The emulsion polymerization is carried out at temperatures from 60 ° to 80 ° C., preferably 70 ° C. The monomers are reacted under nitrogen without first removing any inhibitor that may be present. Ammonium peroxodisulfate is preferably used as the water-soluble radical initiator.
Bei der Emulsionspolymerisation kann auf den Einsatz eines externen Emulgators verzichtet werden, da dessen Funktion im wesentlichen vom Lösungspolymerisat übernom¬ men wird. Vorzugsweise wird aber mit dem anionaktiven Emulgator Natriumalkylsulfat gearbeitet.In the case of emulsion polymerization, the use of an external emulsifier can be dispensed with, since its function is essentially carried out by the solution polymer. However, the anionic emulsifier sodium alkyl sulfate is preferably used.
Für besonders hohe Ansprüche an das als Bindemittel ein¬ gesetzte Emulsionspolymerisat werden als externe Emulga- toren solche eingesetzt, die im Verlaufe der Emulsions¬ polymerisation eingebaut werden. Vorzugsweise wird Mono- natriumsulfopropylmonododecylmaleat verwendet.For particularly high demands on the emulsion polymer used as a binder, external emulsifiers are those which are incorporated in the course of the emulsion polymerization. Monosodium sulfopropyl monododecyl maleate is preferably used.
Beispiel 1:Example 1:
1.1 Monomersynthese1.1 Monomer synthesis
In 131,5 g Glycidylmethacrylat (GMA) , das 0,005 Masse-% Hydrochinonmono ethylether enthält, werden 0,25 g Tetraethylammoniu bromid gelöst und anschlie¬ ßend mit 250 g So abohnenölfettsäure vermischt. Das Gemisch wird unter Stickstoff in einer Ampulle einge¬ schmolzen und in einem Ölbad von 155°C für 90 Minuten erwärmt. Die Umsetzung der Carboxylgruppen wird über die Bestimmung der Säurezahl bzw. die des GMA ga- schromatographisch kontrolliert. Das erhaltene Mono- mere (1.1) weist eine Säurezahl unterhalb 3% des An¬ fangswertes auf.0.25 g of tetraethylammonium bromide are dissolved in 131.5 g of glycidyl methacrylate (GMA), which contains 0.005% by mass of hydroquinone monoethyl ether, and then mixed with 250 g of soybean oil fatty acid. The mixture is melted under nitrogen in an ampoule and heated in an oil bath at 155 ° C. for 90 minutes. The conversion of the carboxyl groups is checked by gas chromatography by determining the acid number or that of the GMA. The monomer (1.1) obtained has an acid number below 3% of the initial value.
1.2 Lösungspolymerisation
Figure imgf000009_0001
1.2 solution polymerization
Figure imgf000009_0001
- 1 -- 1 -
In ein 1,5 1-Reaktionsgefäß werden 280 g Butoxyetha¬ nol vorgelegt und unter Stickstoff auf 120°C erwärmt. Bei kräftiger Rührung wird im Verlaufe von 1 h ein Gemisch aus 322,6 g des Monomeren (1.1), 52,2 g Me¬ thacrylsäure, 150 g Butoxyethanol und darin 21,5 g gelöste 2,2'-Azo-bis (2,4-dimethylvaleronitril) über eine Dosierpumpe dazugegeben. Nach 10 Minuten erfolgt die erste und nach weiteren 10 Minuten die zweite Zugabe von jeweils 2,2 ' -Azo-bis (isobutyronitril) . Nach anschließenden 10 Minuten wird das Reaktionsge¬ misch abgekühlt und am Rotationsverdampfer soweit eingeengt, daß das Produkt (1.2) aus 75 Masse-% Lό- sungspolymerisat und 25 Masse-% Butoxylethanol be¬ steht.280 g of butoxyethanol are placed in a 1.5 liter reaction vessel and heated to 120 ° C. under nitrogen. With vigorous stirring, a mixture of 322.6 g of the monomer (1.1), 52.2 g of methacrylic acid, 150 g of butoxyethanol and 21.5 g of 2,2'-azo-bis (2 , 4-dimethylvaleronitrile) added via a metering pump. After 10 minutes, the first and after a further 10 minutes the second addition of 2,2'-azobis (isobutyronitrile). After 10 minutes thereafter, the reaction mixture is cooled and concentrated on a rotary evaporator to such an extent that the product (1.2) consists of 75% by weight solution polymer and 25% by weight butoxylethanol.
1.3 Neutralisation1.3 Neutralization
In ein 1,5 1-Reaktionsgefäß werden 146 g des Produk¬ tes (1.2), 560 g Wasser und 9,3 ml Ammoniaklösung (25 Masse-% NH3 in Wasser) miteinander vermischt.146 g of the product (1.2), 560 g of water and 9.3 ml of ammonia solution (25% by weight of NH 3 in water) are mixed together in a 1.5 l reaction vessel.
1.4 Emulsionspolymerisation1.4 emulsion polymerization
Das Produkt (1.3) wird mit 4,4 g Natriu dodecylSul¬ fat, 68 g Methylmethacrylat und 250 g n- Butylmethacrylat versetzt und unter Stickstoff durch kräftige Rührung eine Emulsion hergestellt. Nach ei¬ ner Erwärmung auf 70°C werden 0,86 g Ammoniumperoxo- disulfat, gelöst in 20 ml Wasser, der Emulsion zuge¬ fügt und die Umsetzung nach 7 Stunden beendet.The product (1.3) is mixed with 4.4 g of sodium dodecyl sulfate, 68 g of methyl methacrylate and 250 g of n-butyl methacrylate, and an emulsion is prepared under vigorous stirring under nitrogen. After heating to 70 ° C., 0.86 g of ammonium peroxodisulfate, dissolved in 20 ml of water, are added to the emulsion and the reaction is ended after 7 hours.
Die Polymerteilchen haben eine durchschnittliche Grö¬ ße von 220 nm.The polymer particles have an average size of 220 nm.
Beispiele 2 und 3 Die Polymerdispersionen werden analog der des Beispiels 1 hergestellt, nur werden statt der 52,2 g Methacrylsäu¬ re in der Stufe 1.2 im Beispiel 2 80,7 g Methacrylsäure und im Beispiel 3 67,5 g Acrylsäure eingesetzt. Wegen der Erhöhung des Gehaltes der Säuren wird in der Stufe der Neutralisation auch der Anteil der Ammoniak-Lösung von 9.3 auf 13,4 ml erhöht.Examples 2 and 3 The polymer dispersions are prepared analogously to that of Example 1, except that instead of the 52.2 g of methacrylic acid in stage 1.2, 80.7 g of methacrylic acid and Example 3 67.5 g of acrylic acid are used in Example 2. Because of the increase in the acid content, the proportion of ammonia solution is increased from 9.3 to 13.4 ml in the neutralization stage.
In Beispiel 2 erreichen die Teilchengrößen einen durch¬ schnittlichen Wert von 70 nm, im Beispiel 3 beträgt die¬ ser 280 nm.In example 2 the particle sizes reach an average value of 70 nm, in example 3 this is 280 nm.
geispiel 4example 4
Die Polymerdispersion wird analog der des Beispiels 2 hergestellt, nur werden in der Stufe 1.4 statt der 68 g Methylmethacrylat 68 g Styren eingesetzt.The polymer dispersion is prepared analogously to that of Example 2, only 68 g of styrene are used instead of 68 g of methyl methacrylate in stage 1.4.
Die Teilchengrößen haben einen durchschnittlichen Wert von 230 nm.The particle sizes have an average value of 230 nm.
Beispiel 5Example 5
Die Polymerdispersion wird analog der des Beispiels 4 hergestellt, nur daß in der Stufe 1.2 statt der Metha¬ crylsäure 67,5 g Acrylsäure und in der Stufe 1.3 13,4 ml Ammoniaklösung eingesetzt werden.The polymer dispersion is prepared analogously to that of Example 4, except that 67.5 g of acrylic acid are used instead of methacrylic acid in stage 1.2 and 13.4 ml of ammonia solution in stage 1.3.
Die Teilchengrößen haben einen durchschnittlichen Wert von 310 nm.The particle sizes have an average value of 310 nm.
Beispiel 6Example 6
Die Polymerdispersion wird analog der des Beispiels 2 hergestellt, nur werden als Emulgator statt der 4,4 g Na-Dodecylsulfat die gleiche Menge an Mononatriumsulfo- propylmonododecylmaleat eingesetzt.The polymer dispersion is prepared analogously to that of Example 2, except that the emulsifier instead of the 4.4 g Na dodecyl sulfate used the same amount of monosodium sulfopropyl monododecyl maleate.
Die Teilchengrößen haben einen durchschnittlichen Wert von 85 nm.The particle sizes have an average value of 85 nm.
Selbstverständlich können die erfindungsgemäßen Emul¬ sionspolymerisate auch in anderen Fällen und nicht nur für Lacke, beispielsweise für Bodenpflegemittel, einge¬ setzt werden. Of course, the emulsion polymers according to the invention can also be used in other cases and not only for lacquers, for example for floor care products.

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung eines wässrigen, autoxida- tiv trocknenden Emulsionspolymerisates durch1. Process for the preparation of an aqueous, autoxidatively drying emulsion polymer
a) übliche Lösungspolymerisationa) usual solution polymerization
aa) eines Monomeren, welches durch Addition einer unge¬ sättigten Fettsäure an Glycidylacrylat bzw. -metha- crylat entsteht, mita a ) of a monomer which is formed by adding an unsaturated fatty acid to glycidyl acrylate or methacrylate
ab) einer ungesättigten Carbonsäure, ausgewählt aus der Gruppe Acrylsäure, Methacrylsäure, Crotonsäure, Fu- marsäure, Iaconsäure sowie Maleinsäureanhydrid allein oder in Kombination, wobeia b ) an unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, Iaconic acid and maleic anhydride, alone or in combination, where
ac) das Lösungspolymerisat eine Säurezahl zwischen 20 und 160 und ein Zahlenmittel der Molmasse M^ von 1 500 bis 80 000 aufweist, und die ungesättigte(n) Fettsäu¬ re(n) 15 bis 60 Masse-% des Lösungspolymerisates bil¬ den,a c ) the solution polymer has an acid number between 20 and 160 and a number average molecular weight M ^ of 1,500 to 80,000, and the unsaturated fatty acid (s) form 15 to 60% by weight of the solution polymer,
b) Teilneutralisation des Lösungspolymerisates durch Zugabe von Aminen oder Ammoniak auf einen Neutralisa¬ tionsgrad zwischen 0,4 und 0, 9 undb) Partial neutralization of the solution polymer by adding amines or ammonia to a degree of neutralization between 0.4 and 0.9 and
c) übliche Emulsonspolymerisationen des teilneutrali¬ sierten Lösungspolymerisates mit mindestens einem Monomeren aus der Gruppe Styren,
Figure imgf000012_0001
-Methylstyrol, p-Methylstyrol und Methylmethacrylat kombiniert mit mindestens einem aus der Gruppe Methyl-, Ethyl-, Butyl-, 2-Ethylhexylacrylat bzw. Butyl- und 2-Ethylhexylmethacrylat, wobei das Lösungspolymerisat 15 bis 35 Masse-% bezogen auf den Feststoffanteil im Emulsionspolymerisat bildet. c) customary emulsion polymerizations of the partially neutralized solution polymer with at least one monomer from the group styrene,
Figure imgf000012_0001
-Methylstyrene, p-methylstyrene and methyl methacrylate combined with at least one from the group consisting of methyl, ethyl, butyl, 2-ethylhexyl acrylate or butyl and 2-ethylhexyl methacrylate, the solution polymer being 15 to 35% by mass, based on the solids content in the Emulsion polymer forms.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet. daß als ungesättigte Carbonsäure 5 bis 25 Masse-% Metha¬ crylsäure oder Maleinsäureanhydrid bezogen auf das Lö¬ sungspolymerisat eingesetzt werden.2. The method according to claim 1, characterized. that 5 to 25% by mass of methacrylic acid or maleic anhydride, based on the solution polymer, is used as the unsaturated carboxylic acid.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet. daß als ungesättigte Fettsäure trocknende Öl-Fettsäuren, insbesondere Sojabohnenöl-Fettsäure, Linol- und/oder Linolensäure, verwendet werden.3. The method according to claim 1, characterized. that drying oil fatty acids, in particular soybean oil fatty acid, linoleic and / or linolenic acid, are used as the unsaturated fatty acid.
4. Verfahren nach Anspruch 1 oder 3, dadurch gekenn¬ zeichnet, daß die ungesättigten Fettsäuren 35 bis 50 Masse-% bezogen auf die Masse des Lösungspolymerisateε bilden.4. The method according to claim 1 or 3, characterized gekenn¬ characterized in that the unsaturated fatty acids form 35 to 50 mass% based on the mass of the solution polymer.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Lösungspolymerisat 20 bis 25 Masse-% bezogen auf den Feststoffanteil im Emulsionspo¬ lymerisat bildet.5. The method according to any one of claims 1 to 4, characterized in that the solution polymer forms 20 to 25% by mass based on the solids content in the emulsion polymer.
6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Lösungspolymerisat ein Zahlen¬ mittel der Molmassen 1% von 30 000 bis 40 000 aufweist. 6. The method according to any one of claims 1 to 4, characterized in that the solution polymer has a number average molecular weight 1% of 30,000 to 40,000.
PCT/DE1992/000107 1991-02-15 1992-02-13 Process for producing an aqueous, autoxidatively drying emulsion polymer, preferably used as binder for lacquers WO1992014763A1 (en)

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