EP0046171A1 - Storable and flowable aqueous suspensions of sodium aluminosilicates - Google Patents

Storable and flowable aqueous suspensions of sodium aluminosilicates Download PDF

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EP0046171A1
EP0046171A1 EP81104542A EP81104542A EP0046171A1 EP 0046171 A1 EP0046171 A1 EP 0046171A1 EP 81104542 A EP81104542 A EP 81104542A EP 81104542 A EP81104542 A EP 81104542A EP 0046171 A1 EP0046171 A1 EP 0046171A1
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weight
suspension
phosphoric acid
stabilizer
content
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German (de)
French (fr)
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Günter Sorbe
Jürgen Bollwerk
Horst-Dieter Dr. Wasel-Nielen
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C11D3/1286—Stabilised aqueous aluminosilicate suspensions

Definitions

  • the invention relates to storage-stable and flowable aqueous suspensions of water-insoluble sodium aluminum silicates with a silicate content of about 20 to 60% by weight, based on the weight of the suspension, and an additional content of a suspension stabilizer.
  • Water-insoluble sodium aluminum silicates such. B. is known from DE-OS 24 12 837, used in the form of zeolites as phosphate substitutes in detergents.
  • the disadvantage here lies in the need to use a component system which is present in such an amount as a percentage that the proportion of sodium aluminum silicate in the finished formulations is already noticeably reduced.
  • expensive organic substance must be used, which makes the use in detergents less profitable, and which also causes wastewater problems.
  • the subject of DE-OS 28 24 443 attempts to overcome the aforementioned disadvantages by stabilizing silicate suspensions as stabilizers by at least one hydroxyl-free, saturated or unsaturated aliphatic dicarboxylic acid with 3 to 10 carbon atoms or its alkali salt in an amount of 0. 5 - 15% by weight, based on the weight of the suspension, is proposed.
  • the stabilization effect which can be achieved with these substances is satisfactory for zeolite / water suspensions in a weight ratio of 1: 1 during a storage time of 24 hours if the amount of dispersion stabilizer added, such as malonic acid, succinic acid or maleic acid, is at least 5% by weight.
  • the aforementioned amount of stabilizer is still relatively high, so that efforts are being made to replace it with substances which are effective in a smaller amount.
  • a simple test is proposed as a method for checking the stability of the suspensions disclosed in DE-AS 25 27 388, in which an aluminum silicate suspension of the desired concentration - for example 31% by weight - is produced, which contains a dispersant in such an amount that Adequate stabilization of the suspension is guaranteed.
  • the influence of the added substance can then be visually observed in the settling behavior of the suspension.
  • a preferred suspension should generally be at most so far removed that the protruding clear or silicate particle-free solution makes up no more than 20%, preferably no more than 10%, in particular no more than 6% of the total height.
  • the settling behavior is checked, for example, in a standing cylinder at room temperature.
  • aqueous aluminum silicate suspensions are well stabilized in the above tests if the dispersants proposed for stabilization are present in a concentration of 1.3-3% by weight, with a silicate content of approximately 50% by weight of the suspension.
  • the present invention largely fulfills the above requirements.
  • the invention relates to storage-stable and flowable aqueous suspensions of water-insoluble sodium aluminum silicates with a silicate content of about 20 to 60% by weight, based on the weight of the suspension and an additional content of a phos phosphoric acid mono- or diesters as suspension stabilizers, which are characterized in that the suspension stabilizer is a phosphoric acid mono- and / or diester of fatty alcohol ethoxylates with about 1 to 6 moles of ethylene oxide per mole of alcohol or a phosphoric acid mono and / or diester of a technical mixture of aliphatic alcohols with at least 20 carbon atoms, the amount of stabilizer being about 0.1 to 5% by weight, based on the weight of the suspension.
  • the sodium aluminum silicate contained in the suspensions according to the invention preferably corresponds to the general formula of a zeolite of type A, Na 2 O Al 2 O 3 . (SiO 2 ) 2 . 4.5 H 2 O, the proportion of the silicate in the suspension usually being between 30 and 50% by weight, based on the weight of the suspension.
  • the mixture of phosphoric acid monoesters and diesters of fatty alcohol ethoxylates is liquid at 20 ° C. and has a density of 1.02 g / cm 3 , an acid number of 128 mg KOH / g, measured up to the second transition point pH 9-10 in water / isopropanol 1: 1 and a P 2 0 5 content of 11% by weight.
  • the mixture of phosphoric acid monoesters and diesters of aliphatic alcohols with at least 20 carbon atoms has a P 2 0 5 content of 10.3% by weight, a total acid number of 140 mg KOH / g Melting range from 65 - 66 ° C and a density of 0.94 g / cm 3 .
  • the aforementioned stabilizer mixtures already have a good stabilizing effect in a concentration of 0.1 to 3.5% by weight, based on the weight of the suspension.
  • the above phosphoric ester mixtures characterized in more detail by their physical properties, are commercially available products from Hoechst Aktiengesellschaft, Frankfurt / Main, and are commercially available under the name ° Knapsack-Phosphor Textreester 122 or ® Knapsack-Phosphor Acidester MDEC.
  • the suspension stabilizers according to the invention are characterized by surprisingly good stabilization effects, in that they already have 90-100% stabilization in concentrations of 0.1-0.5% by weight for 24 hours and more of aqueous sodium aluminum silicate suspensions. To achieve such effects, stabilizer concentrations of at least 5% by weight were previously required.
  • the substances according to the invention have the property, as a component of detergent compositions, to prevent foam formation and, moreover, to be wash-active.
  • the sedimentation behavior of the zeolite was 50% by weight aqueous suspensions in the presence of Stabilisatoren® Knapsack phosphoric acid ester 122 and ®Knapsack phosphoric acid ester MDEC were tested in different concentrations at certain intervals.
  • the first-mentioned stabilizer is a mixture of phosphoric acid monoesters and diesters of fatty alcohol ethoxylates which are liquid at 20 ° C. and have a density of 1.02 g / cm 3 , an acid number of 128 mg KOH / g, measured up to the second transition point pH 9-10 in water-isopropanol 1: 1 and a P 2 0 5 content of 11% by weight.
  • the ®Knapsack phosphoric acid ester MDEC is a mixture of phosphoric acid monoesters and diesters of aliphatic alcohols with at least 20 carbon atoms, the P 2 0 5 content of which is 10.3% by weight and which has a total acid number of 140 mg KOH / g, a melting range of 65 - 66 ° C and a density of 0.94 g / cm 3 is characterized.
  • the suspensions to be tested water was placed in a beaker, heated to 70 ° C. and then zeolite and optionally preheated ester were introduced with stirring at a stirring speed of 1000 rpm. After intensive mixing of the suspension, it was filled into 100 ml standing cylinders and then the settling behavior, ie the volume fractions of clear water standing above the suspension or the volume of the suspension, was measured at various time intervals. that no clear water layer formed and the suspension is completely stable. In the case of the rating number 80, the volume of the suspension is 80% of the total volume and the volume of the clear water density is 20%.
  • the measured values obtained are shown in the table below.
  • the table shows that the esters tested give aqueous zeolite suspensions sufficient stability even in concentrations of 0.1-0.5% by weight and thus outperform the known stabilizers used to date.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

Storable and flowable aqueous suspensions of water-insoluble sodium aluminosilicates having a silicate content of about 20 to 60 % by weight, relative to the weight of the suspension, and an additional content of a phosphoric acid mono- or diester as a suspension stabiliser, characterised in that the suspension stabiliser is a phosphoric acid mono- and/or diester of fatty alcohol ethoxylates having about 1 to 6 mol of ethylene oxide per mol of alcohol or a phosphoric acid mono- and/or diester of a technical mixture of aliphatic alcohols having at least 20 C atoms, the amount of the stabiliser being about 0.1 to 5 % by weight, relative to the weight of the suspension.

Description

Gegenstand der Erfindung sind lagerstabile und fließfähige wäßrige Suspensionen von wasserunlöslichen Natriumaluminiumsilicaten mit einem Silicatgehalt von etwa 20 bis 60 Gew%, bezogen auf das Gewicht der Suspension,und einem zusätzlichen Gehalt eines Suspensionsstabilisators.The invention relates to storage-stable and flowable aqueous suspensions of water-insoluble sodium aluminum silicates with a silicate content of about 20 to 60% by weight, based on the weight of the suspension, and an additional content of a suspension stabilizer.

Wasserunlösliche Natriumaluminiumsilicate werden, wie z. B. aus der DE-OS 24 12 837 bekannt ist, in Form von Zeolithen als Phosphatersatzstoffe in Waschmitteln eingesetzt.Water-insoluble sodium aluminum silicates such. B. is known from DE-OS 24 12 837, used in the form of zeolites as phosphate substitutes in detergents.

Das Problem besteht darin, daß bei der Konfektionsierung solcher Waschmittel diese Silicate in Form von relativ hochkonzentrierten wäßrigen Suspensionen gehandhabt werden müssen, die dann nach den üblichen Verfahren der Zerstäubungstrocknung in trockene Pulver überführt werden. Es hat sich gezeigt, daß beim Lagern und Umpumpen dieser Suspensionen häufig eine starke Sedimentierung der feinkörnigen Silicate eintritt und dadurch eine Herstellung von Waschmitteln mit einem konstanten Silicatgehalt erschwert wird. Nach der DE-OS 26 15 698 versuchte man das Problem dadurch zu lösen, daß man einer wäßrigen Zeolith-Suspension ein Dispergiermittel aus der Klasse der polymeren Carbonsäuren wie Natriumpolyacrylat und ein nichttensidisches phosphorfreies niedermolekulares anorganisches oder organisches Salz als Stabilisierhilfsmittel zusetzte. Als solches Salz wird u. a. Natriumcitrat genannt.The problem is that when such detergents are packaged, these silicates have to be handled in the form of relatively highly concentrated aqueous suspensions, which are then converted into dry powders by the usual spray drying processes. It has been shown that when these suspensions are stored and pumped around, the fine-grained silicates often undergo heavy sedimentation, making it more difficult to produce detergents with a constant silicate content. According to DE-OS 26 15 698, attempts were made to solve the problem by adding a dispersant to an aqueous zeolite suspension from the class of polymeric carboxylic acids such as sodium polyacrylate and a non-surfactant, phosphorus-free, low-molecular inorganic or organic salt as stabilizing agent. Sodium citrate is mentioned as such a salt.

Der Nachteil liegt hier in der Notwendigkeit, ein Komponentensystem einsetzen zu müssen, das prozentual in einer solchen Menge vorhanden ist, daß der Anteil am Natriumaluminiumsili.cat in den fertigen Formulierungen bereits merklich zurückgeht. Außerdem muß teure organische Substanz verwendet werden, die den Einsatz in Waschmitteln weniger rentabel gestaltet, und die zudem Abwasserprobleme mit sich bringt.The disadvantage here lies in the need to use a component system which is present in such an amount as a percentage that the proportion of sodium aluminum silicate in the finished formulations is already noticeably reduced. In addition, expensive organic substance must be used, which makes the use in detergents less profitable, and which also causes wastewater problems.

Die vorgenannten Nachteile werden von dem Gegenstand der DE-OS 28 24 443 zu überwinden versucht, indem zur Stabilisierung von Silicatsuspensionen als Stabilisator mindestens eine hydroxylgruppenfreie, gesättigte oder ungesättigte aliphatische Dicarbonsäure mit 3 - 10 C-Atomen oder ihr Alkalisalz in einer Menge von 0,5 - 15 Gew%, bezogen auf das Gewicht der Suspension, vorgeschlagen wird.The subject of DE-OS 28 24 443 attempts to overcome the aforementioned disadvantages by stabilizing silicate suspensions as stabilizers by at least one hydroxyl-free, saturated or unsaturated aliphatic dicarboxylic acid with 3 to 10 carbon atoms or its alkali salt in an amount of 0. 5 - 15% by weight, based on the weight of the suspension, is proposed.

Der mit diesen Substanzen erzielbare Stabilisierungseffekt ist bei Zeolith/Wasser-Suspensionen im Gewichtsverhältnis von 1 : 1 während einer Lagerungszeit von 24 Stunden dann befriedigend, wenn die Menge des zugesetzten Dispersionsstabilisators wie Malonsäure, Bernsteinsäure oder Maleinsäure mindestens 5 Gew% beträgt. Vorgenannte Stabilisatormenge ist noch relativ hoch, so daß das Bestreben besteht, diese durch in geringerer Menge wirksame Substanzen zu ersetzen.The stabilization effect which can be achieved with these substances is satisfactory for zeolite / water suspensions in a weight ratio of 1: 1 during a storage time of 24 hours if the amount of dispersion stabilizer added, such as malonic acid, succinic acid or maleic acid, is at least 5% by weight. The aforementioned amount of stabilizer is still relatively high, so that efforts are being made to replace it with substances which are effective in a smaller amount.

Schließlich ist in der DE-AS 25 27 388 eine pumpfähige, in ihrer Stabilität verbesserte, als Vorrats-Suspension geeignete wäßrige . Suspension eines wasserunlöslichen, zum Binden von Calcium befähigten Silicats offenbart, welche dadurch gekennzeichnet ist, daß sie, bezogen auf das Gesamtgewicht der wäßrigen Suspension

  • A) als zum Binden von Calcium befähigtes Silicat 20 bis 42 Gew0A einer feinverteilten, gebundenes Wasser enthaltenden, synthetisch hergestellten, wasserunlöslichen Verbindung der allgemeinen Formel
    Figure imgb0001
    in der Kat ein mit Calcium austauschbares Kation der Wertigkeit n, x eine Zahl von 0,7 bis 1,5, Me Bor oder Aluminium und y eine Zahl von 0,8 bis 6 bedeuten, und
  • B) als dispergierend wirkenden Bestandteil 0,5 bis 6 Gew% beispielsweise eines Phosphorsäurealkylesters, der pro Mol Phosphorsäure 1 bis 2 Mol eines gesättigten Alkohols mit 3 - 20 C-Atomen in der Alkylkette aufweist, enthält.
Finally, in DE-AS 25 27 388 is a pumpable, improved in its stability, suitable as a stock suspension suitable. Suspension of a water-insoluble, capable of binding calcium silicate disclosed, which is characterized in that it, based on the total weight of the aqueous suspension
  • A) UNTRAINED of binding calcium silicate 20 till 42 wt 0 A a finely divided, bound water-containing synthetically produced water-insoluble compound of the general formula
    Figure imgb0001
     in the cat a cation exchangeable with calcium of the valence n, x is a number from 0.7 to 1.5, Me boron or aluminum and y is a number from 0.8 to 6, and
  • B) 0.5 to 6% by weight as a dispersing component, for example of a phosphoric acid alkyl ester which contains 1 to 2 mol of a saturated alcohol having 3 to 20 carbon atoms in the alkyl chain per mole of phosphoric acid.

Als Methode zur Überprüfung der Stabilität der in der DE-AS 25 27 388 offenbarten Suspensionen wird ein einfacher Test vorgeschlagen, bei welchem eine Aluminiumsilicatsuspension der gewünschten Konzentration - beispielsweise 31 gew%ig - hergestellt wird, die ein Dispergiermittel in einer solchen Menge enthält, daß eine ausreichende Stabilisierung der Suspension gewährleistet ist. Der Einfluß des zugesetzten Stoffes kann dann im Absetzverhalten der Suspension visuell beobachtet werden. Nach 24-stündigem Stehen soll eine bevorzugte Suspension im allgemeinen höchstens so weit abgesetzt sein, daß die überstehende klare bzw. von Silicatteilchen freie Lösung nicht mehr als 20 %, vorzugsweise nicht mehr als 10 %, insbesondere nicht mehr als 6 % der Gesamthöhe ausmacht. Das Absetzverhalten wird beispielsweise in einem Standzylinder bei Raumtemperatur geprüft.A simple test is proposed as a method for checking the stability of the suspensions disclosed in DE-AS 25 27 388, in which an aluminum silicate suspension of the desired concentration - for example 31% by weight - is produced, which contains a dispersant in such an amount that Adequate stabilization of the suspension is guaranteed. The influence of the added substance can then be visually observed in the settling behavior of the suspension. After standing for 24 hours a preferred suspension should generally be at most so far removed that the protruding clear or silicate particle-free solution makes up no more than 20%, preferably no more than 10%, in particular no more than 6% of the total height. The settling behavior is checked, for example, in a standing cylinder at room temperature.

Gemäß Tabelle 2 der DE-AS 25 27 388 werden wäßrige Aluminiumsilicat-Suspensionen in Anwendung vorstehenden Tests gut stabilisiert, wenn die zur Stabilisierung vorgeschlagenen Dispergiermittel in einer Konzentration von 1,3 - 3 Gew%, bei einem Silicatgehalt von etwa 50 Gew%, in der Suspension vorliegen.According to Table 2 of DE-AS 25 27 388, aqueous aluminum silicate suspensions are well stabilized in the above tests if the dispersants proposed for stabilization are present in a concentration of 1.3-3% by weight, with a silicate content of approximately 50% by weight of the suspension.

Es war das Ziel der vorliegenden Erfindung, Dispergiermittel für Aluminiumsilicat-Suspensionen zu finden, die in möglichst geringer Konzentration eine Stabilisierung über mindestens 24 Stunden bewirken, d. h. ein Absetzen der Feststoffe in der Suspension verhindern und somit letztere fließ- und lagerfähig halten. Ein weiteres Ziel bestand darin, dafür einen möglichst einfach zugänglichen Stoff zu finden, der mit waschaktiven Substanzen verträglich ist, keine Schaumbildung verursacht und sich als Waschmittelkomponente möglichst durch waschaktive Eigenschaften auszeichnet.It was the object of the present invention to find dispersants for aluminum silicate suspensions which, in the lowest possible concentration, bring about stabilization for at least 24 hours, i.e. H. prevent the solids from settling in the suspension and thus keep the latter flowing and storable. Another goal was to find a substance that is as easily accessible as possible, that is compatible with detergent substances, does not cause foaming, and that, as a detergent component, is characterized by detergent properties if possible.

Vorstehende Forderungen werden durch den vorliegenden Erfindungsgegenstand weitgehend erfüllt.The present invention largely fulfills the above requirements.

Gegenstand der Erfindung sind lagerstabile und fließfähige wäßrige Suspensionen von wasserunlöslichen Natriumaluminiumsilicaten mit einem Silicatgehalt von etwa 20 bis 60 Gew%, bezogen auf das Gewicht der Suspension sowie einem zusätzlichen Gehalt eines Phosphösphorsäuremono- oder -diester als Suspensionsstabilisator, welche dadurch gekennzeichnet sind, daß der Suspensionsstabilisator ein Phosphorsäuremono- und/oder -diester von Fettalkoholethoxylaten mit etwa 1 bis 6 Mol Ethylenoxid pro Mol Alkohol oder ein Phosphorsäuremono-und/oder -diester eines technischen Gemisches aliphatischer Alkohole mit mindestens 20 C-Atomen ist, wobei die Menge des Stabilisators etwa 0,1 bis 5 Gew%, bezogen auf das Gewicht der Suspension,beträgt.The invention relates to storage-stable and flowable aqueous suspensions of water-insoluble sodium aluminum silicates with a silicate content of about 20 to 60% by weight, based on the weight of the suspension and an additional content of a phos phosphoric acid mono- or diesters as suspension stabilizers, which are characterized in that the suspension stabilizer is a phosphoric acid mono- and / or diester of fatty alcohol ethoxylates with about 1 to 6 moles of ethylene oxide per mole of alcohol or a phosphoric acid mono and / or diester of a technical mixture of aliphatic alcohols with at least 20 carbon atoms, the amount of stabilizer being about 0.1 to 5% by weight, based on the weight of the suspension.

Das in den erfindungsgemäßen Suspensionen enthaltene Natriumaluminiumsilicat entspricht vorzugsweise der allgemeinen Formel eines Zeolithen vom Typ A, Na2O Al2O3. (SiO2)2. 4,5 H2O, wobei der Anteil des Silicates in der Suspension meistens zwischen 30 und 50 Gew%, bezogen auf das Gewicht der Suspension, liegt.The sodium aluminum silicate contained in the suspensions according to the invention preferably corresponds to the general formula of a zeolite of type A, Na 2 O Al 2 O 3 . (SiO 2 ) 2 . 4.5 H 2 O, the proportion of the silicate in the suspension usually being between 30 and 50% by weight, based on the weight of the suspension.

Nach einer weiteren bevorzugten Ausführungsform der Erfindung ist das Gemisch von Phosphorsäuremono- und -diester von Fettalkoholethoxylaten bei 20° C flüssig und besitzt eine Dichte

Figure imgb0002
von 1,02 g/cm3, eine Säurezahl von 128 mg KOH/g, gemessen bis zum 2. Umschlagspunkt pH 9 - 10 in Wasser/Isopropanol 1 : 1 sowie einen P205-Gehalt von 11 Gew%.According to a further preferred embodiment of the invention, the mixture of phosphoric acid monoesters and diesters of fatty alcohol ethoxylates is liquid at 20 ° C. and has a density
Figure imgb0002
 of 1.02 g / cm 3 , an acid number of 128 mg KOH / g, measured up to the second transition point pH 9-10 in water / isopropanol 1: 1 and a P 2 0 5 content of 11% by weight.

Andererseits ist es von Vorteil, wenn das Gemisch aus Phosphorsäuremono- und -diester von aliphatischen Alkoholen mit mindestens 20 C-Atomen einen P205-Gehalt von 10,3 Gew%, eine Gesamt-Säurezahl von 140 mg KOH/g, einen Schmelzbereich von 65 - 66° C sowie eine Dichte

Figure imgb0003
von 0,94 g/cm3 besitzt.On the other hand, it is advantageous if the mixture of phosphoric acid monoesters and diesters of aliphatic alcohols with at least 20 carbon atoms has a P 2 0 5 content of 10.3% by weight, a total acid number of 140 mg KOH / g Melting range from 65 - 66 ° C and a density
Figure imgb0003
 of 0.94 g / cm 3 .

Die vorgenannten Stabilisatorgemische bewirken bereits in einer Konzentration von 0,1 bis 3,5 Gew%, bezogen auf das Gewicht der Suspension, einen guten Stabilisierungseffekt.The aforementioned stabilizer mixtures already have a good stabilizing effect in a concentration of 0.1 to 3.5% by weight, based on the weight of the suspension.

Die vorstehenden, durch ihre physikalischen Eigenschaften näher charakterisierten Phosphorsäureester-Gemische sind handelsübliche Produkte der Firma Hoechst Aktiengesellschaft, Frankfurt/Main,und unter der Bezeichnung ° Knapsack-Phosphorsäureester 122 bzw.® Knapsack-Phosphorsäureester MDEC käuflich erwerbbar.The above phosphoric ester mixtures, characterized in more detail by their physical properties, are commercially available products from Hoechst Aktiengesellschaft, Frankfurt / Main, and are commercially available under the name ° Knapsack-Phosphorsäureester 122 or ® Knapsack-Phosphorsäureester MDEC.

Wie aus dem nachfolgenden Beispiel in Verbindung mit der Tabelle ersichtlich, zeichnen sich die erfindungsgemäßen Suspensionsstabilisatoren durch überraschend gute Stabilisierungseffekte aus, indem sie bereits in Konzentrationen von 0,1 - 0,5 Gew% während 24 Stunden und mehr eine 90 - 100 %ige Stabilisierung von wäßrigen Natriumaluminiumsilicat-Suspensionen ermöglichen. Zur Erzielung derartiger Effekte waren bisher Stabilisatorkonzentrationen von mindestens 5 Gew% erforderlich. Darüberhinaus besitzen die erfindungsgemäßen Substanzen die Eigenschaft als Bestandteil von Waschmittelkompositionen die Schaumbildung zu verhindern und außerdem waschaktiv zu sein.As can be seen from the following example in conjunction with the table, the suspension stabilizers according to the invention are characterized by surprisingly good stabilization effects, in that they already have 90-100% stabilization in concentrations of 0.1-0.5% by weight for 24 hours and more of aqueous sodium aluminum silicate suspensions. To achieve such effects, stabilizer concentrations of at least 5% by weight were previously required. In addition, the substances according to the invention have the property, as a component of detergent compositions, to prevent foam formation and, moreover, to be wash-active.

Beispielexample

Es wurde ein als Zeolith HAB 40 bekanntes Natriumaluminiumsilicat der Firma Deutsche Gold- und Silber- anstalt,vormals Roessler, Frankfurt/Main mit einer mittleren Teilchengröße von 4 bis 25 /u der ungefähren Formel Na2O Al2O3 · (SiO2)2 · 4,5 H20 verwendet. Das Sedimentationsverhalten des Zeolithen wurde im 50 gew%igen wäßrigen Suspensionen in Gegenwart der Stabilisatoren® Knapsack-Phosphorsäureester 122 und ®Knapsack-Phosphorsäureester MDEC in unterschiedlichen Konzentrationen in bestimmten Zeitabständen geprüft.A sodium aluminum silicate known as Zeolite HAB 40 from Deutsche Gold- und Silberanstalt, formerly Roessler, Frankfurt / Main with an average particle size of 4 to 25 / u of the approximate formula Na 2 O Al 2 O 3. (SiO 2 ) 2 · 4.5 H 2 0 used. The sedimentation behavior of the zeolite was 50% by weight aqueous suspensions in the presence of Stabilisatoren® Knapsack phosphoric acid ester 122 and ®Knapsack phosphoric acid ester MDEC were tested in different concentrations at certain intervals.

Bei dem erstgenannten Stabilisator handelt es sich um ein Gemisch von Phosphorsäuremono- und -diester von Fettalkohlethoxylaten, welche bei 20° C flüssig sind und eine Dichte

Figure imgb0004
von 1,02 g/cm3, eine Säurezahl von 128 mg KOH/g, gemessen bis zum 2. Umschlagpunkt pH 9 - 10 in Wasser-Isopropanol 1 : 1 sowie einen P205-Gehalt von 11 Gew% besitzen. Der ®Knapsack-Phosphorsäureester MDEC stellt ein Gemisch aus Phosphorsäuremono- und -diester von aliphatischen Alkohlen mit mindestens 20 C-Atomen dar, dessen P205-Gehalt 10,3 Gew% beträgt und welches durch eine Gesamt-Säurezahl von 140 mg KOH/g, einen Schmelzbereich von 65 - 66° C sowie eine Dichte
Figure imgb0005
 von 0,94 g/cm3 charakterisiert ist.The first-mentioned stabilizer is a mixture of phosphoric acid monoesters and diesters of fatty alcohol ethoxylates which are liquid at 20 ° C. and have a density
Figure imgb0004
 of 1.02 g / cm 3 , an acid number of 128 mg KOH / g, measured up to the second transition point pH 9-10 in water-isopropanol 1: 1 and a P 2 0 5 content of 11% by weight. The ®Knapsack phosphoric acid ester MDEC is a mixture of phosphoric acid monoesters and diesters of aliphatic alcohols with at least 20 carbon atoms, the P 2 0 5 content of which is 10.3% by weight and which has a total acid number of 140 mg KOH / g, a melting range of 65 - 66 ° C and a density
Figure imgb0005
 of 0.94 g / cm 3 is characterized.

Zur Herstellung der zu prüfenden Suspensionen wurde Wasser in einem Becherglas vorgelegt, auf 70° C erwärmt und anschließend Zeolith und gegebenenfalls vorerwärmter Ester unter Rühren bei einer Rührgeschwindigkeit von 1000 U/min eingetragen. Nach intensiver Durchmischung der Suspension wurde diese in 100 ml-Standzylinder gefüllt und anschließend in verschiedenen Zeitabständen das Absetzverhalten, d. h. die Volumenanteile an klarem, über der Suspension stehendem Wasser bzw. das Volumen der Suspension gemessen.Die Bewertungszahl 100 bedeutet, daß sich keine klare Wasserschicht ausbildete und die Suspension vollkommen stabil ist. Im Falle der Bewertungszahl 80 beträgt das Volumen der Suspension 80 % des Gesamtvolumens und das Volumen der klaren Wasserdichte 20 %.To prepare the suspensions to be tested, water was placed in a beaker, heated to 70 ° C. and then zeolite and optionally preheated ester were introduced with stirring at a stirring speed of 1000 rpm. After intensive mixing of the suspension, it was filled into 100 ml standing cylinders and then the settling behavior, ie the volume fractions of clear water standing above the suspension or the volume of the suspension, was measured at various time intervals. that no clear water layer formed and the suspension is completely stable. In the case of the rating number 80, the volume of the suspension is 80% of the total volume and the volume of the clear water density is 20%.

In der nachfolgenden Tabelle sind die erhaltenen Meßwerte dargestellt. Aus der Tabelle geht hervor, daß die geprüften Ester wäßrigen Zeolith-Suspensionen bereits in Konzentrationen von 0,1 - 0,5 Gew% eine ausreichende Stabilität verleihen und somit die bisher angewandten bekannten Stabilisatoren an Wirksamkeit übertreffen.

Figure imgb0006
The measured values obtained are shown in the table below. The table shows that the esters tested give aqueous zeolite suspensions sufficient stability even in concentrations of 0.1-0.5% by weight and thus outperform the known stabilizers used to date.
Figure imgb0006

Claims (6)

1) Lagerstabile und fließfähige wäßrige Suspensionen von wasserunlöslichen Natriumaluminiumsilicaten mit einem Silicatgehalt von etwa 20 bis 60 Gew%, bezogen auf das Gewicht der Suspension sowie einem zusätzlichen Gehalt eines Phosphorsäuremono- oder -di-esters als Suspensionsstabilisator, dadurch gekennzeichnet, daß der Suspensionsstabilisator ein Phosphorsäuremono- und/oder -diester von Fettalkoholethoxylaten mit etwa 1 bis 6 Mol Ethylenoxid pro Mol Alkohol oder ein Phosphorsäuremono- und/oder -diester eines technischen Gemisches aliphatischer Alkohole mit mindestens 20 C-Atomen ist, wobei die Menge des Stabilisators etwa 0,1 bis 5 Gew%, bezogen auf das Gewicht der Suspension beträgt.1) Storage-stable and flowable aqueous suspensions of water-insoluble sodium aluminum silicates with a silicate content of about 20 to 60% by weight, based on the weight of the suspension and an additional content of a phosphoric acid mono- or di-ester as a suspension stabilizer, characterized in that the suspension stabilizer is a phosphoric acid mono - and / or diesters of fatty alcohol ethoxylates with about 1 to 6 moles of ethylene oxide per mole of alcohol or a phosphoric acid mono- and / or diester of a technical mixture of aliphatic alcohols with at least 20 carbon atoms, the amount of stabilizer being about 0.1 to 5% by weight, based on the weight of the suspension. 2) Suspension nach Anspruch 1, dadurch gekennzeichnet, daß das wasserunlösliche Natriumaluminiumsilicat der allgemeinen Formel eines Zeolithen vom Typ A, Na2O · Al2O3 · (SiO2)2 · 4,5 H20, entspricht.2) Suspension according to claim 1, characterized in that the water-insoluble sodium aluminum silicate of the general formula of a zeolite of the type A, Na 2 O · Al 2 O 3 · (SiO 2 ) 2 · 4.5 H 2 0, corresponds. 3) Suspension nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Anteil des Natriumaluminiumsilicates in der Suspension 30 bis 50 Gew%, bezogen auf das Gewicht der Suspension, beträgt.3) Suspension according to claim 1 or 2, characterized in that the proportion of sodium aluminum silicate in the suspension is 30 to 50% by weight, based on the weight of the suspension. 4) Suspension nach Anspruch 1 bis 3, dadurch gekenn- zeichnet, daß das Gemisch von Phosphorsäuremono-und -diester von Fettalkoholethoxylaten bei 20° C flüssig ist, eine Dichte
Figure imgb0007
von 1,02 g/cm3, eine Säurezahl von 128 mg KOH/g, gemessen bis zum 2. Umschlagspunkt pH 9 -10 in Wasser/Isopropanol 1 : 1 und einen P205-Gehalt von 11 Gew% besitzt.4) Suspension according to claim 1 to 3, characterized in that the mixture of phosphoric acid monoesters and diesters of fatty alcohol ethoxylates is liquid at 20 ° C, a density
Figure imgb0007
 of 1.02 g / cm 3 , an acid number of 128 mg KOH / g, measured up to the second transition point pH 9-10 in water / isopropanol 1: 1 and a P 2 0 5 content of 11% by weight. 5) Suspension nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß das Gemisch aus Phosphorsäuremono-und -diester von aliphatischen Alkoholen mit mindestens 20 C-Atomen einen P205-Gehalt von 10,3 Gew%, eine Gesamt-Säurezahl von 140 mg KOH/g, einen Schmelzbereich von 65 - 66° C sowie eine Dichte
Figure imgb0008
von 0,94 g/cm3 besitzt.5) Suspension according to claim 1 to 3, characterized in that the mixture of phosphoric acid and diesters of aliphatic alcohols with at least 20 carbon atoms has a P 2 0 5 content of 10.3% by weight, a total acid number of 140 mg KOH / g, a melting range of 65 - 66 ° C and a density
Figure imgb0008
 of 0.94 g / cm 3 . 6) Suspension nach Anspruch 1 bis 5, dadurch gekenn- zeichnet, daß die Menge des Stabilisators 0,1 - 3,5 Gew%, bezogen auf das Gewicht der Suspension, beträgt.6) Suspension according to claim 1 to 5, characterized characterized in that the amount of stabilizer is 0.1-3.5% by weight, based on the weight of the suspension.
EP81104542A 1980-08-16 1981-06-12 Storable and flowable aqueous suspensions of sodium aluminosilicates Withdrawn EP0046171A1 (en)

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US4525574A (en) * 1983-02-11 1985-06-25 Centre De Recherche Industrielle De Quebec Polyesters polyols prepared from glutaric acid, succinic acid and adipic acid, and polyurethanes prepared therefrom
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US4525574A (en) * 1983-02-11 1985-06-25 Centre De Recherche Industrielle De Quebec Polyesters polyols prepared from glutaric acid, succinic acid and adipic acid, and polyurethanes prepared therefrom
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