WO1993009091A1 - Method of preparing light-coloured alkenyl sulphate pastes - Google Patents
Method of preparing light-coloured alkenyl sulphate pastes Download PDFInfo
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- WO1993009091A1 WO1993009091A1 PCT/EP1992/002499 EP9202499W WO9309091A1 WO 1993009091 A1 WO1993009091 A1 WO 1993009091A1 EP 9202499 W EP9202499 W EP 9202499W WO 9309091 A1 WO9309091 A1 WO 9309091A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
Definitions
- the invention relates to a process for producing light-colored alkenyl sulfate pastes by sulfonating lauric alcohols and subsequent neutralization and hydrolysis with aqueous bases.
- Anionic surfactants of the alkyl sulfate type in particular those which contain 16 to 18 carbon atoms in the fat residue, show excellent detergent properties and are suitable for the production of detergents, dishwashing detergents and cleaning agents.
- These substances are generally prepared from fatty alcohols which are first converted into the corresponding sulfuric acid semiesters using suitable sulfonating agents, for example gaseous sulfur trioxide, and then neutralized with bases, aqueous pastes of different solids content being obtained [J.Am .011.
- alkyl sulfates based on saturated is limited by the fact that aqueous pastes of these products are gel-like to highly viscous and no longer pumpable even at solids contents of 30 to 40% by weight, so that, for example, the spray drying for the production of powder detergents for further processing is out of the question.
- alkenyl sulfates that is to say sulfation products of unsaturated fatty alcohols, which in comparison have a significantly lower viscosity than the saturated products and, at paste concentrations of 50% by weight, are also flowable at room temperature.
- alkenyl sulfates have the disadvantage that they have a significantly poorer color quality than alkyl sulfates and can therefore, for aesthetic reasons, generally only be used after complex bleaching operations.
- the object of the invention was therefore to develop a process for producing light-colored alkenyl sulfate pastes which is free from the disadvantages described. Description of the invention
- the invention relates to a process for producing light-colored alkenyl sulfate pastes, which is characterized in that it contains lauric alcohols
- R 1 represents a linear, unsaturated, aliphatic hydrocarbon radical having 16 to 22 carbon atoms and 1, 2 or 3 double bonds and
- R 2 represents a linear or branched, saturated, aliphatic hydrocarbon radical having 12 to 22 carbon atoms
- the invention is based on the knowledge that the color of sulfonation products becomes more unsaturated Fatty alcohols deteriorate abruptly if the feedstocks exceed a critical iodine number of 50 and a critical content of polyunsaturated components of 1.5% by weight.
- lauric alcohols are vegetable fatty alcohols, for. B. to understand on the basis of palm oil, palm kernel oil or Ko ⁇ kosöl, which have an iodine number in the range of 10 to 50 and a proportion of polyunsaturated components from 0.1 to 1.5 wt .-% - based on the fatty alcohol .
- Typical examples of unsaturated fatty alcohols of the formula (I) which may be present in the lauric alcohols are palmitoleyl alcohol, oleyl alcohol, elaidyl alcohol, petroseline alcohol, linolyl alcohol, linolenyl alcohol, gadoleyl alcohol or erucyl alcohol.
- the lauric alcohols preferably contain oleyl alcohol.
- Saturated fatty alcohols of the formula (II), which may also be constituents of the lauric alcohols, are, for example, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachyl alcohol and behenyl alcohol.
- the lauric alcohols preferably contain cetyl and / or stearyl alcohol.
- the sulfonation of the lauric alcohols can take place in the manner known for fatty acid lower alkyl esters [J. Falbe (ed.), "Surfactants in consumer products", Springer Verlag, Berlin-Hei ⁇ delberg, 1987, p. 61], with continuous working reactors which operate according to the falling film principle are preferred.
- the lauric alcohols and the sulfur trioxide can be used in a molar ratio of 1: 0.95 to 1: 1.3, preferably 1: 1.05 to 1: 1.1.
- the sulfonation reaction can be carried out at temperatures T 1 of 25 to 90 ° C., but in particular 30 to 50 ° C.
- the acidic sulfonation products obtained in the sulfonation are stirred into aqueous bases, neutralized and hydrolyzed at the same time in order to prevent the compounds from being acidified again.
- the neutralization / hydrolysis can be carried out at temperatures from 70 to 90 ° C.
- proportions of sultons formed are hydrolyzed to form sulfonates without the sulfate group being split off.
- the acidic sulfonation products are neutralized immediately after leaving the reactor without further cooling, the hydrolysis also taking place at the same time.
- bases for the neutralization come alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C2-4-alkanolamines, for example mono-, di - And triethanolamine and primary, secondary or tertiary C ⁇ _4 ⁇ alkylamines into consideration.
- the neutralization bases are preferably used in the form of 20 to 50% by weight aqueous solutions, aqueous sodium hydroxide solutions being preferred.
- the sulfonation products of the lauric alcohols are mixtures which essentially contain alkyl and alkenyl sulfates. Since when unsaturated fatty alcohols are used in the sulfonation, sulfur trioxide also accumulates on the double bond, the mixture also contains substances which can contain an internal sulfonate group or a sulfonate and a sulfate group. The proportion of these internal sulfonation products can usually be 10 to 25% by weight, based on the amount of anionic surfactant.
- the sulfonation products can be bleached in a manner known per se by adding hydrogen peroxide and / or sodium hypochlorite solution. Based on the solids content in the solution of the sulfonation products, 0.2 to 2% by weight hydrogen peroxide, calculated as 100% substance, and / or corresponding amounts of sodium hypochlorite are used.
- the pH of the solutions can be adjusted to 7.5 to 10 by adding alkali. To stabilize against bacterial contamination, a preservation is also recommended, e.g. B. with formaldehyde solution, p-hydroxybenzoate, sorbic acid or other known preservatives.
- the light-colored alkenyl sulfate pastes obtainable by the process according to the invention have excellent detergent properties and a high solubility in cold water. They are therefore suitable for the production of powdered or liquid detergents, dishwashing detergents and cleaning products and products for hair and body care, in which they are used in amounts of 0.1 to 25, preferably 1 to 10% by weight, based on the solid ⁇ substance content of the agents - may be included.
- Anionic surfactant content 65.4% by weight sulfate content 53.1% by weight sulfonate content 12.3% by weight
- the anionic surfactant content and the unsulfonated contents were determined according to the DGF standard methods, Stuttgart, 1950-1984, H-III-10 and G-II-6b.
- the sulfate content was calculated as sodium sulfate, the water content was determined by the Fischer method.
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Abstract
The invention concerns the preparation of light-coloured alkenyl sulphate pastes by reacting with gaseous sulphur trioxide lauric alcohol derivatives including: a) unsaturated fatty alcohols of the formula (I): R?1-OH, in which R?1 is a straight-chain unsaturated aliphatic hydrocarbon group with 16 to 22 carbon atoms and 1, 2 or 3 double bonds, and b) unsaturated fatty alcohols of the formula (II): R?2-OH, in which R?2 is a straight-chain or branched-chain saturated aliphatic hydrocarbon group with 12 to 22 carbon atoms, and subsequently neutralizing and hydrolysing the acid reaction products with aqueous bases.
Description
Verfahren zur Herstellung hellfarbiger Alkenylsulfat-Pasten Process for the preparation of light-colored alkenyl sulfate pastes
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft ein Verfahren zur Herstellung hell¬ farbiger Alkenylsulfat-Pasten durch Sulfierung von Laurical- koholen und nachfolgende Neutralisation und Hydrolyse mit wäßrigen Basen.The invention relates to a process for producing light-colored alkenyl sulfate pastes by sulfonating lauric alcohols and subsequent neutralization and hydrolysis with aqueous bases.
Stand der TechnikState of the art
Anionische Tenside vom Typ der Alkylsulfate, insbesondere solche, die im Fettrest 16 bis 18 Kohlenstoffatome enthalten, zeigen ausgezeichnete Detergenseigenschaften und eignen sich zur Herstellung von Wasch-, Spül- und Reinigungsmitteln.Anionic surfactants of the alkyl sulfate type, in particular those which contain 16 to 18 carbon atoms in the fat residue, show excellent detergent properties and are suitable for the production of detergents, dishwashing detergents and cleaning agents.
Zur Herstellung dieser Stoffe geht man im allgemeinen von Fettalkoholen aus, die zunächst mit geeigneten Sulfiermit- teln, beispielsweise gasförmigem Schwefeltrioxid in die ent¬ sprechenden Schwefelsäurehalbester überführt und anschließend mit Basen neutralisiert werden, wobei wäßrige Pasten unter¬ schiedlichen Feststoffgehaltes erhalten werden [J.Am.011.These substances are generally prepared from fatty alcohols which are first converted into the corresponding sulfuric acid semiesters using suitable sulfonating agents, for example gaseous sulfur trioxide, and then neutralized with bases, aqueous pastes of different solids content being obtained [J.Am .011.
Che .Soc. .36., 208 (i960)]. Bei Einsatz ungesättigter Fettal¬ kohole, müssen die Reaktionsprodukte zusätzlich zur
Neutralisation noch einer Hydrolyse unterworfen werden, um ein Nachsäuern zu verhindern. Entsprechende Verfahren sind beispielsweise in Ten.Surf.Det .15, 299 (1978) und Ind.Eng. Chem.Prod.Res.Develop., .1, 24 (1965) beschrieben.Che. Soc. .36., 208 (i960)]. If unsaturated fatty alcohols are used, the reaction products must be added to the Neutralization can be subjected to hydrolysis to prevent acidification. Corresponding methods are described, for example, in Ten.Surf.Det .15, 299 (1978) and Ind.Eng. Chem.Prod.Res.Develop., .1, 24 (1965).
Die technische Verwendbarkeit von Alkylsulfaten auf Basis gesättigter
wird durch die Tatsache ein¬ geschränkt, daß wäßrige Pasten dieser Produkte schon bei Feststoffgehalten von 30 bis 40 Gew.-% gelartig bis hochvis¬ kos und nicht mehr pumpfähig sind, so daß beispielsweise die für die Herstellung von Pulverwaschmitteln übliche Sprüh¬ trocknung zur Weiterverarbeitung nicht in Betracht kommt.The technical usability of alkyl sulfates based on saturated is limited by the fact that aqueous pastes of these products are gel-like to highly viscous and no longer pumpable even at solids contents of 30 to 40% by weight, so that, for example, the spray drying for the production of powder detergents for further processing is out of the question.
Einen Ausweg bieten wäßrige Pasten von Alkenylsulfaten, also Sulfatierungsprodukten ungesättigter Fettalkohole, die im Vergleich eine deutlich niedrigere Viskosität als die gesät¬ tigten Produkte aufweisen und bei Pastenkonzentrationen von 50 Gew.-% auch noch bei Raumtemperatur fließfähig sind. Al- kenylsulfate besitzen jedoch den Nachteil, daß sie gegenüber Alkylsulfaten eine deutlich schlechtere Farbqualität aufwei¬ sen und somit aus ästhetischen Gründen im allgemeinen nur nach aufwendigen Bleichoperationen weiterverwendet werden können.A way out is provided by aqueous pastes of alkenyl sulfates, that is to say sulfation products of unsaturated fatty alcohols, which in comparison have a significantly lower viscosity than the saturated products and, at paste concentrations of 50% by weight, are also flowable at room temperature. However, alkenyl sulfates have the disadvantage that they have a significantly poorer color quality than alkyl sulfates and can therefore, for aesthetic reasons, generally only be used after complex bleaching operations.
Die Aufgabe der Erfindung bestand somit darin, ein Verfahren zur Herstellung von hellfarbigen Alkenylsulfat-Pasten zu entwickeln, das frei von den geschilderten Nachteilen ist.
Beschreibung der ErfindungThe object of the invention was therefore to develop a process for producing light-colored alkenyl sulfate pastes which is free from the disadvantages described. Description of the invention
Gegenstand der Erfindung ist ein Verfahren zur Herstellung hellfarbiger Alkenylsulfat-Pasten, das sich dadurch aus¬ zeichnet, daß man Lauricalkohole enthaltendThe invention relates to a process for producing light-colored alkenyl sulfate pastes, which is characterized in that it contains lauric alcohols
a) ungesättigte Fettalkohole der Formel (I),a) unsaturated fatty alcohols of the formula (I),
Ri-OH (I)Ri-OH (I)
in der R1 für einen linearen, ungesättigten, aliphati¬ schen Kohlenwasserstoffrest mit 16 bis 22 Kohlenstoff¬ atomen und 1, 2 oder 3 Doppelbindungen steht undin which R 1 represents a linear, unsaturated, aliphatic hydrocarbon radical having 16 to 22 carbon atoms and 1, 2 or 3 double bonds and
b) gesättigte Fettalkohole der Formel (II),b) saturated fatty alcohols of the formula (II),
R2-OH (II)R 2 -OH (II)
in der R2 für einen linearen oder verzweigten, gesät¬ tigten, aliphatischen Kohlenwasserstoffrest mit 12 bis 22 Kohlenstoffatomen steht,in which R 2 represents a linear or branched, saturated, aliphatic hydrocarbon radical having 12 to 22 carbon atoms,
mit gasförmigem Schwefeltrioxid umsetzt und die sauren Reak¬ tionsprodukte anschließend mit wäßrigen Basen neutralisiert und hydrolysiert.is reacted with gaseous sulfur trioxide and the acidic reaction products are then neutralized and hydrolyzed with aqueous bases.
Überraschenderweise wurde festgestellt, daß die Verwendung von pflanzlichen Lauricalkoholen gegenüber Fettalkoholen tierischer Herkunft zu Alkenylsulfaten mit deutlich besserer Farbgualität führt. Die Erfindung beruht auf der Erkenntnis, daß sich die Farbe von Sulfierungsprodukten ungesättigter
Fettalkohole sprunghaft verschlechtert, wenn die Einsatz¬ stoffe eine kritische Iodzahl von 50 und einen kritischen Gehalt von mehrfach ungesättigten Anteilen von 1,5 Gew.-% übersteigen.Surprisingly, it was found that the use of vegetable lauric alcohols compared to fatty alcohols of animal origin leads to alkenyl sulfates with significantly better color quality. The invention is based on the knowledge that the color of sulfonation products becomes more unsaturated Fatty alcohols deteriorate abruptly if the feedstocks exceed a critical iodine number of 50 and a critical content of polyunsaturated components of 1.5% by weight.
Unter Lauricalkohole sind im Sinne der Erfindung pflanzliche Fettalkohole z. B. auf Basis von Palmöl, Palmkernöl oder Ko¬ kosöl zu verstehen, die eine Iodzahl im Bereich von 10 bis 50 und einen Anteil an mehrfach ungesättigten Bestandteilen von 0,1 bis 1,5 Gew.-% - bezogen auf den Fettalkohol - aufweisen.In the context of the invention, lauric alcohols are vegetable fatty alcohols, for. B. to understand on the basis of palm oil, palm kernel oil or Ko¬ kosöl, which have an iodine number in the range of 10 to 50 and a proportion of polyunsaturated components from 0.1 to 1.5 wt .-% - based on the fatty alcohol .
Typische Beispiele für ungesättigte Fettalkohole der Formel (I), die in den Lauricalkoholen enthalten sein können, sind Palmitoleylalkohol, Oleylalkohol, Elaidylalkohol, Petrose- linylalkohol, Linolylalkohol, Linolenylalkohol, Gadoleyl- alkohol oder Erucylalkohol in Betracht. Vorzugsweise enthal¬ ten die Lauricalkohole Oleylalkohol.Typical examples of unsaturated fatty alcohols of the formula (I) which may be present in the lauric alcohols are palmitoleyl alcohol, oleyl alcohol, elaidyl alcohol, petroseline alcohol, linolyl alcohol, linolenyl alcohol, gadoleyl alcohol or erucyl alcohol. The lauric alcohols preferably contain oleyl alcohol.
Gesättigte Fettalkohole der Formel (II), die ebenfalls Be¬ standteile der Lauricalkohole sein können, sind beispiels¬ weise Caprinalkohol, Laurylalkohol, Myristylalkohol, Cetyl- alkohol, Stearylalkohol, Arachylalkohol und Behenylalkohol. Vorzugsweise enthalten die Lauricalkohole Cetyl- und/oder Stearylalkohol.Saturated fatty alcohols of the formula (II), which may also be constituents of the lauric alcohols, are, for example, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachyl alcohol and behenyl alcohol. The lauric alcohols preferably contain cetyl and / or stearyl alcohol.
Die Sulfierung der Lauricalkohole kann in der für Fettsäure- niedrigalkylester bekannten Weise [J.Falbe (ed.), "Surfac- tants in consumer products", Springer Verlag, Berlin- Hei¬ delberg, 1987, S. 61] erfolgen, wobei kontinuierlich arbei¬ tende Reaktoren, die nach dem Fallfilmprinzip arbeiten, be¬ vorzugt sind. Dabei wird das Schwefeltrioxid mit einem
inerten Gas, vorzugsweise Luft oder Stickstoff verdünnt und in Form eines Gasgemisches, welches das Sulfieragens in einer Konzentration von 1 bis 8, insbesondere 2 bis 5 Vol.-% ent¬ hält, eingesetzt.The sulfonation of the lauric alcohols can take place in the manner known for fatty acid lower alkyl esters [J. Falbe (ed.), "Surfactants in consumer products", Springer Verlag, Berlin-Hei¬ delberg, 1987, p. 61], with continuous working reactors which operate according to the falling film principle are preferred. The sulfur trioxide with a inert gas, preferably air or nitrogen, and used in the form of a gas mixture which contains the sulfonating agent in a concentration of 1 to 8, in particular 2 to 5,% by volume.
Die Lauricalkohole und das Schwefeltrioxid können im molaren Verhältnis von 1 : 0,95 bis 1 : 1,3, vorzugsweise 1 : 1,05 bis 1 : 1,1 eingesetzt werden. Die Sulfierreaktion kann bei Temperaturen T^ von 25 bis 90°C, insbesondere jedoch 30 bis 50°C durchgeführt werden.The lauric alcohols and the sulfur trioxide can be used in a molar ratio of 1: 0.95 to 1: 1.3, preferably 1: 1.05 to 1: 1.1. The sulfonation reaction can be carried out at temperatures T 1 of 25 to 90 ° C., but in particular 30 to 50 ° C.
Die bei der Sulfierung anfallenden sauren Sulfierprodukte werden in wäßrige Basen eingerührt, neutralisiert und gleich¬ zeitig hydrolysiert, um ein Nachsäuern der Verbindungen zu verhindern. Die Neutralisation/Hydrolyse kann bei Tempera¬ turen von 70 bis 90°C durchgeführt werden. Hierbei werden Anteile an gebildeten Sultonen unter Bildung von Sulfonaten hydrolysiert, ohne daß es zu einer Abspaltung der Sulfat¬ gruppe kommt. In einer bevorzugten Ausführungsform des er- findungsgemäßen Verfahrens werden die sauren Sulfierprodukte unmittelbar nach Verlassen des Reaktors ohne weitere Abküh¬ lung neutralisiert, wobei die Hydrolyse gleichzeitig miter¬ folgt.The acidic sulfonation products obtained in the sulfonation are stirred into aqueous bases, neutralized and hydrolyzed at the same time in order to prevent the compounds from being acidified again. The neutralization / hydrolysis can be carried out at temperatures from 70 to 90 ° C. Here, proportions of sultons formed are hydrolyzed to form sulfonates without the sulfate group being split off. In a preferred embodiment of the process according to the invention, the acidic sulfonation products are neutralized immediately after leaving the reactor without further cooling, the hydrolysis also taking place at the same time.
Als Basen für die Neutralisation kommen Alkalimetallhydroxide wie Natrium-, Kalium- und Lithiumhydroxid, Erdalkalimetall¬ oxide und -hydroxide wie Magneεiumoxid, Magnesiumhydroxid, Calciumoxid und Calciumhydroxid, Ammoniak, Mono-, Di- und Tri-C2_4-Alkanolamine, beispielsweise Mono-, Di- und Triethanolamin sowie primäre, sekundäre oder tertiäre Cι_4~Alkylamine in Betracht. Die Neutralisationsbasen
gelangen dabei vorzugsweise in Form 20 bis 50 gew.-%iger wäßriger Lösungen zum Einsatz, wobei wäßrige Natriumhy¬ droxidlösungen bevorzugt sind.As bases for the neutralization come alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C2-4-alkanolamines, for example mono-, di - And triethanolamine and primary, secondary or tertiary Cι_4 ~ alkylamines into consideration. The neutralization bases are preferably used in the form of 20 to 50% by weight aqueous solutions, aqueous sodium hydroxide solutions being preferred.
Die Sulfierprodukte der Lauricalkohole stellen Gemische dar, die im wesentlichen Alkyl- und Alkenylsulfate enthalten. Da bei Einsatz ungesättigter Fettalkohole in die Sulfierung auch eine Anlagerung des Schwefeltrioxids an die Doppelbindung stattfindet, sind in der Mischung auch Stoffe enthalten, die eine innenständige Sulfonatgruppe beziehungsweise eine Sulfonat- und eine Sulfatgruppe enthalten können. Der Anteil dieser innenständigen Sulfierprodukte kann üblicherweise 10 bis 25 Gew.-% - bezogen auf die Menge an Aniontensid - be¬ tragen.The sulfonation products of the lauric alcohols are mixtures which essentially contain alkyl and alkenyl sulfates. Since when unsaturated fatty alcohols are used in the sulfonation, sulfur trioxide also accumulates on the double bond, the mixture also contains substances which can contain an internal sulfonate group or a sulfonate and a sulfate group. The proportion of these internal sulfonation products can usually be 10 to 25% by weight, based on the amount of anionic surfactant.
Die Sulfierprodukte können nach Neutralisation in an sich bekannter Weise durch Zusatz von Wasserstoffperoxid- und/oder Natriumhypochloritlösung gebleicht werden. Dabei werden - bezogen auf den Feststoffgehalt in der Lösung der Sulfierprodukte - 0,2 bis 2 Gew.-% Wasserstoffperoxid - be¬ rechnet als 100 %ige Substanz - und/oder entsprechende Mengen Natriumhypochlorit eingesetzt. Der pH-Wert der Lösungen kann durch Zusatz von Alkali auf Werte von 7,5 bis 10 eingestellt werden. Zur Stabilisierung gegen Bakterienbefall emfiehlt sich ferner eine Konservierung, z. B. mit Formaldehydlöung, p-Hydroxybenzoat, Sorbinsäure oder anderen bekannten Konservieungsstoffen.
Gewerbliche AnwendbarkeitAfter neutralization, the sulfonation products can be bleached in a manner known per se by adding hydrogen peroxide and / or sodium hypochlorite solution. Based on the solids content in the solution of the sulfonation products, 0.2 to 2% by weight hydrogen peroxide, calculated as 100% substance, and / or corresponding amounts of sodium hypochlorite are used. The pH of the solutions can be adjusted to 7.5 to 10 by adding alkali. To stabilize against bacterial contamination, a preservation is also recommended, e.g. B. with formaldehyde solution, p-hydroxybenzoate, sorbic acid or other known preservatives. Industrial applicability
Die nach dem erfindungsgemäßen Verfahren erhältlichen hell¬ farbigen Alkenylsulfat-Pasten weisen ausgezeichnete Deter¬ genseigenschaften und eine hohe Kaltwasserlöslichkeif auf. Sie eignen sich daher zur Herstellung von pulverförmigen oder flüssigen Wasch-, Spül- und Reinigungsmitteln sowie Produkten der Haar- und Körperpflege, in denen sie in Mengen von 0,1 bis 25, vorzugsweise 1 bis 10 Gew.-% - bezogen auf den Fest¬ stoffgehalt der Mittel - enthalten sein können.The light-colored alkenyl sulfate pastes obtainable by the process according to the invention have excellent detergent properties and a high solubility in cold water. They are therefore suitable for the production of powdered or liquid detergents, dishwashing detergents and cleaning products and products for hair and body care, in which they are used in amounts of 0.1 to 25, preferably 1 to 10% by weight, based on the solid ¬ substance content of the agents - may be included.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken.
The following examples are intended to explain the subject matter of the invention in more detail without restricting it.
BeispieleExamples
I. Verwendete EinsatzstoffeI. Input materials used
Tab.1; Zusammensetzun und Kennzahlen der Fettalkohole"Tab. 1; Composition and key figures of fatty alcohols "
Beispiel 1;Example 1;
In einem kontinuierlich arbeitenden Fallfilmreaktor (Länge 120 cm, Querschnitt 1 cm, Eduktdurchsatz 600 g/h) mit Man¬ telkühlung und seitlicher Sθ3~Begasung wurden 1300 (5 mol) eines technischen Oleyl-Cetylalkohols auf Basis Palmöl (HD- Palmocenol(R) 45-50, Verkaufsprodukt der Fa.Henkel KGaA, Düsseldorf, FRG) bei T1 = 45°C mit 420 g (5,25 mol) gasför¬ migem Schwefeltrioxid (5 Vol.-% in Luft) - entsprechend einem molaren Einsatzverhältnis Alkohol : SO3 = 1 : 1,05 - umge¬ setzt. Das saure Sulfierprodukt wurde kontinuierlich bei T2 = 80°C in eine 37 gew.-%ige wäßrige Natriumhydroxidlösung ein¬ getragen und dabei gleichzeitig neutralisiert und hydroly¬ siert. Anschließend wurde das Reaktionsprodukt mit Natron¬ lauge auf einen pH-Wert von 10 eingestellt.In a continuously working falling film reactor (length 120 cm, cross section 1 cm, educt throughput 600 g / h) with jacket cooling and side gas aeration, 1300 (5 mol) of a technical oleyl cetyl alcohol based on palm oil (HD palmocenol ( R ) 45-50, sales product from Henkel KGaA, Düsseldorf, FRG) at T 1 = 45 ° C with 420 g (5.25 mol) of gaseous sulfur trioxide (5% by volume in air) - corresponding to a molar ratio of alcohol : SO3 = 1: 1.05 - implemented. The acidic sulfonation product was continuously introduced into a 37% by weight aqueous sodium hydroxide solution at T 2 = 80 ° C. and at the same time neutralized and hydrolyzed. The reaction product was then adjusted to a pH of 10 using sodium hydroxide solution.
Kenndaten des Produktes:Characteristics of the product:
Aniontensidgehalt 65,4 Gew.-% Sulfatanteil 53,1 Gew.-% Sulfonatanteil 12,3 Gew.-%Anionic surfactant content 65.4% by weight sulfate content 53.1% by weight sulfonate content 12.3% by weight
Unsulfierte Anteile 2.3 Gew.-%Unsulphated parts 2.3% by weight
Natriumsulfat 1.4 Gew.-%Sodium sulfate 1.4% by weight
Wasser 30,9 Gew.-%Water 30.9% by weight
Farbzahl 39 Klett
Beispiel 2 ;Color number 39 Velcro Example 2;
Analog Beispiel 1 wurden 1300 g (5 mol) eines technischen Oleyl-Cetylalkohols auf Basis Rindertalg (HD-Talgocenol(R) 50-55, Verkaufsprodukt der Fa.Henkel KGaA, Düsseldorf-, FRG) vorgelegt und bei τ = 45°C mit 420 g (5,25 mol) Schwefel¬ trioxid umgesetzt.Analogously to Example 1, 1300 g (5 mol) of an industrial oleyl cetyl alcohol based on beef tallow (HD-Talgocenol ( R ) 50-55, sales product from Henkel KGaA, Düsseldorf-, FRG) were introduced and at τ = 45 ° C. 420 g (5.25 mol) of sulfur trioxide reacted.
Kenndaten des Produktes?Characteristics of the product?
Anion ensidgehal 65.3 Gew.-% Sulfatanteil 52,9 Gew.-% - Sulfonatanteil 12.4 Gew.-% ünsulfierte Anteile 2,4 Gew.-% Natriumsulfat 1,4 Gew.-% Wasser 30,9 Gew.-%Anion ensidgehal 65.3% by weight sulfate content 52.9% by weight - sulfonate content 12.4% by weight unsulfated content 2.4% by weight sodium sulfate 1.4% by weight water 30.9% by weight
Farbzahl : 74 KlettColor number: 74 Velcro
Der Aniontensidgehalt und die unsulfierten Anteile wurden nach den DGF-Einheitsmethoden, Stuttgart, 1950-1984, H-III-10 bzw. G-II-6b ermittelt. Der Sulfatgehalt wurde als Natrium¬ sulfat berechnet, die Bestimmung des Wassergehaltes erfolgte nach der Fischer-Methode.The anionic surfactant content and the unsulfonated contents were determined according to the DGF standard methods, Stuttgart, 1950-1984, H-III-10 and G-II-6b. The sulfate content was calculated as sodium sulfate, the water content was determined by the Fischer method.
Die Bestimmung der Klett-Farbzahl erfolgte nach 30minütiger Bleiche mit 1 Gew.-% einer 35 gew.-%igen wäßrigen Wasser- stoffperoxidlösung. Die Messung wurde bei einer Konzentration von 5 Gew.-% Aniontensid, pH = 7 und unter Verwendung einer 1 cm Rundküvette sowie eines Blaufilters (400 bis 465 nm) durchgeführt.
The Klett color number was determined after 30 minutes of bleaching with 1% by weight of a 35% by weight aqueous hydrogen peroxide solution. The measurement was carried out at a concentration of 5% by weight of anionic surfactant, pH = 7 and using a 1 cm round cuvette and a blue filter (400 to 465 nm).
Claims
1. Verfahren zur Herstellung hellfarbiger Alkenylsulfat- Pasten, dadurch gekennzeichnet, daß man Lauricalkohole enthaltend1. A process for the preparation of light-colored alkenyl sulfate pastes, characterized in that containing lauric alcohols
a) ungesättigte Fettalkohole der Formel (I),a) unsaturated fatty alcohols of the formula (I),
R!-0H (I)R! -0H (I)
in der R für einen linearen, ungesättigten, aliphatischen Kohlenwasserstoffrest mit 16 bis 22in the R for a linear, unsaturated, aliphatic hydrocarbon radical with 16 to 22
Kohlenstoffatomen und 1, 2 oder 3 Doppelbindungen steht undCarbon atoms and 1, 2 or 3 double bonds and
b) gesättigte Fettalkohole der Formel (II),b) saturated fatty alcohols of the formula (II),
R2-OH (II)R 2 -OH (II)
in der R2 für einen linearen oder verzweigten, ge¬ sättigten, aliphatischen Kohlenwasserstoffrest mit 12 bis 22 Kohlenstoffatomen steht,in which R 2 represents a linear or branched, saturated, aliphatic hydrocarbon radical having 12 to 22 carbon atoms,
mit gasförmigem Schwefeltrioxid umsetzt und die sauren Reaktionsprodukte anschließend mit wäßrigen Basen neu¬ tralisiert und hydrolysiert.reacted with gaseous sulfur trioxide and the acidic reaction products then neutralized and hydrolyzed with aqueous bases.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Lauricalkohole auf Basis von Palmöl, Palmkernöl oder Kokosöl einsetzt, die eine Iodzahl im Bereich von 10 bis 50 aufweisen. 2. The method according to claim 1, characterized in that lauric alcohols based on palm oil, palm kernel oil or coconut oil are used which have an iodine number in the range from 10 to 50.
3. Verfahren nach den Ansprüchen 1 und 2, dadurch gekenn¬ zeichnet, daß man Lauricalkohole einsetzt, deren Anteil an mehrfach ungesättigten Bestandteilen 0,1 bis 1,5 Gew.-% - bezogen auf den Fettalkohol - beträgt.3. Process according to claims 1 and 2, characterized gekenn¬ characterized in that lauric alcohols are used, the proportion of polyunsaturated constituents of 0.1 to 1.5 wt .-% - based on the fatty alcohol.
4. Verfahren nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man Lauricalkohole und Schwefeltrioxid im molaren Verhältnis von 1 : 0.95 bis 1 : 1,3 einsetzt.4. The method according to at least one of claims 1 to 3, characterized in that lauric alcohols and sulfur trioxide are used in a molar ratio of 1: 0.95 to 1: 1.3.
5. Verfahren nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Sulfierung bei einer Temperatur von 25 bis 90°C durchführt.5. The method according to at least one of claims 1 to 4, characterized in that one carries out the sulfonation at a temperature of 25 to 90 ° C.
6. Verfahren nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Neutralisation/Hy¬ drolyse mit 20 bis 50 gew.-%igen Lösungen von Alkalihy¬ droxiden durchführt. 6. The method according to at least one of claims 1 to 5, characterized in that one carries out the neutralization / hydrolysis with 20 to 50 wt .-% solutions of alkali metal hydroxides.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5508156A JPH07500829A (en) | 1991-11-08 | 1992-10-30 | Manufacturing method of light-colored alkenyl sulfate paste |
| EP92922761A EP0613460A1 (en) | 1991-11-08 | 1992-10-30 | Method of preparing light-coloured alkenyl sulphate pastes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4136784.7 | 1991-11-08 | ||
| DE19914136784 DE4136784A1 (en) | 1991-11-08 | 1991-11-08 | PROCESS FOR PRODUCING LIGHT-COLORED ALKENYLSULPATE PASTE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993009091A1 true WO1993009091A1 (en) | 1993-05-13 |
Family
ID=6444359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1992/002499 WO1993009091A1 (en) | 1991-11-08 | 1992-10-30 | Method of preparing light-coloured alkenyl sulphate pastes |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0613460A1 (en) |
| JP (1) | JPH07500829A (en) |
| DE (1) | DE4136784A1 (en) |
| WO (1) | WO1993009091A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19939565A1 (en) * | 1999-08-20 | 2001-02-22 | Cognis Deutschland Gmbh | Branched unsaturated fatty alcohol sulfates of improved stability to auto-oxidation are useful in e.g. detergents, cosmetics and pharmaceutical preparations and are prepared from dimerized fatty acids |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2214254A (en) * | 1939-01-18 | 1940-09-10 | Procter & Gamble | Method for reacting higher alcohols with sulphating agents |
| US3763208A (en) * | 1970-10-19 | 1973-10-02 | Electric Reduction Co Ltd | Use of amine compounds in the sulfation of alcohols |
| WO1992016606A1 (en) * | 1991-03-21 | 1992-10-01 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing highly concentrated fatty alcohol sulphate pastes |
-
1991
- 1991-11-08 DE DE19914136784 patent/DE4136784A1/en not_active Withdrawn
-
1992
- 1992-10-30 EP EP92922761A patent/EP0613460A1/en not_active Withdrawn
- 1992-10-30 WO PCT/EP1992/002499 patent/WO1993009091A1/en not_active Application Discontinuation
- 1992-10-30 JP JP5508156A patent/JPH07500829A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2214254A (en) * | 1939-01-18 | 1940-09-10 | Procter & Gamble | Method for reacting higher alcohols with sulphating agents |
| US3763208A (en) * | 1970-10-19 | 1973-10-02 | Electric Reduction Co Ltd | Use of amine compounds in the sulfation of alcohols |
| WO1992016606A1 (en) * | 1991-03-21 | 1992-10-01 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing highly concentrated fatty alcohol sulphate pastes |
Non-Patent Citations (3)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 75, no. 1, 5. Juli 1971, Columbus, Ohio, US; abstract no. 5154, D. NOVAK ET AL. 'Sulfating of unsaturated aliphatic alcohols by gaseous sulfur trioxide.' Seite 432 ;Spalte 1 ; * |
| CHEMICAL ABSTRACTS, vol. 88, no. 8, 20. Februar 1978, Columbus, Ohio, US; abstract no. 52288m, A.S. YUSUPOV ET AL. 'Sulfating of unsaturated aliphatic alcohols by gaseous sulfur trioxide.' Seite 84 ;Spalte 2 ; * |
| TENSIDE DETERGENTS Bd. 15, Nr. 6, 1978, Seiten 299 - 306 M. MORAK ET AL. 'Sulfatierung von unges{ttigten Fettalkoholen' in der Anmeldung erw{hnt * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19939565A1 (en) * | 1999-08-20 | 2001-02-22 | Cognis Deutschland Gmbh | Branched unsaturated fatty alcohol sulfates of improved stability to auto-oxidation are useful in e.g. detergents, cosmetics and pharmaceutical preparations and are prepared from dimerized fatty acids |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07500829A (en) | 1995-01-26 |
| DE4136784A1 (en) | 1993-05-13 |
| EP0613460A1 (en) | 1994-09-07 |
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