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WO1991004966A1 - Method for preparing technical mixtures of sulphated 2-alkylimidazoline derivatives - Google Patents

Method for preparing technical mixtures of sulphated 2-alkylimidazoline derivatives Download PDF

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Publication number
WO1991004966A1
WO1991004966A1 PCT/EP1990/001591 EP9001591W WO9104966A1 WO 1991004966 A1 WO1991004966 A1 WO 1991004966A1 EP 9001591 W EP9001591 W EP 9001591W WO 9104966 A1 WO9104966 A1 WO 9104966A1
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Prior art keywords
weight
hydroxyethyl
alkylimidazoline
derivatives
general formula
Prior art date
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Ceased
Application number
PCT/EP1990/001591
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German (de)
French (fr)
Inventor
Ansgar Behler
Uwe Ploog
Günter Uphues
Frank Clasen
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of WO1991004966A1 publication Critical patent/WO1991004966A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
    • C07D233/12—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
    • C07D233/12—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D233/14—Radicals substituted by oxygen atoms

Definitions

  • the invention relates to a process for the preparation of industrial mixtures of sulfonated 2-alkylimidazoline derivatives of general formula I.
  • R is a mixture of various straight-chain alkyl groups in the chain length range from 5 to 17 carbon atoms and
  • n is a number from 0 to 9
  • the location of the protonation of the sulfonated 2-alkylimidazoline derivatives of the general form obtained according to the invention has not yet been conclusively clarified; it is quite conceivable that the proton is located on the other nitrogen atom of the imidazoline ring.
  • the sulfonated 2-alkylimidazoline derivatives of the general formula I obtained according to the invention are amphoteric compounds which can be neutralized or deprotonated with bases, for example with LiOH, NaOH, a2C03, K0H, K2CO3, Mg (0H) 2.
  • CaO Ca (OH) 2, Sr (0H) 2, Ba (0H) 2, NH3, mono-C ⁇ -C4-alkylamines, di-C ⁇ -C4-alkylamines, tri-C ⁇ -C4-alkylamines, mono-C ⁇ - C4-hydroxyalkylamines, di-C ⁇ -C4-hydroxyalkylamines or tri- C ⁇ -C4-hydroxyalkylamines, the corresponding salts being obtained; the use of aqueous sodium hydroxide solution is preferred.
  • the hydroxyethyl-2-alkylimidazoline derivatives can be converted into the corresponding sulfonation products if the starting products and the sulfonating agent are used in molar ratios of at most 1 : 1 implements.
  • the type of technical mixtures of the hydroxyethyl-2-alkylimidazoline derivatives used as the starting material and the selected sulfonation conditions ensure a viscosity which is sufficiently low for the continuous production method.
  • the starting materials provided for the process of the invention can be prepared analogously to the above-mentioned procedure from technical fatty acid mixtures of appropriate chain length distribution and aminoethylethanolamines.
  • Technical fatty acid mixtures such as are available from natural, renewable raw materials, in particular from vegetable fats such as coconut oil or palm kernel oil, are preferably used.
  • fatty acids used for the preparation of the starting compound of the general formula II or the starting compounds of the general formula II contain small amounts of olefinically unsaturated compounds, this does not interfere with the process of the invention.
  • technical mixtures of the hydroxyethyl-2-alkylimidazoline derivatives of the following composition are used:
  • sulfethylated hydroxyethyl-2-alkylimidazoline derivatives of the general formula II in which R is as defined above and n 0.
  • sulfation is carried out at a temperature in the range from 80 to 120 ° C.
  • a preferred molar ratio of sulfur trioxide to hydroxyethyl-2-alkylimidazoline derivatives of the general formula II from 0.7: 1 to 0.95: 1.
  • the end products of the process of the invention are expediently placed in water immediately after sulfonation; the solutions obtained can be used as such as surface-active agents.
  • a neutralization with bases is only necessary in view of the molar ratios of the starting product and sulfonating agents used if the title compounds are to be prepared as salts.
  • the sulfonation was carried out in a falling film reactor made of glass, which essentially consisted of a tube surrounded by a heating and cooling jacket, 1100 mm long and 6 mm inside diameter.
  • the head of the reactor was provided with a feed device for the starting material and a gas inlet pipe.
  • Gaseous sulfur trioxide, produced by heating oleum, was used in the form of a mixture with nitrogen (5% by volume SO3).
  • the starting material was fed in at a constant speed of 550 g / h.
  • the desired molar ratio of sulfur trioxide to the starting compound was set via the feed amount of the sulfur trioxide-nitrogen mixture.
  • the reaction temperature was adjusted through the reactor jacket using a water circuit.
  • the l-hydroxyethyl-2-alkylimidazoline had been obtained by reacting a distilled, technical fatty acid ex hydrogenated coconut oil with 2-aminoethylethanol in, the fatty acid mixture having the following chain length distribution:

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Abstract

Technical mixtures of sulphated 2-alkylimidazoline derivatives of general formula (I), where R is a mixture of various straight-chain alkyl groups with a chain length of 5 to 17 carbon atoms and n is a number between 0 and 9, and their neutralization products with bases, can be prepared by sulphurization of technical mixtures of hydroxyethyl-2-alkylimidazoline derivatives of general formula (II), where R and n have the above-mentioned meanings, with sulphur trioxide. To this end, technical mixtures of the hydroxyethyl-2-alkylimidazoline derivatives, of which at least 40 wt. % are substituted with a 2-undecyl group, at least 15 wt- % with a 2-tridecyl group and not more than 33 wt. % with a 2-heptadecyl group and/or a straight-chain alkyl group with more than 17 carbon atoms, are reacted continuously in a thin layer with a mixture of gaseous sulphur trioxide and an inert carrier gas at temperatures between 70 and 120 C in a molar ratio of sulphur trioxide to hydroxyethyl-2-alkylimidazoline derivates between 0.5:1 and 1.0:1; if necessary, the sulphurization products are neutralized with bases.

Description

Verfahren zur Herstellung von technischen Gemischen sulfier 2-Alkylimidazolinderivate. Process for the preparation of technical mixtures of sulfier 2-alkylimidazoline derivatives.

Die Erfindung betrifft ein Verfahren zur Herstellung von technischen Gemischen sulfierter 2-Alkylimidazolinderivate allgemeinen Formel IThe invention relates to a process for the preparation of industrial mixtures of sulfonated 2-alkylimidazoline derivatives of general formula I.

Figure imgf000003_0001
Figure imgf000003_0001

in derin the

R ein Gemisch verschiedener geradkettiger Alkylgruppen im Kettenlängenbereich von 5 bis 17 Kohlenstoffatomen undR is a mixture of various straight-chain alkyl groups in the chain length range from 5 to 17 carbon atoms and

n eine Zahl im Bereich von 0 bis 9n is a number from 0 to 9

bedeuten, sowie ihrer Neutralisationsprodukte mit Basen.mean, and their neutralization products with bases.

Es ist bekannt, daß Fettsäuren mit Aminoethyl-ethanola inen unter Abspaltung von 2 mol Wasser l-Hydroxyethyl-2-alkyl- imidazoline ergeben, vgl. U. Ploog et al., Fette, Seifen, An¬ strichmittel .82., 57-59 (1980). Die erhaltenen I idazolinderivate lassen sich mit Ethylenoxid zu Polyethoxylierungsprodukten umsetzen.It is known that fatty acids with aminoethyl ethanol ine with elimination of 2 mol of water give l-hydroxyethyl-2-alkylimidazolines, cf. U. Ploog et al., Fette, Seifen, An¬ Anspichmittel .82., 57-59 (1980). The idazoline derivatives obtained can be reacted with ethylene oxide to give polyethoxylation products.

Weiterhin ist aus der US-B 2 985 662 bekannt, Hydroxy- ethyl-2-alkylimidazolinderivate in Anwesenheit von inerten Lösemitteln mit Sulfierungsmitteln wie Schwefeltrioxid oder insbesondere Chlorsulfonsäure zu sulfieren. Dabei wird her¬ vorgehoben, daß das Sulfierungsmittel im Überschuß zugesetzt werden muß, da sich zunächst Imidazoliniumsulfate bilden, bevor die seitenständige Hydroxylgruppe sulfiert wird; es wird daher empfohlen, mindestens 2 mol des Sulfierungs ittels auf 1 mol der AusgangsVerbindung einzusetzen.Furthermore, it is known from US Pat. No. 2,985,662 to sulfate hydroxyethyl-2-alkylimidazoline derivatives in the presence of inert solvents with sulfating agents such as sulfur trioxide or in particular chlorosulfonic acid. It is emphasized that the sulfating agent must be added in excess, since imidazolinium sulfates first form before the pendant hydroxyl group is sulfated; it is therefore recommended to use at least 2 mol of the sulfonating agent per 1 mol of the starting compound.

Es ist weiterhin bekannt, hydroxylgruppenhaltige Verbindungen mit gasförmigem Schwefeltrioxid, erzeugt durch Austreiben aus rauchender Schwefelsäure (Oleum) oder durch katalytische Oxidation von Schwefeldioxid, zu sulfieren, wobei die Aus¬ gangsprodukte in dünner Schicht mit dem Schwefeltrioxid zusammengebracht werden; derartige Verfahren sind z.B. in G. Dieckelmann, H.J. Heinz, The Basics of Industrial Oleo- chemistry, 1988, Peter Pomp GmbH, Essen, S. 113-119 beschrie¬ ben; dabei werden insbesondere Reaktoren vom Typ der Fall¬ filmreaktoren verwendet. Setzt man jedoch entsprechend der Lehre der US-B 2 985 662 die dort beschriebenen Hydroxyethyl- i idazoline mit gasförmigem Schwefeltrioxid in Fallfilmreak¬ toren um, erhält man nicht die gewünschtenIt is also known to sulfate compounds containing hydroxyl groups with gaseous sulfur trioxide, produced by expulsion from fuming sulfuric acid (oleum) or by catalytic oxidation of sulfur dioxide, the starting products being brought together with the sulfur trioxide in a thin layer; such methods are e.g. in G. Dieckelmann, H.J. Heinz, The Basics of Industrial Oleochemistry, 1988, Peter Pomp GmbH, Essen, pp. 113-119; reactors of the Fall¬ film type are used in particular. However, if, according to the teaching of US Pat. No. 2,985,662, the hydroxyethyl idazolines described there are reacted with gaseous sulfur trioxide in falling film reactors, the desired ones are not obtained

Sulfierungsprodukte, da die Viskosität des ReaktionsSystems zu groß ist. Demgemäß ist das in der US-B 2 985 662 beschriebene Verfahren nur auf diskontinuierliche bzw. Batch-Verfahren anwendbar. Demgemäß ist die Erfindung auf ein Verfahren zur Sulfierun von Hydroxyethyl-2-alkylimidazolinderivaten gerichtet, das kontinuierlich durchführbar ist.Sulfation products because the viscosity of the reaction system is too high. Accordingly, the process described in US Pat. No. 2,985,662 is only applicable to batch processes. Accordingly, the invention is directed to a process for the sulfonation of hydroxyethyl-2-alkylimidazoline derivatives which can be carried out continuously.

Diese Aufgabe wird er indungsgemäß dadurch gelöst, daß man technische Gemische der Hydroxyethyl-2-alkylderivate der allgemeinen Formel II,This object is achieved according to the invention in that technical mixtures of the hydroxyethyl-2-alkyl derivatives of the general formula II,

Figure imgf000005_0001
Figure imgf000005_0001

(cιι 2_cιι_ 2o)n-cn 2„cιι 2_oπ(cιι 2_cιι_ 2o) n-cn 2 "cιι 2_oπ

von denen mindestens 40 Gew.-% mit einer 2-Undecyl-, minde¬ stens 15 Gew.-% mit einer 2-Tridecyl- und höchstens 33 Gew. mit einer 2-Heptadecylgruppe und/oder einer mehr als 17 Kohlenstoffatome aufweisenden geradkettigen Alkylgruppe substituiert sind, kontinuierlich in dünner Schicht mit ei Gemisch von gasförmigem Schwefeltrioxid und einem inerten Trägergas bei Temperaturen im Bereich von 70 bis 120°C bei einem Molverhältnis von Schwefeltrioxid zu Hydroxyethyl-2- kylimidazolinderivaten im Bereich von 0,5 : 1 bis 1,0 : 1 umsetzt sowie gegebenenfalls die erhaltenen Sulfierungspro dukte mit Basen neutralisiert.at least 40% by weight with a 2-undecyl, at least 15% by weight with a 2-tridecyl and at most 33% with a 2-heptadecyl group and / or a straight-chain alkyl group having more than 17 carbon atoms are substituted, continuously in a thin layer with a mixture of gaseous sulfur trioxide and an inert carrier gas at temperatures in the range from 70 to 120 ° C. at a molar ratio of sulfur trioxide to hydroxyethyl-2-kylimidazoline derivatives in the range from 0.5: 1 to 1.0 : 1 and optionally neutralized the sulfonation products obtained with bases.

Der Ort der Protonierung der erfindungsgemäß erhaltenen sulfierten 2-Alkylimidazolinderivate der allgemeinen Forme ist noch nicht abschließend geklärt; es ist durchaus denkb daß sich das Proton an dem anderen Stickstoffatom des Imidazolinringes befindet. Die erfindungsgemäß erhaltenen sulfierten 2-Alkylimidazolin- derivate der allgemeinen Formel I sind amphotere Verbindungen, die mit Basen neutralisiert bzw. deprotoniert werden können, z.B. mit LiOH, NaOH, a2C03, K0H, K2CO3, Mg(0H)2. CaO, Ca(OH)2, Sr(0H)2, Ba(0H)2, NH3, Mono-Cχ-C4-alkylaminen, Di-Cι-C4-alkylaminen, Tri-Cι-C4-alkylaminen, Mono-Cι-C4-hy- droxyalkylaminen, Di-Cι-C4-hydroxyalkylaminen oder Tri- Cι-C4-hydroxyalkylaminen, wobei die entsprechenden Salze erhalten werden; die Verwendung von wäßriger Natronlauge ist bevorzugt.The location of the protonation of the sulfonated 2-alkylimidazoline derivatives of the general form obtained according to the invention has not yet been conclusively clarified; it is quite conceivable that the proton is located on the other nitrogen atom of the imidazoline ring. The sulfonated 2-alkylimidazoline derivatives of the general formula I obtained according to the invention are amphoteric compounds which can be neutralized or deprotonated with bases, for example with LiOH, NaOH, a2C03, K0H, K2CO3, Mg (0H) 2. CaO, Ca (OH) 2, Sr (0H) 2, Ba (0H) 2, NH3, mono-Cχ-C4-alkylamines, di-Cι-C4-alkylamines, tri-Cι-C4-alkylamines, mono-Cι- C4-hydroxyalkylamines, di-Cι-C4-hydroxyalkylamines or tri- Cι-C4-hydroxyalkylamines, the corresponding salts being obtained; the use of aqueous sodium hydroxide solution is preferred.

Überraschenderweise hat sich nämlich gezeigt, daß entgegen der Lehre der US-B 2 985 662 im Verfahren der Erfindung die Hydroxyethyl-2-alkylimidazolinderivate sich durchaus zu den entsprechenden Sulfierungsprodukten umsetzen lassen, wenn man die Ausgangsprodukte und das Sulfierungsmittel in Molverhält¬ nissen von maximal 1 : 1 umsetzt. Die Art der als Ausgangsma¬ terial eingesetzten technischen Gemische der Hydroxy- ethyl-2-alkylimidazolinderivate und die ausgewählten Sul- fierungsbedingungen gewährleisten dabei eine für die kontinu¬ ierliche Herstellungsweise ausreichend niedrige Viskosität.Surprisingly, it has been shown that contrary to the teaching of US Pat. No. 2,985,662 in the process of the invention, the hydroxyethyl-2-alkylimidazoline derivatives can be converted into the corresponding sulfonation products if the starting products and the sulfonating agent are used in molar ratios of at most 1 : 1 implements. The type of technical mixtures of the hydroxyethyl-2-alkylimidazoline derivatives used as the starting material and the selected sulfonation conditions ensure a viscosity which is sufficiently low for the continuous production method.

Die für das Verfahren der Erfindung vorgesehenen Ausgangsma¬ terialien lassen sich, analog zu der oben erwähnten Arbeits¬ weise aus technischen Fettsäuregemischen entsprechender Kettenlängenverteilung und Aminoethyl-ethanolaminen her¬ stellen. Dabei kommen bevorzugt technische Fettsäuregemische zum Einsatz, wie sie aus natürlichen, nachwachsenden Roh¬ stoffen, insbesondere aus Pflanzenfetten wie Kokosöl oder Palmkernöl, zugänglich sind.The starting materials provided for the process of the invention can be prepared analogously to the above-mentioned procedure from technical fatty acid mixtures of appropriate chain length distribution and aminoethylethanolamines. Technical fatty acid mixtures such as are available from natural, renewable raw materials, in particular from vegetable fats such as coconut oil or palm kernel oil, are preferably used.

Falls die zur Herstellung der Ausgangsverbindung der allge¬ meinen Formel II eingesetzten Fettsäuren bzw. die Ausgangs¬ verbindungen der allgemeinen Formel II geringe Anteile an olefinisch ungesättigten Verbindungen enthalten, stört dies im Verfahren der Erfindung nicht. Gemäß einer bevorzugten Ausführungsform des Verfahrens der Erfindung setzt man technische Gemische der Hydroxy- ethyl-2-alkylimidazolinderivate der folgenden Zusammensetzung ein:If the fatty acids used for the preparation of the starting compound of the general formula II or the starting compounds of the general formula II contain small amounts of olefinically unsaturated compounds, this does not interfere with the process of the invention. According to a preferred embodiment of the process of the invention, technical mixtures of the hydroxyethyl-2-alkylimidazoline derivatives of the following composition are used:

Derivat Anteil am technischen GemischDerivative Share in the technical mixture

2-Pentyl 0 - 1 Gew.-%2-pentyl 0-1% by weight

2-Heptyl 3 - 7 Gew.-%2-heptyl 3 - 7% by weight

2-Nonyl 1 - 6 Gew.-%2-nonyl 1-6% by weight

2-Undecyl 40 - 53 Gew.-%2-undecyl 40-53% by weight

2-Tridecyl 15 - 23 Gew.-%2-tridecyl 15-23% by weight

2-Pentadecyl 8 - 15 Gew.-%2-pentadecyl 8 - 15% by weight

wobei die Summe der Gewichtsanteile maximal 100 Gew.-% ergibt und ein gegebenenfalls zu 100 Gew.-% fehlender Anteil von 2-Heptadecyl- und/oder mehr als 17 Kohlenstoffatome aufwei¬ senden 2-Alkylgruppen gebildet ist.wherein the sum of the parts by weight amounts to a maximum of 100% by weight and a possibly 100% by weight missing part of 2-heptadecyl and / or 2-alkyl groups having more than 17 carbon atoms is formed.

Gemäß einer weiteren vorteilhaften Ausführungsform des Ver¬ fahrens der Erfindung sulfiert man Hydroxyethyl-2-alkylimida- zolinderivate der allgemeinen Formel II, in der R wie oben definiert und n = 0 ist. Das Verfahren ist jedoch ohne weiteres auch auf Anlagerungsprodukte von im Mittel 2 bis 9 mol Ethylenoxid an Hydroxyethyl-2-alkylimidazolinderivate der allgemeinen Formel II (n = 2 - 9) anwendbar.According to a further advantageous embodiment of the process of the invention, sulfethylated hydroxyethyl-2-alkylimidazoline derivatives of the general formula II in which R is as defined above and n = 0. However, the process is also readily applicable to adducts of on average 2 to 9 mol of ethylene oxide with hydroxyethyl-2-alkylimidazoline derivatives of the general formula II (n = 2-9).

Gemäß einer weiteren vorteilhaften Ausführungsform der Erfin¬ dung sulfiert man bei einer Temperatur im Bereich von 80 bis 120°C. Ein bevorzugtes molares Verhältnis von Schwefeltrioxid zu Hydroxyethyl-2-alkylimidazolinderivaten der allgemeinen Formel II von 0,7 : 1 bis 0,95 : 1.According to a further advantageous embodiment of the invention, sulfation is carried out at a temperature in the range from 80 to 120 ° C. A preferred molar ratio of sulfur trioxide to hydroxyethyl-2-alkylimidazoline derivatives of the general formula II from 0.7: 1 to 0.95: 1.

Weiterhin bevorzugt ist, das Verfahren der Erfindung vom Typ der oben erwähnten Fallfilmreaktoren durchzuführen, wobei man bevorzugt mit einem Stickstoff-Schwefeltrioxid-Gemisch mit einem Schwefeltrioxidgehalt im Bereich von 1 bis 10 Vol.-% sulfiert. Obwohl das Verfahren der Erfindung in Gegenwart von inerten Lösemitteln durchgeführt werden kann, ist es bevor¬ zugt, die technischen Gemische der Hydroxyethyl-2-alkylimida- zolinderivate der allgemeinen Formel II, in der R und n wie oben definiert sind, in Abwesenheit von Lösemitteln zu sulfieren.It is further preferred to carry out the process of the invention of the type of the falling film reactors mentioned above, wherein preferably sulfated with a nitrogen-sulfur trioxide mixture with a sulfur trioxide content in the range from 1 to 10% by volume. Although the process of the invention can be carried out in the presence of inert solvents, it is preferred to use the technical mixtures of the hydroxyethyl-2-alkylimidazoline derivatives of the general formula II, in which R and n are as defined above, in the absence of solvents to sulfate.

Zweckmäßigerweise werden die Endprodukte des Verfahrens der Erfindung unmittelbar nach der Sulfierung in Wasser gegeben; die dabei erhaltenen Lösungen können als solche als oberflächenaktive Mittel eingesetzt werden. Eine Neutralisa¬ tion mit Basen ist in Anbetracht der eingesetzten molaren Verhältnisse von Ausgangsprodukt und Sulfierungsmitteln nur erforderlich, wenn die Titelverbindungen als Salze hergestellt werden sollen. The end products of the process of the invention are expediently placed in water immediately after sulfonation; the solutions obtained can be used as such as surface-active agents. A neutralization with bases is only necessary in view of the molar ratios of the starting product and sulfonating agents used if the title compounds are to be prepared as salts.

Das Verfahren der Erfindung wird im folgenden anhand von bevorzugten Ausführungsbeispielen näher erläutert.The method of the invention is explained in more detail below on the basis of preferred exemplary embodiments.

Die Sulfierung wurde in einem Fallfilmreaktor aus Glas vorge¬ nommen, der im wesentlichen aus einem von einem Heiz- und Kühlmantel umgebenen Rohr von 1100 mm Länge und 6 mm Innen¬ durchmesser bestand. Der Reaktor war am Kopf mit einer Aufga- bevorrichtung für das Ausgangsmaterial und einem Gaseinlei¬ tungsrohr versehen. Gasförmiges Schwefeltrioxid, erzeugt durch Erhitzen von Oleu , wurde in Form einer Mischung mit Stick¬ stoff (5 Vol.-% SO3) eingesetzt.The sulfonation was carried out in a falling film reactor made of glass, which essentially consisted of a tube surrounded by a heating and cooling jacket, 1100 mm long and 6 mm inside diameter. The head of the reactor was provided with a feed device for the starting material and a gas inlet pipe. Gaseous sulfur trioxide, produced by heating oleum, was used in the form of a mixture with nitrogen (5% by volume SO3).

Das Ausgangsmaterial wurde mit einer konstanten Geschwindig¬ keit von 550 g/h aufgegeben. Das gewünschte Molverhältnis von Schwefeltrioxid zu Ausgangsverbindung wurde über die Zufuhr¬ menge des Schwefeltrioxid-Stickstoff-Gemisches eingestellt. Weiterhin wurde die Reaktionstemperatur mit Hilfe eines Wasserkreislaufs durch den Reaktormantel eingestellt.The starting material was fed in at a constant speed of 550 g / h. The desired molar ratio of sulfur trioxide to the starting compound was set via the feed amount of the sulfur trioxide-nitrogen mixture. Furthermore, the reaction temperature was adjusted through the reactor jacket using a water circuit.

Beispiel 1.Example 1.

Unter Verwendung des zuvor beschriebenen Reaktors wurde ein l-Hydroxyethyl-2-alkylimidazolin der allgemeinen Formel II (n = 0, R = C7~Ci7-Alkyl) bei einem Molverhältnis von Schwefeltrioxid zu Im'idazolinderivat von 0,9 : 1 und einer Reaktortemperatur von 98°C sulfiert. Das l-Hydroxyethyl-2-al- kylimidazolin war durch Umsetzung einer destillierten, tech¬ nischen Fettsäure ex hydriertem Kokosfett mit 2-Aminoethyl- ethanola in erhalten worden, wobei das Fettsäuregemisch die folgende Kettenlängenverteilung aufwies:Using the reactor described above, an l-hydroxyethyl-2-alkylimidazoline of the general formula II (n = 0, R = C7 ~ Ci7-alkyl) was obtained at a molar ratio of sulfur trioxide to im ' idazoline derivative of 0.9: 1 and a reactor temperature sulfated at 98 ° C. The l-hydroxyethyl-2-alkylimidazoline had been obtained by reacting a distilled, technical fatty acid ex hydrogenated coconut oil with 2-aminoethylethanol in, the fatty acid mixture having the following chain length distribution:

C6 = 1 %, C8 = 7 %, C10 = 6 %, C12 = 48 %, C14 = 19 %, C16 = 9 %, Cig = 10 %. Die Säurezahl des Fettsäuregemisches betrug 266 bis 276, die Jodzahl weniger als 0,5. Das Sulfiergemisch wurde unmittelbar nach dem Verlassen des Reaktors in Wasser gegeben. Das erhaltene Produkt wies die folgenden Kenndaten auf:C 6 = 1%, C 8 = 7%, C10 = 6%, C 12 = 48%, C 14 = 19%, C 16 = 9%, Cig = 10%. The acid number of the fatty acid mixture was 266 to 276, the iodine number less than 0.5. The sulfonation mixture was placed in water immediately after leaving the reactor. The product obtained had the following characteristics:

Gesamtschwefel 4,12 %Total sulfur 4.12%

Sulfat 1,2 % unsulfierte Substanz 6,5 %Sulphate 1.2% unsulphated substance 6.5%

Sulfiergrad 86,2 %Degree of sulfonation 86.2%

Wassergehalt 46,0 %.Water content 46.0%.

Beispiel 2.Example 2.

Die Sulfierung gemäß Beispiel 1 wurde wiederholt, wobei das molare Verhältnis von Schwefeltrioxid zu Imidazolinderivat 0,7 : 1 und die Sulfiertemperatur 95°C betrug. Das Reaktions¬ produkt wies die folgenden Kenndaten auf:The sulfonation according to Example 1 was repeated, the molar ratio of sulfur trioxide to imidazoline derivative being 0.7: 1 and the sulfonation temperature being 95.degree. The reaction product had the following characteristics:

Gesamtschwefel 2,2 %Total sulfur 2.2%

Sulfat 0,79 % unsulfierte Substanz 0,79 %Sulphate 0.79% unsulphated substance 0.79%

Sulfiergrad 66,0 %Degree of sulfation 66.0%

Wassergehalt 69,8 %. Water content 69.8%.

Claims

Patentansprüche Claims Verfahren zur Herstellung von technischen Gemischen sulfierter 2-Alkylimidazolinderivate der allgemeinen Formel IProcess for the preparation of technical mixtures of sulfonated 2-alkylimidazoline derivatives of the general formula I.
Figure imgf000011_0001
Figure imgf000011_0001
 in derin the R ein Gemisch verschiedener geradkettiger Alkylgruppen i Kettenlängenbereich von 5 bis 17 Kohlenstoffatomen undR is a mixture of various straight-chain alkyl groups in the chain length range from 5 to 17 carbon atoms and n eine Zahl im Bereich von 0 bis 9n is a number from 0 to 9 bedeuten, sowie ihrer Neutralisationsprodukte mit Basen durch Sulfierung technischer Gemische von Hydroxyethyl-2-alkylimidazolinderivaten der allgemeinen Formel IImean, and their neutralization products with bases by sulfonation of technical mixtures Hydroxyethyl-2-alkylimidazoline derivatives of the general formula II
Figure imgf000012_0001
Figure imgf000012_0001
 (CII-ClI-O) -CII-CII 0H 2 2 n 2 2(CII-ClI-O) -CII-CII 0H 2 2 n 2 2 in der R und n wie oben definiert sind, mit Schwefeltri¬ oxid, dadurch gekennzeichnet, daß man technische Gemische der Hydroxyethyl-2-alkylimidazolinderivate, von denen mindestens 40 Gew.-% mit einer 2-Undecyl-, mindestens 15 Gew.-% mit einer 2-Tridecyl- und höchstens 33 Gew.-% mit einer 2-Heptadecylgruppe und/oder einer mehr als 17 Kohlenstoffatome aufweisenden geradkettigen Alkylgruppe substituiert sind, kontinuierlich in dünner Schicht mit einem Gemisch von gasförmigem Schwefeltrioxid und einem inerten Trägergas bei Temperaturen im Bereich von 70 bis 120°C bei einem Molverhältnis von Schwefeltrioxid zu Hydroxyethyl-2-alkylimidazolinderivaten im Bereich von 0,5 : 1 bis 1,0 : 1 umsetzt sowie gegebenenfalls die erhaltenen Sulfierungsprodukte mit Basen neutralisiert.in which R and n are as defined above, with sulfur trioxide, characterized in that technical mixtures of the hydroxyethyl-2-alkylimidazoline derivatives, of which at least 40% by weight with a 2-undecyl, at least 15% by weight with a 2-tridecyl and at most 33 wt .-% with a 2-heptadecyl group and / or a straight-chain alkyl group having more than 17 carbon atoms, continuously in a thin layer with a mixture of gaseous sulfur trioxide and an inert carrier gas at temperatures in the range from 70 to 120 ° C. with a molar ratio of sulfur trioxide to hydroxyethyl-2-alkylimidazoline derivatives in the range from 0.5: 1 to 1.0: 1 and optionally neutralizing the sulfonation products obtained with bases. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß di technischen Gemische der Hydroxyethyl-2-alkylimidazolin- derivate die folgende Zusammensetzung aufweisen: Derivat Anteil am technischen GemischA method according to claim 1, characterized in that the technical mixtures of the hydroxyethyl-2-alkylimidazoline derivatives have the following composition: Derivative Share in the technical mixture 2-Pentyl 0 - 1 Gew.-%2-pentyl 0-1% by weight 2-Heptyl 3 - 7 Gew.-%2-heptyl 3 - 7% by weight 2-Nonyl 1 - 6 Gew.-%2-nonyl 1-6% by weight 2-Undecyl 40 - 53 Gew.-%2-undecyl 40-53% by weight 2-Tridecyl 15 - 23 Gew.-%2-tridecyl 15-23% by weight 2-Pentadecyl 8 - 15 Gew.-%2-pentadecyl 8 - 15% by weight wobei die Summe der Gewichtsanteile maximal 100 Gew.-% ergibt und ein gegebenenfalls zu 100 Gew.-% fehlender Anteil von 2-Heptadecyl- und/oder mehr als 17 Kohlen¬ stoffatome aufweisenden 2-Alkylgruppen gebildet ist.wherein the sum of the parts by weight amounts to a maximum of 100% by weight and a possibly 100% by weight missing part of 2-heptadecyl and / or more than 17 carbon atoms having 2-alkyl groups is formed. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man ein Hydroxyethyl-2-alkylimidazolinderivat der allgemeinen Formel II sulfiert, in der R wie oben defi¬ niert und n = 0 ist.3. The method according to claim 1 or 2, characterized in that sulfonating a hydroxyethyl-2-alkylimidazoline derivative of the general formula II, in which R is defined as above and n = 0. 4. Verfahren nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man bei einer Temperatur im Bereich von 80 bis 120°C sulfiert.4. The method according to at least one of claims 1 to 3, characterized in that sulfonating at a temperature in the range of 80 to 120 ° C. 5. Verfahren nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man bei einem molaren Ver¬ hältnis von Schwefeltrioxid zu Hydroxyethyl-2-alkyl- imidazolinderivaten der allgemeinen Formel II von 0,7 : 1 bis 0,95 : 1 sulfiert.5. The method according to at least one of claims 1 to 4, characterized in that sulfating at a molar ratio of sulfur trioxide to hydroxyethyl-2-alkyl-imidazoline derivatives of the general formula II from 0.7: 1 to 0.95: 1 . 6. Verfahren nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man in einem Fallfilmreaktor sulfiert.6. The method according to at least one of claims 1 to 5, characterized in that sulfated in a falling film reactor. 7. Verfahren nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man mit einem Stickstoff- Schwefeltrioxid-Gemisch mit einem Schwefeltrioxidgehalt im Bereich von 1 bis 10 Vol.-% sulfiert.7. The method according to at least one of claims 1 to 6, characterized in that with a nitrogen Sulfur trioxide mixture with a sulfur trioxide content in the range of 1 to 10 vol .-% sulfated. Verfahren nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die technischen Gemische der Hydroxyethyl-2-alkylimidazolinderivate der allgemeinen Formel II, in der R und n wie oben definiert sind, in Abwesenheit von Lösemitteln sulfiert. Process according to at least one of Claims 1 to 7, characterized in that the technical mixtures of the hydroxyethyl-2-alkylimidazoline derivatives of the general formula II, in which R and n are as defined above, are sulfonated in the absence of solvents.
PCT/EP1990/001591 1989-09-28 1990-09-19 Method for preparing technical mixtures of sulphated 2-alkylimidazoline derivatives Ceased WO1991004966A1 (en)

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US2967868A (en) * 1959-05-15 1961-01-10 Petrolite Corp Certain sulfur trioxide treated imidazoline derivatives
US2985662A (en) * 1958-07-16 1961-05-23 Nalco Chemical Co Process of preparing 2-alkyl-1-hydroxyalkyl sulfates
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US2967868A (en) * 1959-05-15 1961-01-10 Petrolite Corp Certain sulfur trioxide treated imidazoline derivatives
GB985321A (en) * 1961-01-25 1965-03-10 Armour & Co Fabric softening process

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