DE102006054233A1 - Silylating poly-, oligo-, disaccharides derivatives comprises dissolving the poly-, oligo- disaccharides in an ionic liquid and reacting the obtained mixture with a silylating agent - Google Patents

Abstract

Silylating poly-, oligo-, disaccharides or their derivatives comprises dissolving the poly-, oligo- disaccharides in an ionic liquid and reacting the obtained mixture with a silylating agent. An independent claim is included for a method for the acylation of silylated poly-, oligo- or disaccharides comprising dissolving the poly-, oligo- disaccharides in an ionic liquid, reacting the obtained mixture with a silylating agent and subsequently acylating the obtained mixture.

Description

The The present invention describes a process for the silylation of Cellulose by adding cellulose with a silylating agent in one ionic liquid implements.

cellulose is the most important renewable resource and represents an important Starting material for example the textile, paper and nonwovens industries. It also serves as raw material for Derivatives and modifications of cellulose, which include cellulose ethers, such as. Methylcellulose and carboxymethylcellulose, cellulose esters based on organic acids, such as. Cellulose acetate, cellulose butyrate, and cellulose esters based on inorganic acids, such as. Cellulose nitrate, silylated celluloses, e.g. trimethylcellulose, and others count. These derivatives and modifications find many uses, for example in the textile, food, construction and paint industry. Of special Interest is inter alia. silylated celluloses.

Usually in silylation of cellulose, silylating agents such as Trialkylchlorosilanes, for example trimethylchlorosilane, hexamethyldisilazane or N, O-bis (trimethylsilyl) acetamide used in the case of trialkylchlorosilanes according to stoichiometric Amounts of auxiliary base, e.g. Pyridine must be added. by virtue of their bad solubility But the cellulose must be activated in an upstream step become. For this purpose, the cellulose is mixed with ammonia, an alkylamine or mixtures thereof pretreated. To these heterogeneous Systems are then given the silylating agent and the silylation carried out. Of particular disadvantage here is that the reaction mixture initially heterogeneous is going through a homogeneous phase and usually becomes heterogeneous again at high DS values (W. Mormann, Cellulose 10, 271 (2003) and Lieratur cited therein). This phenomenon makes a technical implementation practically impossible.

Furthermore, silylations of cellulose in dimethylacetamide / LiCl mixtures are described. These are silylations in a homogeneous phase - however, an upstream activation is necessary in order to obtain a homogeneous phase. This makes the process very expensive ( W. Schempp et al., The Paper, 38, 607 (1984) ).

It Therefore, the task was a simple method for silylation of polysaccharides, in particular cellulose, wherein the Polysaccharide, preferably the cellulose, without prior activation can be converted into the corresponding silylated product and the latter can be easily isolated from the reaction mixture.

It has now become a method for the preparation of silylated polysaccharides, especially cellulose, found by adding the appropriate polysaccharide in an ionic liquid triggers, thus a homogeneous solution of the polysaccharide and with a silylating agent treated.

• (A) Salze der allgemeinen Formel (I) [A] + / n[Y]^n– (I),in der n für 1, 2, 3 oder 4 steht, [A]⁺ für ein quartäres Ammonium-Kation, ein Oxonium-Kation, ein Sulfonium-Kation oder ein Phosphonium-Kation und [Y]^n– für ein ein-, zwei-, drei- oder vierwertiges Anion steht;
• (B) gemischte Salze der allgemeinen Formeln (II) [A¹]⁺[A²]⁺[Y]^n– (IIa),wobei n = 2; [A¹]⁺[A²]⁺[A³]⁺[Y]^n– (IIb),wobei n = 3; oder [A¹]⁺[A²]⁺[A³]⁺[A⁴]⁺[Y]^n– (IIc),wobei n = 4 und wobei [A¹]⁺, [A²]⁺, [A³]⁺ und [A⁴]⁺ unabhängig voneinander aus den für [A]⁺ genannten Gruppen ausgewählt sind und [Y]^n– die unter (A) genannte Bedeutung besitzt.

Ionic liquids in the sense of the present invention are preferred

• (A) Salts of the general formula (I) [A] + / n [Y] ^n- (I), in which n is 1, 2, 3 or 4, [A] ^{+ is} a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and [Y] ^{n- is} a one, two or more -, tri- or tetravalent anion stands;
• (B) mixed salts of the general formulas (II) [A ¹ ] ⁺ [A ² ] ⁺ [Y] ^n- (IIa), where n = 2; [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ^n- (IIb), where n = 3; or [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ^{n -} (IIc) wherein n = 4 and wherein [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ and [Y] ^{n- has} the meaning given under (A).

Preferably own the ionic liquids a melting point of less than 180 ° C. Particularly preferred is the melting point in a range of -50 ° C to 150 ° C, particularly preferably in the range from -20 ° C to 120 ° C and extraordinary preferably below 100 ° C.

at the inventive ionic liquids these are organic compounds, i. that at least a cation or an anion of the ionic liquid is an organic one Contains rest.

Compounds which are suitable for forming the cation [A] ⁺ of ionic liquids are, for example, from DE 102 02 838 A1 known. Thus, such compounds may contain oxygen, phosphorus, sulfur or in particular nitrogen atoms, for example at least one nitrogen atom, preferably 1 to 10 nitrogen atoms, more preferably 1 to 5, most preferably 1 to 3 and especially 1 to 2 nitrogen atoms. Optionally, other heteroatoms such as oxygen, sulfur or phosphorus atoms may be included. The nitrogen atom is a suitable carrier of the positive charge in the cation of the ionic liquid from which, in equilibrium, a proton or an alkyl radical can then be transferred to the anion to produce an electrically neutral molecule.

In the case, that the nitrogen atom of the carrier is the positive charge in the cation of the ionic liquid can, at the Synthesis of ionic liquids first quaternization on the nitrogen atom of, for example, an amine or nitrogen heterocycle produces a cation become. The quaternization can be achieved by alkylation of the nitrogen atom respectively. Depending on the Alkylierungsreagens used salts with different Get anions. In cases, in which it is not possible is, the desired Anion already formed during quaternization, this can be done in one further synthesis step. Starting, for example, from an ammonium halide, the halide can be reacted with a Lewis acid become, whereby from halide and Lewis acid a complex anion formed becomes. Alternatively, the replacement of a halide ion against the wished Anion possible. This can be done by adding a metal salt with precipitation of the formed metal halide, about an ion exchanger or by displacement of the halide ion by a strong acid (With liberation of the hydrohalic acid) happen. Suitable methods are for example in Angew. Chem. 2000, 112, pp. 3926-3945, and therein cited literature.

Suitable alkyl radicals by which the nitrogen atom may be quaternized in the amines or nitrogen heterocycles, for example, are C ₁ -C ₁₈ -alkyl, preferably C ₁ -C ₁₀ -alkyl, particularly preferably C ₁ -C ₆ alkyl and most preferably Methyl. The alkyl group may be unsubstituted or have one or more identical or different substituents.

Prefers are those compounds which contain at least one 5- to 6-membered heterocycle, in particular a five-membered one Heterocycle, containing at least one nitrogen atom as well optionally an oxygen or sulfur atom. Also those compounds which are at least one of them are particularly preferred five to contain six-membered heterocycle, the one, two or three Has nitrogen atoms and a sulfur or an oxygen atom, most preferably those having two nitrogen atoms. Farther preferred are aromatic heterocycles.

Especially preferred compounds are those having a molecular weight below 1000 g / mol, most preferably below 500 g / mol and in particular below 350 g / mol.

sowie Oligomere, die diese Strukturen enthalten.Furthermore, preference is given to those cations which are selected from the compounds of the formulas (IIIa) to (IIIw)

and oligomers containing these structures.

sowie Oligomere, die diese Strukturen enthalten.Further suitable cations are compounds of the general formula (IIIx) and (IIIy)

and oligomers containing these structures.

• • der Rest R für Wasserstoff, einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen; und
• • die Reste R¹ bis R⁹ unabhängig voneinander für Wasserstoff, eine Sulfo-Gruppe oder einen Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder ar aliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 20 Kohlenstoffatomen, wobei die Reste R¹ bis R⁹, welche in den oben genannten Formeln (III) an ein Kohlenstoffatom (und nicht an ein Heteroatom) gebunden sind, zusätzlich auch für Halogen oder eine funktionelle Gruppe stehen können; oder zwei benachbarte Reste aus der Reihe R¹ bis R⁹ zusammen auch für einen zweibindigen, Kohlenstoff enthaltenden organischen, gesättigten oder ungesättigten, acyclischen oder cyclischen, aliphatischen, aromatischen oder araliphatischen, unsubstituierten oder durch 1 bis 5 Heteroatome oder funktionelle Gruppen unterbrochenen oder substituierten Rest mit 1 bis 30 Kohlenstoffatomen.

In the abovementioned formulas (IIIa) to (IIIy)

• • the radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms; and
• • the radicals R ¹ to R ^{9 are} independently hydrogen, a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups substituted radicals having 1 to 20 carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (III) are bonded to a carbon atom (and not to a heteroatom), additionally may also stand for halogen or a functional group; or two adjacent radicals from the series R ¹ to R ⁹ together also represent a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups with 1 to 30 carbon atoms.

Suitable hetero atoms in the definition of the radicals R and R ¹ to R ^{9 are in} principle all heteroatoms in question which are capable of formally a -CH ₂ -, a -CH =, a -C≡ or a = C = group to replace. When the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable. Particularly preferred groups which may be mentioned are -O-, -S-, -SO-, -SO ₂ -, -NR'-, -N =, -PR'-, -PR ' ₃ and -SiR' ₂ -, where the radicals R 'are the remainder of the carbon-containing radical. The radicals R ¹ to R ⁹ are, in the cases in which they are in the above formulas (III) to a carbon atom (and not to a heteroatom) attached, also be bound directly via the heteroatom.

Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom and which do not react with silylating reagents. As suitable examples may be mentioned = O (in particular as carbonyl group), -NR ₂ ', = NR', -CONH ₂ (carboxamide), and -CN (cyano). Fractional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide) or -CONR'- (tertiary amide), are included, for example, di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₄ alkyloxycarbonyl or C ₁ -C ₄ alkyloxy. The R 'radicals are the remainder of the carbon-containing radical.

When Halogens are called fluorine, chlorine, bromine and iodine.

• • unverzweigtes oder verzweigtes, unsubstituiertes oder ein bis mehrfach mit Halogen, Phenyl, Cyano und/oder C₁-C₆-Alkoxycarbonyl substituiertes C₁-C₁₈-Alkyl mit insgesamt 1 bis 20 Kohlenstoffatomen, wie beispielsweise Methyl, E thyl, 1-Propyl, 2-Propyl, 1-Butyl, 2-Butyl, 2-Methyl-1-propyl, 2-Methyl-2-propyl, 1-Pentyl, 2-Pentyl, 3-Pentyl, 2-Methyl-1-butyl, 3-Methyl-1-butyl, 2-Methyl-2-butyl, 3-Methyl-2-butyl, 2,2-Dimethyl1-propyl, 1-Hexyl, 2-Hexyl, 3-Hexyl, 2-Methyl-1-pentyl, 3-Methyl-1-pentyl, 4-Methyl-1-pentyl, 2-Methyl-2-pentyl, 3-Methyl-2-pentyl, 4-Methyl-2-pentyl, 2-Methyl-3-pentyl, 3-Methyl-3-pentyl, 2,2-Dimethyl-1-butyl, 2,3-Dimethyl-1-butyl, 3,3-Dimethyl-1-butyl, 2-Ethyl-1-butyl, 2,3-Dimethyl-2-butyl, 3,3-Dimethyl-2-butyl, 1-Heptyl, 1-Octyl, 1-Nonyl, 1-Decyl, 1-Undecyl, 1-Dodecyl, 1-Tetradecyl, 1-Hexadecyl, 1-Octadecyl, Benzyl, 3-Phenylpropyl, 2-Cyanoethyl, 2-(Methoxycarbonyl)-ethyl, 2-(Ethoxycarbonyl)-ethyl, 2-(n-Butoxy-carbonyl)-ethyl, Trifluormethyl, Difluormethyl, Fluormethyl, Pentafluorethyl, Heptafluorpropyl, Heptafluorisopropyl, Nonafluorbutyl, Nonafluorisobutyl, Undecylfluorpentyl und Undecylfluorisopentyl;
• • Glykole, Butylenglykole und deren Oligomere mit 1 bis 100 Einheiten, wobei alle voranstehenden Gruppen einen C₁-C₈-Alkyl-Rest als Endgruppe tragen, also beispielsweise R^AO-(CHR^B-CH₂-O)_m-CHR^B-CH₂- oder R^AO-(CH₂CH₂CH₂CH₂O)_m-CH₂CH₂CH₂CH₂- mit R^A und R^B bevorzugt Methyl oder Ethyl und m bevorzugt 0 bis 3, insbesondere 3-Oxabutyl, 3-Oxapentyl, 3,6-Dioxaheptyl, 3,6-Dioxaoctyl, 3,6,9-Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9,12-Tetraoxatridecyl und 3,6,9,12-Tetraoxatetradecyl;
• • Vinyl;
• • 1-Propen-1-yl, 1-Propen-2-yl und 1-Propen-3-yl; und
• • N,N-Di-C₁-C₆-alkyl-amino, wie beispielsweise N,N-Dimethylamino und N,N-Diethylamino.

Preferably, the radical R is for

• C ₁ -C ₁₈ -alkyl which is unbranched or branched, unsubstituted or monosubstituted to polysubstituted by halogen, phenyl, cyano and / or C ₁ -C ₆ -alkoxycarbonyl and has a total of 1 to 20 carbon atoms, such as, for example, methyl, ethyl, 1- Propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1 pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3- Dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1 Octadecyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, trifluoromethyl, difluoromethyl, Fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl and undecylfluoroisopentyl;
• Glycols, butylene glycols and their oligomers having from 1 to 100 units, all of the above groups having a C ₁ -C ₈ -alkyl radical as end group, that is to say, for example, R ^A O- (CHR ^B -CH ₂ -O) _m -CHR ^B -CH ₂ - or R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ O) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^B preferably methyl or ethyl and m preferably 0 to 3, in particular 3 Oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9 , 12-tetraoxatetradecyl;
• • vinyl;
• 1-propen-1-yl, 1-propen-2-yl and 1-propen-3-yl; and
• N, N-di-C ₁ -C ₆ -alkyl-amino, such as N, N-dimethylamino and N, N-diethylamino.

Particularly preferably, the radical R is unbranched and unsubstituted C ₁ -C ₁₈ -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1 Decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 1-propen-3-yl, in particular methyl, ethyl, 1-butyl and 1-octyl and CH ₃ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - with m equal to 0 to 3.

• • Wasserstoff;
• • Halogen;
• • eine geeignete funktionelle Gruppe;
• • gegebenenfalls durch geeignete funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes und/oder durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₁-C₁₈-Alkyl;
• • gegebenenfalls durch geeignete funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes und/oder durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C₂-C₁₈-Alkenyl;
• • gegebenenfalls durch geeignete funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₆-C₁₂-Aryl;
• • gegebenenfalls durch geignete funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₅-C₁₂-Cycloalkyl;
• • gegebenenfalls durch geeignete funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituiertes C₅-C₁₂-Cycloalkenyl; oder
• • einen gegebenenfalls durch geeignete funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituierten fünf- bis sechsgliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus bedeuten; oder

zwei benachbarte Reste zusammen für

• • einen ungesättigten, gesättigten oder aromatischen, gegebenenfalls durch geeignete funktionelle Gruppen, Aryl, Alkyl, Aryloxy, Alkyloxy, Halogen, Heteroatome und/oder Heterocyclen substituierten und gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenen Ring.

The radicals R ¹ to R ⁹ are preferably each independently

• • hydrogen;
• • halogen;
• • a suitable functional group;
• Optionally C ₁ interrupted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups C ₁₈ alkyl;
• Optionally C ₂ interrupted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups C ₁₈ alkenyl;
• Optionally substituted by appropriate functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted C ₆ -C ₁₂ -aryl;
• Optionally C ₅ -C ₁₂ -cycloalkyl substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles;
• Optionally substituted by appropriate functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C ₅ -C ₁₂ cycloalkenyl; or
• • a optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five to six-membered, oxygen, nitrogen and / or sulfur atoms having heterocycle; or

two adjacent radicals together for

• • an unsaturated, saturated or aromatic, optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted ring.

Optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₁ -C ₁₈ alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl , 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl 1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3 pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2, 3-Dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, 1-nonyl, 1- Decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1-octadecyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, Cyc lohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, benzyl (phenylmethyl), diphenylmethyl (benzhydryl), triphenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, α, α-dimethylbenzyl, p-tolylmethyl, 1- (p-butylphenyl ) -ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl ) -ethyl, methoxy, ethoxy, formyl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1, 3-dioxolan-2-yl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2 -Methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, acetyl, C _m F _{2 (m-a) + (1-b)} H _{2a + b} with m equal to 1 to 30, 0 ≤ a ≤ m and b = 0 or 1 (ex CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C _(m-2) F _{2 (m-2) +1} , C ₆ F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C ₁₂ F ₂₅ ) , Chloromethyl, 2-chloroethyl, trichloromethyl, 1,1-dimethyl-2-chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 2-methoxyisopropyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa octyl, 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy 3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-penta-decyl, 9 Ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

In the case of C ₂ optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups C ₁₈ -alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or
C _m F _{2 (m-a) - (1-b)} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

When optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₆ -C ₁₂ aryl is preferably phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4 Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, t-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2 , 6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4 -Dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C ₆ F _(5-a) H _a with 0 ≤ a ≤ 5.

C ₅ -C ₁₂ -cycloalkyl optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl , Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F _{2 (m-a) - (1-b)} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1 and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

May optionally be substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C ₅ -C ₁₂ cycloalkenyl is preferably 3-cyclo pentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl or C _n F _{2 (m-a) -3 (1-b)} H _2a-3b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

at an optionally substituted by suitable functional groups, aryl, Alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl, Pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, Benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, Methoxyfuryl, dimethoxypyridyl or difluoropyridyl.

Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally by one or more oxygen and / or sulfur atoms and / or or more than one substituted or unsubstituted imino groups interrupted ring, it is preferably 1,3-propylene, 1,4-butylene, 1,5-pentylene, 2-oxa-1,3-propylene, 1-oxa-1.3 -propylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propenylene, 3-oxa-1,5-pentylene, 1-aza-1,3-propenylene, 1-C ₁ -C ₄ -Alkyl-1-aza-1,3-propenylene, 1,4-buta-1,3-dienylene, 1-aza-1,4-buta-1,3-dienylene or 2-aza-1,4-buta -1,3-dienylene.

Contain the abovementioned radicals oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number is the oxygen and / or Sulfur atoms and / or imino groups not limited. As a rule, it is not more than 5 in the remainder, preferably not more than 4 and more especially preferably not more than 3.

Contain the above-mentioned radicals heteroatoms, so are between two heteroatoms usually at least one carbon atom, preferably at least two carbon atoms.

• • Wasserstoff;
• • unverzweigtes oder verzweigtes, unsubstituiertes oder ein bis mehrfach mit Halogen, Phenyl, Cyano und/oder C₁-C₆-Alkoxycarbonyl substituiertes C₁-C₁₈-Alkyl mit insgesamt 1 bis 20 Kohlenstoffatomen, wie beispielsweise Methyl, Ethyl, 1-Propyl, 2-Propyl, 1-Butyl, 2-Butyl, 2-Methyl-1-propyl, 2-Methyl-2-propyl, 1-Pentyl, 2-Pentyl, 3-Pentyl, 2-Methyl-1-butyl, 3-Methyl-1-butyl, 2-Methyl-2-butyl, 3-Methyl-2-butyl, 2,2-Dimethyl-1-propyl, 1-Hexyl, 2-Hexyl, 3-Hexyl, 2-Methyl-1-pentyl, 3-Methyl-1-pentyl, 4-Methyl-1-pentyl, 2-Methyl-2-pentyl, 3-Methyl-2-pentyl, 4-Methyl-2-pentyl, 2-Methyl-3-pentyl, 3-Methyl-3-pentyl, 2,2-Dimethyl-1-butyl, 2,3-Dimethyl-1-butyl, 3,3-Dimethyl-1-butyl, 2-Ethyl-1-butyl, 2,3-Dimethyl-2-butyl, 3,3-Dimethyl-2-butyl, 1-Heptyl, 1-Octyl, 1-Nonyl, 1-Decyl, 1-Undecyl, 1-Dodecyl, 1-Tetradecyl, 1-Hexadecyl, 1-Octadecyl, Benzyl, 3-Phenylpropyl, 2-Cyanoethyl, 2-(Methoxycarbonyl)-ethyl, 2-(Ethoxycarbonyl)-ethyl, 2-(n-Butoxy-carbonyl)-ethyl, Trifluormethyl, Difluormethyl, Fluormethyl, Pentafluorethyl, Heptafluorpropyl, Heptafluorisopropyl, Nonafluorbutyl, Nonafluorisobutyl, Undecylfluorpentyl und Undecylfluorisopentyl;
• • Glykole, Butylenglykole und deren Oligomere mit 1 bis 100 Einheiten, wobei alle voranstehenden Gruppen einen C₁-C₈-Alkyl-Rest als Endgruppe tragen, also beispielsweise R^AO-(CHR^B-CH₂-O)_m-CHR^B-CH₂- oder R^AO-(CH₂CH₂CH₂CH₂O)_m-CH₂CH₂CH₂CH₂- mit R^A und R^B bevorzugt, Methyl oder Ethyl und n bevorzugt 0 bis 3, insbesondere 3-Oxabutyl, 3-Oxapentyl, 3,6-Dioxaheptyl, 3,6-Dioxaoctyl, 3,6,9-Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9,12-Tetraoxatridecyl und 3,6,9,12-Tetraoxatetradecyl;
• • Vinyl;
• • 1-Propen-1-yl, 1-Propen-2-yl und 1-Propen-3-yl; und
• • N,N-Di-(C₁-C₆-alkyl)-amino, wie beispielsweise N,N-Dimethylamino und N,N-Diethylamino;

wobei wenn IIIw für III steht, dann steht R³ nicht für Wasserstoff.Particularly preferably, the radicals R ¹ to R ⁹ are each independently

• • hydrogen;
• • straight-chain or branched, unsubstituted or mono- to polysubstituted by halogen, phenyl, cyano and / or C ₁ -C ₆ -alkoxycarbonyl-substituted C ₁ -C ₁₈ -alkyl having a total of 1 to 20 carbon atoms, such as, for example, methyl, ethyl, 1-propyl , 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3 Methyl 1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1 -pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl , 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3 Dimethyl 2-butyl, 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1 Octadecyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, trifluoromethyl, difluoromethyl, Fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl and undecylfluoroisopentyl;
• Glycols, butylene glycols and their oligomers having from 1 to 100 units, all of the above groups having a C ₁ -C ₈ -alkyl radical as end group, that is to say, for example, R ^A O- (CHR ^B -CH ₂ -O) _m -CHR ^B -CH ₂ - or R ^A O- (CH ₂ CH ₂ CH ₂ CH ₂ O) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^B preferably, methyl or ethyl and n preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6, 9,12-tetraoxatetradecyl;
• • vinyl;
• 1-propen-1-yl, 1-propen-2-yl and 1-propen-3-yl; and
• N, N-di (C ₁ -C ₆ alkyl) amino, such as N, N-dimethylamino and N, N-diethylamino;

wherein when IIIw is III, then R ³ is not hydrogen.

Most preferably, the radicals R ¹ to R ⁹ independently of one another are hydrogen or C ₁ -C ₁₈ -alkyl, such as, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, for phenyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N-diethylamino, for chlorine and for CH ₃ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - and CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _m -CH ₂ CH ₂ - with m equal to 0 to 3.

• • einer der Reste R¹ bis R⁵ Methyl, Ethyl oder Chlor ist und die verbleibenden Reste R¹ bis R⁵ Wasserstoff sind;
• • R³ Dimethylamino ist und die verbleibenden Reste R¹, R², R⁴ und R⁵ Wasserstoff sind;
• • alle Reste R¹ bis R⁵ Wasserstoff sind;
• • R² Carboxamid ist und die verbleibenden Reste R¹, R², R⁴ und R⁵ Wasserstoff sind; oder
• • R¹ und R² oder R² und R³ 1,4-Buta-1,3-dienylen ist und die verbleibenden Reste R¹, R², R⁴ und R⁵ Wasserstoff sind;

und insbesondere solche, bei denen

• • R¹ bis R⁵ Wasserstoff sind; oder
• • einer der Reste R¹ bis R⁵ Methyl oder Ethyl ist und die verbleibenden Reste R¹ bis R⁵ Wasserstoff sind.

Very particular preference is given as Pyridiniumionen (IIIIa) such, in which

• • one of the radicals R ¹ to R ^{5 is} methyl, ethyl or chlorine and the remaining radicals R ¹ to R ^{5 are} hydrogen;
• • R ^{3 is} dimethylamino and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen;
• • all radicals R ¹ to R ^{5 are} hydrogen;
• • R ^{2 is} carboxamide and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen; or
• • R ¹ and R ² or R ² and R ^{3 is} 1,4-buta-1,3-dienylene and the remaining radicals R ¹ , R ² , R ⁴ and R ^{5 are} hydrogen;

and in particular those in which

• • R ¹ to R ^{5 are} hydrogen; or
• • one of the radicals R ¹ to R ^{5 is} methyl or ethyl and the remaining radicals R ¹ to R ^{5 are} hydrogen.

When very particularly preferred pyridinium ions (IIIa) are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) -pyridinium, 1- (1-octyl) -pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1,2-dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2-methylpyridinium, 1- (1-tetra-decyl) -2-methyl-pyridinium, 1- (1-hexadecyl) -2-methyl-pyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium, 1- (1-tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium, 1,5-diethyl-2-methylpyridinium, 1- (1-Butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium and 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-Tetradecyl) -2-methyl-3-ethylpyridinium and 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium.

• • R¹ bis R⁴ Wasserstoff sind; oder
• • einer der Reste R¹ bis R⁴ Methyl oder Ethyl ist und die verbleibenden Reste R¹ bis R⁴ Wasserstoff sind.

Very particularly preferred pyridazinium ions (IIIb) are those in which

• • R ¹ to R ^{4 are} hydrogen; or
• • one of the radicals R ¹ to R ^{4 is} methyl or ethyl and the remaining radicals R ¹ to R ^{4 are} hydrogen.

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind; oder
• • R¹ Wasserstoff, Methyl oder Ethyl ist, R² und R⁴ Methyl sind und R³ Wasserstoff ist.

Very particularly preferred pyrimidinium ions (IIIc) are those in which

• • R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl; or
• • R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen.

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind;
• • R¹ Wasserstoff, Methyl oder Ethyl ist, R² und R⁴ Methyl sind und R³ Wasserstoff ist;
• • R¹ bis R⁴ Methyl sind; oder
• • R¹ bis R⁴ Methyl Wasserstoff sind.

Very particularly preferred pyrazinium ions (IIId) are those in which

• • R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl;
• • R ^{1 is} hydrogen, methyl or ethyl, R ² and R ^{4 are} methyl and R ^{3 is} hydrogen;
• • R ¹ to R ^{4 are} methyl; or
• • R ¹ to R ^{4 are} methyl hydrogen.

• • R² bis R⁴ unabhängig voneinander Wasserstoff sind; vorzugsweise R² bis R⁴ unabhängig voneinander Wasserstoff, und R und R¹ unabhängig voneinander C₁-C₄-Alkyl oder Allyl sind.

Very particularly preferred imidazolium ions (IIIe) are those in which

• • R ² to R ^{4 are} independently hydrogen; preferably R ² to R ^{4 are} independently hydrogen, and R and R ^{1 are} independently C ₁ -C ₄ alkyl or allyl.

• • R³ und R⁴ unabhängig voneinander Wasserstoff sind; vorzugsweise R³ und R⁴ unabhängig voneinander Wasserstoff, und R, R¹ und R² unabhängig voneinander C₁-C₄-Alkyl oder Allyl; insbesondere vorzugsweise R³ und R⁴ unabhängig voneinander Wasserstoff, R und R¹ unabhängig voneinander C₁-C₄-Alkyl, und R² C₁-C₄-Alkyl oder Allyl sind.

Likewise very particularly preferably employed as imidazolium ions (IIIe) are those in which

• • R ³ and R ^{4 are} independently hydrogen; preferably R ³ and R ^{4 are} independently hydrogen, and R, R ¹ and R ^{2 are} independently C ₁ -C ₄ alkyl or allyl; in particular preferably R ³ and R ⁴ independently of one another are hydrogen, R and R ^1, independently of one another, are C ₁ -C ₄ -alkyl, and R ^{2 is} C ₁ -C ₄ -alkyl or allyl.

• • R¹ Wasserstoff, Methyl, Ethyl, 1-Propyl, 1-Butyl, 1-Pentyl, 1-Hexyl, 1-Octyl, 1-Propen-3-yl oder 2-Cyanoethyl, und R² bis R⁴ unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind.

Likewise particularly preferred as imidazolium ions (IIIe) are those in which

• R ^{1 is} hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 1-propen-3-yl or 2-cyanoethyl, and R ² to R ^{4 are} independently hydrogen , Methyl or ethyl.

As very particularly preferred imidazolium ions (IIIe) may be mentioned 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1 (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl ) -3-ethylimidazolium, 1- (1-hexyl) -3-methyl-imidazolium, 1- (1-hexyl) -3-ethyl-imidazolium, 1- (1-hexyl) -3-butyl-imidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1 Dodecyl) -3-ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl ) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) - 3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dime thylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethyl-imidazolium, 1- (1-octyl) -2, 3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1, 4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3- octylimidazolium and 1- (prop-1-en-3-yl) -3-methylimidazolium.

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred pyrazolium ions (IIIf), (IIIg) or (IIIg ') are those in which

• • R ^{1 is} hydrogen, methyl or ethyl and R ² to R ^{4 are} independently hydrogen or methyl.

• • R¹ bis R⁴ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred pyrazolium ions (IIIh) are those in which

• • R ¹ to R ^{4 are} independently hydrogen or methyl.

• • unabhängig voneinander R¹ bis R⁶ Wasserstoff oder Methyl sind.

Very particular preference is given as 1-pyrazolinium (IIIi) such as those in which

• • independently of one another R ¹ to R ^{6 are} hydrogen or methyl.

• • R¹ Wasserstoff, Methyl, Ethyl oder Phenyl ist und R² bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using 2-pyrazolinium ions (IIIj) or (IIIj ') as those in which

• • R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{6 are} independently hydrogen or methyl.

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl, Ethyl oder Phenyl sind und R³ bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using as 3-pyrazolinium ions (IIIk) or (IIIk ') those in which

• • R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ³ to R ^{6 are} independently hydrogen or methyl.

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl, Ethyl, 1-Butyl oder Phenyl sind, R³ und R⁴ unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind und R⁵ und R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred imidazolinium ions (1111) are those in which

• • R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl, 1-butyl or phenyl, R ³ and R ^{4 are} independently hydrogen, methyl or ethyl, and R ⁵ and R ^{6 are} independently hydrogen or methyl.

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind und R³ bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using as imidazolinium ions (IIIm) or (IIIm ') those in which

• • R ¹ and R ^{2 are} independently hydrogen, methyl or ethyl and R ³ to R ^{6 are} independently hydrogen or methyl.

• • R¹ bis R³ unabhängig voneinander Wasserstoff, Methyl oder Ethyl sind und R⁴ bis R⁶ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using as imidazolinium ions (IIIn) or (IIIn ') those in which

• • R ¹ to R ^{3 are} independently hydrogen, methyl or ethyl and R ⁴ to R ^{6 are} independently hydrogen or methyl.

• • R¹ Wasserstoff, Methyl, Ethyl oder Phenyl ist und R² und R³ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particular preference is given to using thiazolium ions (IIIo) or (IIIo ') and oxazolium ions (IIIp) as those in which

• • R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² and R ^{3 are} independently hydrogen or methyl.

• • R¹ und R² unabhängig voneinander Wasserstoff, Methyl, Ethyl oder Phenyl sind und R³ Wasserstoff, Methyl oder Phenyl ist.

Very particular preference is given to using as 1,2,4-triazolium (IIIq), (IIIq ') or (IIIq''), those in which

• • R ¹ and R ^{2 are} independently hydrogen, methyl, ethyl or phenyl and R ^{3 is} hydrogen, methyl or phenyl.

• • R¹ Wasserstoff, Methyl oder Ethyl ist und R² und R³ unabhängig voneinander Wasserstoff oder Methyl sind, oder R² und R³ zusammen 1,4-Buta-1,3-dienylen ist.

Very particular preference is given as 1,2,3-triazolium ions (IIIr), (IIIr ') or (IIIr'') such, in which

• • R ^{1 is} hydrogen, methyl or ethyl, and R ² and R ^{3 are} independently hydrogen or methyl, or R ² and R ³ together are 1,4-buta-1,3-dienylene.

• • R¹ Wasserstoff, Methyl, Ethyl oder Phenyl ist und R² bis R⁹ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred pyrrolidinium ions (IIIs) are those in which

• • R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² to R ^{9 are} independently hydrogen or methyl.

• • R¹ und R⁴ unabhängig voneinander Wasserstoff, Methyl, Ethyl oder Phenyl sind und R² und R³ sowie R⁵ bis R⁸ unabhängig voneinander Wasserstoff oder Methyl sind.

Very particularly preferred imidazolidinium ions (IIIt) are those in which

• • R ¹ and R ^{4 are} independently hydrogen, methyl, ethyl or phenyl and R ² and R ³ and R ⁵ to R ^{8 are} independently hydrogen or methyl.

• • R¹ bis R³ unabhängig voneinander C₁-C₁₈-Alkyl sind; oder
• • R¹ und R² zusammen 1,5-Pentylen oder 3-Oxa-1,5-pentylen sind und R³ C₁-C₁₈-Alkyl oder 2-Cyanoethyl ist.

Very particular preference is given to using as ammonium ions (IIIu) those in which

• • R ¹ to R ^{3 are} independently C ₁ -C ₁₈ alkyl; or
• • R ¹ and R ² together are 1,5-pentylene or 3-oxa-1,5-pentylene and R ^{3 is} C ₁ -C ₁₈ alkyl or 2-cyanoethyl.

When Very particularly preferred ammonium ions (IIIu) are methyltri (1-butyl) ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.

Examples for the tertiary Amines, of which the quaternary Ammonium ions of the general formula (IIIu) by quaternization with the radicals R mentioned are diethyl-n-butylamine, diethyl-tert-butylamine, Diethyl-n-pentylamine, diethylhexylamine, diethyloctylamine, diethyl (2-ethylhexyl) -amine, di-n-propylbutylamine, Di-n-propyl-n-pentylamine, Di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2-ethylhexyl) amine, Di-isopropylethylamine, di-iso-propyl-n-propylamine, di-isopropylbutylamine, Di-isopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, Di-iso-propyl (2-ethylhexyl) -amine, Di-n-butylethylamine, di-n-butyl-n-propylamine, di-n-butyl-n-pentylamine, Di-n-butylhexylamine, di-n-butyl-octylamine, di-n-butyl (2-ethylhexyl) -amine, N-n-butylpyrrolidine, N-sec-butylpyrrodidine, N-tert-butylpyrrolidine, N-n-pentylpyrrolidine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-di-n-butylcyclohexylamine, N-n-propylpiperidine, N-isopropylpiperidine, N-n-butylpiperidine, N-sec-butylpiperidine, N-tert-butylpiperidine, N-n-pentylpiperidine, N-n-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, N-n-pentylmorpholine, N-benzyl-N-ethylaniline, N-benzyl-N-n-propylaniline, N-benzyl-N-iso-propylaniline, N-benzyl-N-n-butylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di-n-butyl-p-toluidine, diethylbenzylamine, di-n-propylbenzylamine, Di-n-butylbenzylamine, diethylphenylamine, di-n-propylphenylamine and Di-n-butylphenylamine.

preferred quaternary Ammonium ions of the general formula (IIIu) are those which are of following tertiary Derive amines by quaternization with the said radicals R, such as di-iso-propylethylamine, diethyl-tert-butylamine, di-iso-propylbutylamine, Di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines from pentyl isomers.

Especially preferred tertiary Amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers. Another preferred tertiary Amine having three identical residues is triallylamine.

• • R¹ bis R⁵ Methyl sind.

Very particular preference is given to guanidinium ions (IIIv) as those in which

• • R ¹ to R ^{5 are} methyl.

When very particularly preferred guanidinium ion (IIIV) is N, N, N ', N', N ", N" -hexamethylguanidinium.

• • R¹ und R² unabhängig voneinander Methyl, Ethyl, 1-Butyl oder 1-Octyl sind und R³ Methyl, Ethyl oder Acetylist;
• • R¹ Methyl, Ethyl, 1-Butyl oder 1-Octyl ist, R² eine -CH₂-CH₂-OR⁴-Gruppe ist und R³ und R⁴ unabhängig voneinander, Methyl, Ethyl oder Acetyl sind; oder
• • R¹ eine -CH₂-CH₂-OR⁴-Gruppe ist, R² eine -CH₂-CH₂-OR⁵-Gruppe ist und R³ bis R⁵ unabhängig voneinander Methyl, Ethyl oder Acetyl sind.

Very particular preference is given to using as cholinium ions (IIIw) those in which

• • R ¹ and R ^{2 are} independently methyl, ethyl, 1-butyl or 1-octyl and R ^{3 is} methyl, ethyl or acetyl;
• • R ^{1 is} methyl, ethyl, 1-butyl or 1-octyl, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁴ group and R ³ and R ^{4 are} independently methyl, ethyl or acetyl; or
• • R ^{1 is} a -CH ₂ -CH ₂ -OR ⁴ group, R ^{2 is} a -CH ₂ -CH ₂ -OR ⁵ group and R ³ to R ^{5 are} independently methyl, ethyl or acetyl.

Particularly preferred cholinium ions (IIIw) are those in which R ^{3 is} selected from methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy-3, 6,9-trioxa undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5- oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxo-octyl, 11-ethoxy-3,6,9-trioxa undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14- ethoxy-5,10-oxa-tetradecyl.

• • R¹ bis R³ unabhängig voneinander C₁-C₁₈-Alkyl, insbesondere Butyl, Isobutyl, 1-Hexyl oder 1-Octyl sind.

Very particularly preferred as phosphonium ions (IIIx) are those in which

• • R ¹ to R ^{3 are} independently C ₁ -C ₁₈ alkyl, especially butyl, isobutyl, 1-hexyl or 1-octyl.

Among the heterocyclic cations mentioned above are the pyridinium ions, pyrazolinium, Pyrazoliumionen and imidazolinium and imidazolium ions are preferred. Furthermore, ammonium ions are preferred.

Especially preferred are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-dodecyl) -pyridinium, 1- (1-tetradecyl) -pyridinium, 1- (1-hexadecyl) -pyridinium, 1,2-dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2-methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium, 1- (1-tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium, 1,5-diethyl-2-methylpyridinium, 1- (1-Butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium, 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium, 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethyl-imidazolium, 1- (1-hexyl) -2,3-dimethyl-imidazolium and 1- (1-octyl) -2,3-dimethyl-imidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium and 1- (prop-1-en-3-yl) -3-methylimidazolium.

When Anions are in principle all anions usable.

• • der Gruppe der Halogenide und halogenhaltigen Verbindungen der Formel: F^–, Cl^–, Br^–, I^–, BF₄ ^–, PF₆ ^–, CF₃SO₃ ^–, (CF₃SO₃)₂N^–, CF₃CO₂ ^–, CCl₃CO₂ ^–, CN^–, SCN^–, OCN^–
• • der Gruppe der Sulfate, Sulfite und Sulfonate der allgemeinen Formel: SO₄ ^2–, HSO₄ ^–, SO₃ ^2–, HSO₃ ^–, R^aOSO₃ ^–, R^aSO₃ ^–
• • der Gruppe der Phosphate der allgemeinen Formel PO₄ ^3–, HPO₄ ^2–, H₂PO₄ ^–, R^aPO₄ ^2–, HR^aPO₄ ^–, R^aR^bPO₄ ^–
• • der Gruppe der Phosphonate und Phosphinate der allgemeinen Formel: R^aHPO₃ ^–, R^aR^bPO₂ ^–, R^aR^bPO₃ ^–
• • der Gruppe der Phosphite der allgemeinen Formel: PO₃ ^3–, HPO₃ ^2–, H₂PO₃ ^–, R^aPO₃ ^2–, R^aHPO₃ ^–, R^aR^bPO₃ ^–
• • der Gruppe der Phosphonite und Phosphinite der allgemeinen Formel: R^aR^bPO₂ ^–, R^aHPO₂ ^–, R^aR^bPO^–, R^aHPO^–
• • der Gruppe der Carbonsäuren der allgemeinen Formel: R^aCOO^–
• • der Gruppe der Borste der allgemeinen Formel: BO₃ ^3–, HBO₃ ^2–, H₂BO₃ ^–, R^aR^bBO₃ ^–, R^aHBO₃ ^–, R^aBO₃ ^2–, B(OR^a)(OR^b)(OR^c)(OR^d)^–, B(HSO₄)^–, B(R^aSO₄)^–
• • der Gruppe der Boronate der allgemeinen Formel: R^aBO₂ ^2–, R^aR^bBO^–
• • der Gruppe der Silikate und Kieselsäuresäureester der allgemeinen Formel: SiO₄ ^4–, HSiO₄ ^3–, H₂SiO₄ ^2–, H₃SiO₄ ^–, R^aSiO₄ ^3–, R^aR^bSiO₄ ^2–, R^aR^bR^cSiO₄ ^–, HR^aSiO₄ ^2–, H₂R^aSiO₄ ^–, HR^aR^bSiO₄ ^–
• • der Gruppe der Alkyl- bzw. Arylsilan-Salze der allgemeinen Formel: R^aSiO₃ ^3–, R^aR^bSiO₂ ^2–, R^aR^bR^cSiO^–, R^aR^bR^cSiO₃ ^–, R^aR^bR^cSiO₂ ^–, R^aR^bSiO₃ ^2–
• • der Gruppe der Carbonsäureimide, Bis(sulfonyl)imide und Sulfonylimide der allgemeinen Formel:
  
• • der Gruppe der Methide der allgemeinen Formel:
  

The anion [Y] ^{n of} the ionic liquid is for example selected from

• The group of halides and halogen ^- containing compounds of the formula: F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₃ ) ₂ N ^- , CF ₃ CO ₂ ^-, CCl ₃ CO ₂ ^-, CN ^-, SCN ^-, OCN ^-
• • the group of sulfates, sulfites and sulfonates of the general formula: SO ₄ ^2- , HSO ₄ ^- , SO ₃ ^2- , HSO ₃ ^- , R ^a OSO ₃ ^- , R ^a SO ₃ ^-
• • the group of phosphates of the general formula PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , R ^a PO ₄ ^2- , HR ^a PO ₄ ^- , R ^a R ^b PO ₄ ^-
• The group of phosphonates and phosphinates of the general formula: R ^a HPO ₃ ^- , R ^a R ^b PO ₂ ^- , R ^a R ^b PO ₃ ^-
• The group of phosphites of the general formula: PO ₃ ^3- , HPO ₃ ^2- , H ₂ PO ₃ ^- , R ^a PO ₃ ^2- , R ^a HPO ₃ ^- , R ^a R ^b PO ₃ ^-
• The group of phosphonites and phosphinites of the general formula: R ^a R ^b PO ₂ ^- , R ^a HPO ₂ ^- , R ^a R ^b PO ^- , R ^a HPO ^-
• • the group of carboxylic acids of the general formula: R ^a COO ^-
• • the group of bristles of the general formula: BO ₃ ^3- , HBO ₃ ^2- , H ₂ BO ₃ ^- , R ^a R ^b BO ₃ ^- , R ^a HBO ₃ ^- , R ^a BO ₃ ^2- , B (OR ^a ) (OR ^b ) (OR ^c ) (OR ^d ) ^- , B (HSO ₄ ) ^- , B (R ^a SO ₄ ) ^-
• The group of boronates of the general formula: R ^a BO ₂ ^2- , R ^a R ^b BO ^-
• The group of silicates and silicic acid esters of the general formula: SiO ₄ ^4- , HSiO ₄ ^3- , H ₂ SiO ₄ ^2- , H ₃ SiO ₄ ^- , R ^a SiO ₄ ^3- , R ^a R ^b SiO ₄ ^2- , R ^a R ^b R ^c SiO ₄ ^- , HR ^a SiO ₄ ^2- , H ₂ R ^a SiO ₄ ^- , HR ^a R ^b SiO ₄ ^-
• • the group of alkylsilane and arylsilane salts of the general formula: R ^a SiO ₃ ^3-, R ^a R ^b SiO ₂ ^2-, R ^a R ^b R ^c SiO ^-, R ^a R ^b R ^c SiO ₃ ^-, R ^a R ^b R ^c SiO ₂ ^- , R ^a R ^b SiO ₃ ^2-
• The group of the carboxylic imides, bis (sulfonyl) imides and sulfonyl imides of the general formula:
  
• The group of methides of the general formula:
  

In this R ^a , R ^b , R ^c and R ^d are each independently hydrogen, C ₁ -C ₃₀ -alkyl, optionally by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups interrupted C ₂ -C ₁₈ alkyl, C ₆ -C ₁₄ aryl, C ₅ -C ₁₂ cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle, wherein two of them together form an unsaturated , saturated or aromatic, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups ring, said radicals each additionally by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, Halogen, heteroatoms and / or heterocycles can be substituted.

These are optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles substituted C ₁ -C ₁₈ alkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert. Butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hetadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3 , 3-tetramethylbutyl, benzyl, 1-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, m-ethoxybenzyl , 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1 , 3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl, 2-isopropoxyethyl , 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, trichloromethyl, trifluoromethyl, 1,1-D imethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6- Dimethylaminohexyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl.

Optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino interrupted C ₂ -C ₁₈ alkyl, for example, 5-methoxy-3-oxapentyl, 8-methoxy-3,6- dioxo-octyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9- Methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxo-octyl, 11-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy 4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetradecyl.

When two radicals form a ring, these radicals can be taken together, for example, as fused building blocks, 1,3-propylene, 1,4-butylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa 1,3-propenylene, 1-aza-1,3-propenylene, 1-C ₁ -C ₄ -alkyl-1-aza-1,3-propenylene, 1,4-buta-1,3-dienylene, 1 -Aza-1,4-buta-1,3-dienylene or 2-aza-1,4-buta-1,3-dienylene mean.

The Number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited or limited automatically by the size of the rest or the ring module. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferred not more than 3. Furthermore, there are two heteroatoms usually at least one, preferably at least two carbon atom (s).

substituted and unsubstituted imino groups may be, for example, imino, Methylimino, iso-propylimino, n-butylimino or tert-butylimino be.

The term "functional groups" is to be understood as meaning, for example, the following: carboxamide, di- (C ₁ -C ₄ -alkyl) -amino, C ₁ -C ₄ -alkyloxycarbonyl, cyano or C ₁ -C ₄ -alkoxy C ₁ -C ₄ -alkyl methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

Optionally C ₆ -C ₁₄ -aryl substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles are, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl , Dichlorophenyl, trichlorophenyl, difuorphenyl, methylphenyl, dimethyl phenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2 , 6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl.

Optionally C ₅ -C ₁₂ -cycloalkyl which is substituted by suitable functional groups, aryl, alkyl, aryloxy, halogen, heteroatoms and / or heterocycles are, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl , Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.

One five to six-membered, oxygen, nitrogen and / or sulfur atoms heterocycle having, for example, furyl, thiophenyl, Pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, Benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, Methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, Isopropylthiophenyl or tert-butylthiophenyl.

Preferred anions are selected from the group of halides and halogen-containing compounds, the group of sulfates, sulfites and sulfonates, the group of phosphates, and the group of carboxylic acids, in particular from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group containing SO4 ^2- , SO3 ^2- , R ^a OSO ₃ ^- and R ^a SO ₃ ^- , and the group containing PO ₄ ^3- and R ^a R ^b PO ₄ ^- .

Preferred anions are in particular chloride, bromide, iodide, SCN ^-, OCN ^-, CN ^-, acetate, propionate, benzoate, C ₁ -C ₄ alkyl sulfates, R ^a -COO ^-, R ^a SO ₃ ^-, R ^a R ^b PO ₄ ^- , methanesulfonate, tosylate or di- (C ₁ -C ₄ -alkyl) phosphates.

Particularly preferred anions are Cl-, CH ₃ COO ^-, C ₂ H ₅ COO ^-, C ₃ H ₇ COO ^-, C ₆ H ₅ COO ^-, CH ₃ SO ₃ ^-, (CH ₃ O) ₂ PO ₂ ^- or ( C ₂ H ₅ O) ₂ PO ₂ ^- .

Especially preferred anions are Cl ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or (C ₂ H ₅ O) ₂ PO ₂ ^- .

Also particularly preferred are CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₃ H ₇ COO ^- or C ₆ H ₅ COO ^- .

In a further preferred embodiment, ionic liquids of the formula I with
[A] _n ⁺ 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methyl-imidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3 ethyl imidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1 Octyl) -3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1 Dodecyl) -3-ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- ( 1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1 - (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium, 1,2,3-trimethylimidazolium , 1-ethyl 2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5- Trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium, or 1- (prop-1-en-3yl) -3-methylimidazolium; and
[Y] ^{n +} Cl ^- , CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₃ H ₇ COO ^- , C ₆ H ₅ COO ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or ( C ₂ H ₅ O) ₂ PO ₂ ^- ; in particular Cl ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or (C ₂ H ₅ O) ₂ PO ₂ ^- ; also in particular CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₃ H ₇ COO ^- or C ₆ H ₅ COO ^- ; used.

In a further preferred embodiment, ionic liquids are used whose anions are selected from the group comprising HSO ₄ ^- , HPO ₄ ^2- , H ₂ PO ₄ ^- and HR ^a PO ₄ ^- ; especially HSO ₄ ^- .

In particular, ionic liquids of formula I with
[A] _n ⁺ 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-Dode cyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methyl-imidazolium, 1- (1-butyl) -3 Methylimidazolium, 1- (1-Butyl) -3-ethylimidazolium, 1- (1-Hexyl) -3-methylimidazolium, 1- (1-Hexyl) -3-ethylimidazolium, 1- (1-Hexyl) 3-butylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) 3-methylimidazolium, 1- (1-dodecyl) -3-ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1 Tetradecyl) -3-methyl-imidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butyl-imidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- ( 1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1 , 2-Dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethyl -imidazolium, 1- (1-Oct yl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 1,4-dimethyl-3-butylimidazolium, 1,4-dimethyl-3 octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5 Trimethyl-3-octylimidazolium or 1- (prop-1-en-3-yl) -3-methylimidazolium; and
[Y] ^{n +} HSO ₄ ^- ;
used.

In the method according to the invention becomes an ionic liquid of formula I or a mixture of ionic liquids of the formula I, preferably an ionic liquid of the formula I is used.

In a further embodiment of the invention Is it possible an ionic liquid of formula II or a mixture of ionic liquids of formula II, preferably becomes an ionic liquid of the formula II used.

In a further embodiment of the invention Is it possible a mixture of ionic liquids of formulas I and II.

wobei die Reste folgende Bedeutung haben:
R^x, R^y, R^z C₁-C₃₀-Alkyl, C₂-C₃₀-Alkenyl, C₂-C₃₀-Alkinyl, C₃-C₁₂-Cycloalkyl, C₅-C₁₂-Cycloalkenyl oder Aryl, wobei diese sechs Reste ggf. substituiert sein können;
X Halogen, Imidazol-1-yl, NH₂, Di-(C₁-C₆-alkyl)-amin, NH-SiR^xR^yR^z, NH-CO-NH-SiR^xR^yR^z, NHCO-(C₁-C₆-alkyl), N(C₁-C₆-alkyl)-CO-(C₁-C₆-alkyl), N(C₁-C₆-alkyl)-CO-(C₁-C₆-halogenalkyl), O-SO₂-(C₁-C₆-alkyl), O-SO₂-(C₁-C₆-halogenalkyl), O-C(=N-SiR^xR^yR^z)-(C₁-C₆-alkyl) oder O-C(=N-SiR^xR^yR^z)-(C₁-C₆-halogenalkyl);
eingesetzt.Silylierungsmitttel the purposes of this invention are those which are able to transmit a SiR ^x R ^y R ^z group to a hydroxyl ^group, to form a O-SiR ^x R ^y R group. Preferably silylating agents of formula IV

where the radicals have the following meaning:
R ^x , R ^y , R ^{z is} C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, C ₂ -C ₃₀ -alkynyl, C ₃ -C ₁₂ -cycloalkyl, C ₅ -C ₁₂ -cycloalkenyl or aryl, these six radicals may optionally be substituted;
X is halogen, imidazol-1-yl, NH ₂ , di- (C ₁ -C ₆ -alkyl) -amine, NH-SiR ^x R ^y R ^z , NH-CO-NH-SiR ^x R ^y R ^z , NHCO- (C ₁ -C ₆ -alkyl), N (C ₁ -C ₆ -alkyl) -CO- (C ₁ -C ₆ -alkyl), N (C ₁ -C ₆ -alkyl) -CO- (C ₁ -) C ₆ haloalkyl), O-SO ₂ - (C ₁ -C ₆ alkyl), O-SO ₂ - (C ₁ -C ₆ haloalkyl), OC (= N-SiR ^x R ^y R ^z ) - ( C ₁ -C ₆ -alkyl) or OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ -haloalkyl);
used.

As optionally substituted C ₁ -C ₃₀ -alkyl radicals for R ^x , R ^y and R ^z are in particular unsubstituted C ₁ -C ₃₀ -alkyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen Called heteroatoms and / or heterocycles substituted C ₁ -C ₃₀ -alkyl radicals,
preferably C ₁ -C ₃₀ -alkyl radicals, such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1 Pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1 -propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl 2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3 , 3-Dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4 Trimethylpentyl, 1,1,3,3-tetramethylbutyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-hepta decyl, Named 1-octadecyl and 1-eicosan-yl, particularly preferably methyl, ethyl, 1-propyl, 1-butyl, 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl; or
preferably C ₁ -C ₃₀ -alkyl radicals which are substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, methoxycarbonylmethyl, 2- Methoxycarbonylethyl, ethoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2- (butoxycarbonyl) -ethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, formyl, dimethyl aminomethyl, phenoxymethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, methoxymethyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, ethoxymethyl, 2- Ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, 2-butoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 2-methoxyisopropyl, dimethoxymethyl, diethoxymethyl, 2,2-diethoxymethyl, 2, 2-diethoxyethyl, acetyl, propionyl, C _m F _{2 (m-a) + (1-b)} H _{2a + b} with m being 1 to 30, 0 ≤ a ≤ m and b = 0 or 1 (for example CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C _(m-2) F _{2 (m-2) +1} , C ₆ F ₁₃ , C ₅ F ₁₇ , C ₁₀ F ₂₁ , C ₁₂ F ₂₅ ), chloromethyl, 2 Chloroethyl, trichloromethyl, 1,1-dimethyl-2-chloroethyl, methylthiomethyl, ethylthiomethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl , 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy 3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy 5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetradecyl.

Unsubstituted C ₂ -C ₃₀ -alkenyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen may be mentioned as unsubstituted or substituted C ₂ -C ₃₀ -alkenyl radicals for R ^x , R ^y and R ^z Called heteroatoms and / or heterocycles substituted C ₂ -C ₃₀ alkenyl radicals,
preferably C ₂ -C ₃₀ -alkenyl radicals, such as, for example, vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl or trans-2-butenyl, particularly preferably vinyl or 2-propenyl; or
preferably C ₂ -C ₃₀ alkenyl radicals substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as C _m F _{2 (m-a) - (1-b )} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

Unsubstituted C ₂ -C ₃₀ -alkynyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen may be mentioned as optionally substituted C ₂ -C ₃₀ -alkynyl radicals for R ^x , R ^y and R ^z , heteroatoms and / or heterocycles substituted C ₂ -C ₃₀ alkynyl radicals mentioned,
preferably C ₂ -C ₃₀ -alkynyl radicals, such as, for example, ethynyl, 1-propyn-3-yl, 1-propyn-1-yl or 3-methyl-1-propyn-3-yl, particularly preferably ethynyl or 1-propyne -3-yl.

Unsubstituted C ₃ -C ₈ -cycloalkyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen may be mentioned as unsubstituted or substituted C ₃ -C ₁₂ -cycloalkyl radicals for R ^x , R ^y and R ^z Called heteroatoms and / or heterocycles substituted C ₃ -C ₁₂ -cycloalkyl radicals,
preferably C ₃ -C ₁₂ -cycloalkyl radicals, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl or butylcyclohexyl, and also bicyclic systems such as norbornyl, preferably cyclopentyl or cyclohexyl; or
preferably C ₃ -C ₁₂ -cycloalkyl radicals which are substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for example, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F _{2 (m-a) - (1-b)} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

As optionally substituted C ₅ -C ₁₂ cycloalkenyl radicals for R ^x , R ^y and R ^z are in particular unsubstituted C ₃ -C ₈ cycloalkenyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen Called heteroatoms and / or heterocycles substituted C ₃ -C ₈ cycloalkenyl radicals,
preferably C ₃ -C ₈ -cycloalkenyl radicals, such as, for example, 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl, and also bicyclic systems such as norbornyl, more preferably 3-cyclopentenyl, 2-cyclohexenyl or 3- cyclohexenyl; or
preferably C ₃ -C ₈ -cycloalkenyl radicals which are substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for example, C _n F _{2 (m-a) -3 (1 b)} H _2a-3b with m ≤ 12, 0 ≤ a ≤ m and b = 0 or 1.

Unsubstituted C ₆ -C ₁₂ -aryl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles may be mentioned as unsubstituted or substituted aryl radicals for R ^x , R ^y and R ^z called substituted C ₆ -C ₁₂ aryl radicals,
preferably C ₆ -C ₁₂ -aryl radicals, such as, for example, phenyl, α-naphthyl or β-naphthyl, particularly preferably phenyl; or
preferably by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted C ₆ -C ₁₂ aryl radicals such as tolyl, xylyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difuorphenyl , Methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4- Acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C ₆ F _(5-a) H _a with 0 ≤ a ≤ 5, more preferably 4-tolyl.

As a C ₁ -C ₆ -alkyl radicals as substituents Sub-meaning of X are, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2- Methyl 2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl 2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3- Dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl or 3,3-dimethyl-2-butyl, preferably methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl or 1-hexyl, especially methyl or ethyl.

C ₁ -C ₆ -haloalkyl radicals as sub-substituents of X may be, for example, C ₁ -C ₆ -alkyl radicals as described above which are partially or completely substituted by fluorine, chlorine, bromine and / or iodine, eg chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, iodomethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluorobutyl, 4- Chlorobutyl, 4-bromobutyl, nonafluorobutyl, 1, 1,2,2-tetrafluoroethyl, 1-trifluoromethyl-1,2,2,2,2-tetrafluoroethyl, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl or tridecafluorohexyl, preferably chloromethyl or trifluoromethyl.

The silylating agents R ^x R ^y R ^z Si-NH-SiR ^x R ^y R ^z , R ^x R ^y R ^z Si-OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ -alkyl) and R ^x R ^y R ^z Si-OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ -haloalkyl) can not only transfer one of the R ^x R ^y R ^z Si groups contained in the respective molecule but all.

In one embodiment of the present invention silylating agents of the formula IV are used, where the radicals have the following meanings:
R ^x , R ^y , R ^{z is} C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, C ₂ -C ₃₀ -alkynyl, C ₃ -C ₁₂ -cycloalkyl, C ₅ -C ₁₂ -cycloalkenyl or aryl, these six radicals may optionally be substituted; in particular C ₁ -C ₃₀ -alkyl or aryl, where these radicals may optionally be substituted, preferably C ₁ -C ₆ -alkyl or phenyl; in particular C ₁ -C ₄ -alkyl or phenyl, preferably C ₁ -C ₄ -alkyl;
X is halogen, imidazol-1-yl, di- (C ₁ -C ₆ -alkyl) -amine, NH-SiR ^x R ^y R ^z , NH-CO-NH-SiR ^x R ^y R ^z , NHCO- (C ₁ -C ₆ -alkyl), N (C ₁ -C ₆ -alkyl) -CO- (C ₁ -C ₆ -alkyl), N (C ₁ -C ₆ -alkyl) -CO- (C ₁ -C ₆ -) haloalkyl), O-SO ₂ - (C ₁ -C ₆ -alkyl), O-SO ₂ - (C ₁ -C ₆ -haloalkyl), OC (= N-SiR ^x R ^y R ^z ) - (C ₁ - C ₆ alkyl) or OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ haloalkyl); in particular halogen, imidazol-1-yl, di- (C ₁ -C ₆ -alkyl) -amine, NH-SiR ^x R ^y R ^z , OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ -alkyl) or OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ -haloalkyl), preferably chlorine, di (C ₁ -C ₄ -alkyl) amine, NH-SiR ^x R ^y R ^z , OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₄ alkyl) or OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₄ haloalkyl); preferably chlorine, diethylamine, NH-SiR ^x R ^y R ^z , OC (= N-SiR ^x R ^y R ^z ) -CH ₃ or OC (= N-SiR ^x R ^y R ^z ) CF ₃ .

In a particular embodiment of the present invention are used as silylating agents of the formula IV hexamethyldisilazane (HMDS), trimethylsilyl-diethylamine or N, O-bis (trimethylsilyl) acetamide used.

For the silylation according to the invention of cellulose Celluloses from a variety of sources are used such as. made of cotton, flax, ramie, straw, bacteria etc., or made of wood or bagasse, in the cellulose-enriched form.

The inventive method but not only for the silylation of cellulose but generally for Silylation of poly-, oligo- and disaccharides, as well as derivatives thereof, used. As examples of polysaccharides are besides Cellulose and hemicellulose, starch, To name glycogen, dextran and tunicin. Likewise count to this the polycondensates of D-fructose, such as inulin, as well as u.a. chitin, Chitosan and alginic acid. Sucrose is an example of a disaccharide. Suitable cellulose derivatives are those whose DS is <3, et al Cellulose ethers, such as methylcellulose and carboxymethylcellulose, Cellulose esters, such as cellulose acetate, cellulose butyrate and cellulose nitrate, each with a DS <3. The corresponding versions apply here accordingly.

In an embodiment The present invention is a process according to the invention Polysaccharide, e.g. Cellulose, hemicellulose, starch, glycogen, Dextran, tunicin, inulin, chitin, chitosan or alginic acid, preferably Cellulose, silylated.

In a further embodiment The present invention is according to the inventive method a disaccharide, e.g. Sucrose, silylated.

In a further embodiment The present invention is according to the inventive method a cellulose derivative whose DS <3 is, e.g. a cellulose ether such as methyl cellulose and carboxymethyl cellulose, a cellulose ester such as cellulose acetate, cellulose butyrate as well Cellulose nitrate, each with a DS <3, silylated.

The following versions not only apply to Cellulose but according to the other poly-, oligo- and disaccharides, as well as derivatives thereof, analogous.

at the method according to the invention becomes a solution of cellulose in ionic liquid, produced. The concentration of cellulose can be in large areas be varied. Usually it is in the range of 0.1 to 50 wt .-%, based on the total weight the solution, preferably at 0.2 to 40 wt .-%, particularly preferably 0.3 to 30 wt .-% and particularly preferably at 0.5 to 20% wt .-%.

This solution process can be carried out at room temperature or under heating, but above the melting or softening temperature of the ionic Liquid, usually at a temperature of 0 to 200 ° C, preferably at 20 to 180 ° C, especially preferably at 50 to 150 ° C. It is also possible the dissolution process by intensive stirring or mixing and by entry of microwave or ultrasonic energy or by speeding up their combination.

To this solution thus obtained Now, the silylating agent of formula IV is given.

The Silylating agent of the formula IV can be used in bulk, in an ionic liquid or in a suitable solvent solved be added. As a solvent For example, ethers such as diethyl ether, methyl tert-butyl ether, Tetrahydrofuran or dioxane, or ketones, such as dimethyl ketone, halogenated hydrocarbons, such as dichloromethane, trichloromethane or dichloroethane, or hydrocarbons, for example, aromatic hydrocarbons, such as benzene, toluene, Xylene or mesitylene. The amount of solvent used to solve the silylating agent of formula IV should be sized so that no precipitation of the cellulose in the Addition occurs. As an ionic liquid Preferably, the one in which the cellulose yourself - like described above - is solved.

In a particular embodiment the silylating agent of formula IV is added in bulk.

In another particular embodiment becomes the silylating agent of the formula IV in an ionic liquid solved added, with particular preference the ionic liquid which is also used to solve the cellulose is used.

In another embodiment become the ionic liquid and the silylating agent of formula IV premixed and the cellulose solved in this mixture.

It there is also the possibility that one or more further solvents, be added to the reaction mixture, or already with the ionic liquid or the silylating agent of the formula IV. As a solvent come here in such solvents in question, what the solubility do not adversely affect the cellulose, such as aprotic dipolar Solvent, for example, dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane. Furthermore you can also nitrogenous bases, such as pyridine, etc., additionally added become.

In a particular embodiment contains the reaction mixture in addition to the ionic liquid and possibly the solvent, in which the silylating agent of the formula IV is dissolved, less than 5% by weight, preferably less than 2% by weight, in particular less than 0.1% by weight, based on the total weight of the reaction mixture, on further solvents and / or additional nitrogenous bases.

It is also possible to carry out the process according to the invention in the presence of a catalyst. Mono- or disaccharides, for example glucose or sucrose, or saccharin, preferably saccharin, are suitable for this purpose. The catalyst is usually used in amounts of up to 10 mol%, preferably up to 5 mol%, based on the silylating agent of the formula IV.

On a case-by-case basis, it may also be advantageous to carry out the silylation in the presence of a tertiary amine such as triethylamine, an aromatic nitrogen base such as pyridine, or mixtures thereof; especially when an acid is released during silylation. This can be especially with the use of silylating agents of formula IV with X = halogen, O-SO ₂ - (C ₁ -C ₆ alkyl), O-SO ₂ - (C ₁ -C ₆ haloalkyl), OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ alkyl) or OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ haloalkyl). The teriary amine, the aromatic nitrogen base or the mixtures thereof are usually used in a stoichiometric ratio. On a case-by-case basis, an excess or a deficit can also be beneficial.

The Implementation becomes dependent from the ionic liquid used and the reactivity of the used Silylation of the formula IV usually at a temperature of melting point of the ionic liquid to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C carried out.

The reaction usually takes place at ambient pressure. However, it may also be advantageous on a case-by-case basis to work at overpressure, especially if a volatile silylating agent of the formula IV is used. In general, the reaction is carried out in air or under a protective gas atmosphere, that is, for example, under N ₂ , a noble gas, or mixtures thereof.

In dependence from the desired The degree of substitution of the cellulose is the amount of silylating agent used - in each case in relation to to the cellulose used - the Reaction time and optionally set the reaction temperature.

For example, if it is desired to completely silylate the cellulose, which is composed on average of u anhydroglucose units, 3u equivalents of silylating agent of the formula IV are required in the event that the silylating agent transfers a silyl group. Preferably, the stoichiometric amount of silylating agent of the formula IV (n _{silylating agent} / s _{anhydroglucose units} = 3) or an excess is used, preferably an excess of from 10 to 500 mol%, in particular from 10 to 300 mol%, particularly preferably from 10 to 200 mol%, based on u. In the event that the silylating agent can transfer more silyl groups, the amounts of silylating agent used of formula IV decreases accordingly.

If it is desired to partially silylate the cellulose, which is composed on average of u anhydroglucose units, then the amounts of silylating agent used of formula IV are usually adjusted (n _{silylating agent} (s) _{anhydroglucose units} <3, in the case where the silylating agent of the Formula IV transfers a silyl group). The smaller the quotient n _{silylating agent} (s) _{anhydroglucose units} , the lower will be the average degree of substitution of the silylated cellulose under otherwise identical conditions and the same reaction time. In the event that the silylating agent can transfer more silyl groups, the amounts of silylating agent used of the formula IV or the reaction time is reduced accordingly.

Farther Is it possible abort the silylation reaction when the desired degree achieved by silylation is achieved by the silylated cellulose is separated off the reaction mixture. This can be done, for example Adding a surplus on a suitable solvent, in which the silylated cellulose is insoluble, the ionic liquid but easily soluble is such as a lower alcohol such as methanol, ethanol, propanol or butanol, or with a ketone, for example diethyl ketone etc., or mixtures thereof, take place. The choice of the suitable solvent is also determined by the respective degree of substitution and the substituents determined the cellulose. Preferably, an excess of methanol is used.

The Work-up of the reaction mixture is usually carried out by the silylated Cellulose precipitated as described above and silylated Cellulose is filtered off. But it is also possible separation by centrifugation perform. From the filtrate or the centrifugate can by conventional methods, the ionic liquid be recovered by the volatile components, such. the precipitant, or excess silylating agent of the formula IV (or reaction products and / or hydrolysis products the silylating agent of the formula IV) etc. are distilled off. The remaining ionic liquid can again in the inventive method be used.

But it is also possible the reaction mixture in methanol or in another suitable solution in which the silylated cellulose is not soluble, but the ionic liquid is slightly soluble, such as another lower alcohol, such as ethanol, propanol or butanol, or a ketone, for example diethyl ketone, etc., or mixtures thereof, and, depending on the embodiment, for example Fibers to obtain films of silylated cellulose. The choice of suitable Lösusungsmittels is also determined by the respective degree of substitution and the substituents of the cellulose. The filtrate is worked up as described above.

Farther Is it possible abort the silylation reaction when the desired degree is achieved by silylation by cooling the reaction mixture and worked up. The work-up can be described after the above Methods are done.

Of the Termination of the silylation reaction can also be done so that At a given time still existing silylating the Formula IV from the reaction mixture by distillation, stripping or Extract with a solvent, that with the ionic liquid forms two phases, is removed.

In the case, that the silylated cellulose during the reaction of the ionic liquid or separates the reaction mixture, it may be advantageous to the silylated Cellulose after completion of the reaction by filtration to separate and optionally with a suitable solvent to wash. Alternatively, after completion of the reaction, a suitable Solvent, which is immiscible with the reaction mixture but which is silylated Dissolves cellulose, be added. After phase separation, the silylated cellulose from the extract by distilling off the added solvent won. Come as a solvent therefor for example hydrocarbons, such as aromatic hydrocarbons, e.g. Benzene, toluene, xylene, mesitylene or mixtures thereof, in Consideration. On a case-by-case basis, it can also be an advantage solvent right at the start of the reaction, the implementation then in a two-phase (liquid / liquid) system takes place.

In a further embodiment of the present invention, the cellulose is reacted with a silylating agent of the formula IV in an ionic liquid of the formula I wherein [Y] ^n- R ^{a is} COO ^- . From case to case, in addition to the silylation of the cellulose, an acylation of the cellulose may occur, with the remainder R ^a COO being transferred.

In another embodiment of the present invention the cellulose with two or more silylating agents of the formula IV are implemented, which transfer different silyl groups. Here, a mixture of two (or more) silylating agents of formula IV used in analogy to the above procedure become. It is also possible first with the first silylating agent of the formula IV, the reaction up to a DS = a (<3) perform and then with a second silylating agent of formula IV the Conversion up to a DS = b, where a <b ≦ 3, perform.

at this embodiment, silylated celluloses are obtained, which two (or more) different silyl radicals (depending on of the silylating agents of the formula IV) used.

In the case, that the ionic liquid guided in circulation mode is, the ionic liquid can up to 15% by weight, preferably up to 10% by weight, in particular up to 5% by weight of precipitant (s) as described above, but provided that that these do not decompose the silylating agent used to lead.

The Method may be discontinuous, semi-continuous or continuous, carried out become.

Farther It may be beneficial to the reaction in the absence of moisture to carry out, there Silylating agents are usually sensitive to moisture. To For this purpose, the reagents used, solvents, etc. according to usual Dried laboratory methods, the ionic liquid used and the cellulose can for example, under heating be dried in vacuo, optionally used solvents and protective gases according to methods known to the expert, etc. It is, however, too possible to refrain from these arrangements, then, however, accordingly higher Consumed quantities of silylating agent.

In a further embodiment, the cellulose used can be dissolved in an ionic liquid of the formula I or II or mixtures thereof, and in step a1) the cellulose is degraded in the presence of an acid, optionally with the addition of water to a desired average degree of polymerization DP, and in a step b) subjected to the thus obtained degraded cellulose silylation who as described above.

Step a1) can be carried out as follows:
As the acid, inorganic acids, organic acids or mixtures thereof can be used.

Examples of inorganic acids are hydrohalic acids such as HF, HCl, HBr or HI, perhalogenic acids such as HClO ₄ , halogen acids such as HClO ₃ , sulfur-containing acids such as H ₂ SO ₄ , polysulfuric acid or H ₂ SO ₃ , nitrogen-containing acids , such as HNO ₃ , or phosphorus-containing acids, such as H ₃ PO ₄ , polyphosphoric acid or H ₃ PO ₃ . Preference is given to using hydrohalic acids, such as, for example, HCl or HBr, H ₂ SO ₄ , HNO ₃ or H ₃ PO ₄ , in particular HCl, H ₂ SO ₄ or H ₃ PO ₄ .

• • C₁-C₆-Alkancarbonsäuren, beispielsweise Essigsäure, Propionsäure, n-Butancarbonsäure oder Pivalinsäure,
• • Di- bzw. Polycarbonsäuren, beispielsweise Bernsternsäure, Maleinsäure oder Fumarsäure,
• • Hydroxycarbonsäuren, beispielsweise Hydroxyessigsäure, Milchsäure, Apfelsäure oder Citronensäure,
• • halogenierte Carbonsäuren, beispielsweise C₁-C₆-Halogenalkancarbonsäuren, z. B. Fluoressigsäure, Chloressigsäure, Bromessigsäure, Difluoressigsäure, Dichloressigsäure, Chlorfluoressigsäure, Trifluoressigsäure, Trichloressigsäure, 2-Chlorpropionsäure, Perfluorpropionsäure oder Perfluorbutancarbonäure,
• • aromatische Carbonsäuren, beipielsweise Arylcarbonsäuren, wie Benzoesäure;

oder Sulfonsäuren, wie

• • C₁-C₆-Alkansulfonsäuren, beispielsweise Methansulfonsäure oder Ethansulfonsäure,
• • halogenierte Sulfonsäuren, beispielsweise C₁-C₆-Halogenalkansulfonsäuren, wie Trifluormethansulfonsäure,
• • aromatische Sulfonsäuren, beispielsweise Arylsulfonsäuren, wie Benzolsulfonsäure oder 4-Methylphenylsulfonsäure.

Examples of organic acids are carboxylic acids, such as

• C ₁ -C ₆ -alkanecarboxylic acids, for example acetic acid, propionic acid, n-butanecarboxylic acid or pivalic acid,
• Di- or polycarboxylic acids, for example succinic acid, maleic acid or fumaric acid,
• Hydroxycarboxylic acids, for example hydroxyacetic acid, lactic acid, malic acid or citric acid,
• Halogenated carboxylic acids, for example C ₁ -C ₆ -haloalkanecarboxylic acids, eg. Fluoroacetic acid, chloroacetic acid, bromoacetic acid, difluoroacetic acid, dichloroacetic acid, chlorofluoroacetic acid, trifluoroacetic acid, trichloroacetic acid, 2-chloropropionic acid, perfluoropropionic acid or perfluorobutanecarboxylic acid,
• Aromatic carboxylic acids, for example arylcarboxylic acids, such as benzoic acid;

or sulfonic acids, such as

• C ₁ -C ₆ -alkanesulfonic acids, for example methanesulfonic acid or ethanesulfonic acid,
• Halogenated sulfonic acids, for example C ₁ -C ₆ -haloalkanesulfonic acids, such as trifluoromethanesulfonic acid,
• Aromatic sulfonic acids, for example arylsulfonic acids, such as benzenesulfonic acid or 4-methylphenylsulfonic acid.

C ₁ -C ₆ -alkanecarboxylic acids, for example acetic acid or propionic acid, halogenated carboxylic acids, for example C ₁ -C ₆ -haloalkanecarboxylic acids, eg. Fluoroacetic acid, chloroacetic acid, difluoroacetic acid, dichloroacetic acid, chlorofluoroacetic acid, trifluoroacetic acid, trichloroacetic acid or perfluoropropionic acid, or sulfonic acids such as C ₁ -C ₆ -alkanesulfonic acids, for example methanesulfonic acid or ethanesulfonic acid, halogenated sulfonic acids, for example C ₁ -C ₆ -haloalkanesulfonic acids, such as trifluoromethanesulfonic acid, or arylsulfonic acids, such as benzenesulfonic acid or 4-methylphenylsulfonic acid. Preferably, acetic acid, chlorofluoroacetic acid, trifluoroacetic acid, perfluoropropionic acid, methanesulfonic acid, trifluoromethanesulfonic acid or 4-methylphenylsulfonic acid are used.

In a particular embodiment of the invention be called acid Sulfuric acid, Acetic acid, trifluoroacetic, methane or 4-methylphenylsulfonic acid used. For the case where 4-methylphenyl sulfonic acid monohydrate is used, is already an equivalent Water with in front.

In a particular embodiment become ionic liquids and acids used, whose anions are identical. Preferably, these are Anions acetate, trifluoroacetate, chloride or bromide.

In another particular embodiment become ionic liquids and acids used, whose anions are not identical.

To the solution of cellulose in ionic liquid becomes the acid and possibly water. The addition of water may be necessary if the water adhering to the cellulose used does not suffice is, the desired Achieve degree of degradation. In general, the proportion of water is common cellulose in the range of 5 to 10 wt .-%, based on the total weight of used cellulose (cellulose per se + adherent water). In order to achieve a partial degradation of the cellulose, are substoichiometric Quantities of water and acid added or the reaction is stopped at a given time.

In another embodiment become the ionic liquid, Acid and if necessary pre-mixed with water and the cellulose dissolved in this mixture.

There is also the possibility that one or more further solvents to the Reaktionsge be mixed or already added with the ionic liquid and / or the acid and / or optionally the water. Suitable solvents here are those which do not adversely affect the solubility of the cellulose, such as aprotic-dipolar solvents, for example dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane.

In a particular embodiment contains the reaction mixture is less than 5% by weight, preferably less than 2% by weight, in particular less than 0.1% by weight, of further solvents, based on the total weight of the reaction mixture.

The Hydrolysis becomes dependent of the ionic liquid and acid used at a temperature of the melting point of the ionic liquid up to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C carried out.

Usually the reaction takes place at ambient pressure. It may be case by case but also be advantageous in case of overpressure to work, especially if volatile acids are used.

As a rule, the reaction is carried out in air. But it is also possible under inert gas, so for example, under N ₂ , to work a noble gas, or a mixture thereof.

In dependence from the desired Degree of degradation is the amount of acid used, which may be added Water, - each in relation to to the cellulose used - the Reaction time and optionally set the reaction temperature.

If it is desired to convert the cellulose, which is composed on average of x anhydroglucose units, into a cellulose whose number of hydro-glucose units is less than x, the amounts of water used and acid used are usually adjusted in accordance with the _{degree of} degradation (n _{anhydroglucose units} / n _acid > 1). The larger the quotient n _{anhydroglucose units} / n _acid , the lower will be the average degradation of cellulose under otherwise identical reaction conditions and the same reaction time. The larger the quotient n _{anhydroglucose units} / n of _water , the lower will be the average degradation of cellulose under otherwise identical reaction conditions and the same reaction time.

It is possible, too to stop the hydrolysis reaction when the desired level of degradation is reached is by the acid intercepted with a base. Suitable bases are both inorganic Bases, e.g. Alkali hydroxides, carbonates, bicarbonates, but also organic bases such as e.g. Amines in stoichiometric relationship to the acid or in excess be used. In a further embodiment, as the base Hydroxide can be used, which is characterized in that whose cation corresponds to that of the ionic liquid used.

Farther Is it possible to stop the degradation reaction when the desired degree of degradation is reached is by adding appropriate amounts of silylating agent of the formula IV are added, which react with remaining water.

The so obtained solution will now be used in step b) as described above.

In In another embodiment, the cellulose used in an ionic liquid of the formula I or II or mixtures thereof, and in step a2) the cellulose optionally with the addition of water at elevated temperature are treated, and in a step b) the resulting degraded Cellulose be subjected to a silylation, as above described.

Step a2) can be carried out as follows:
If ionic liquids are used which have no acidic functions, the degradation is usually carried out at temperatures of 50 to 200 ° C, preferably from 80 ° C to 180, in particular from 80 to 150 ° C. Suitable ionic liquids are those whose anions are selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group containing SO ₄ ^2- , SO ₃ ^2- , R ^a OSO ₃ ^- and R ^a SO ₃ ^- , And the group containing PO ₄ ^3- and R ^a R ^b PO ₄ ^- . Preferred anions here are chloride, bromide, iodide, SCN ^-, OCN ^-, CN ^-, acetate, C ₁ -C ₄ alkyl, R ^a COO ^-, R ^a SO ₃ ^-, R ^a R ^b PO ₄ ^-, methanesulfonate, Tosylate or C ₁ -C ₄ dialkyl phosphates; and especially before anions are Cl ^- , CH ₃ COO ^- , C ₂ H ₅ COO ^- , C ₆ H ₅ COO ^- , CH ₃ SO ₃ ^- , (CH ₃ O) ₂ PO ₂ ^- or (C ₂ H ₅ O ) ₂ PO ₂ ^- .

If ionic liquids are used which have acidic functions then it is possible to carry out the degradation of the cellulose at a temperature of 0 to 150 ° C, preferably from 20 to 150 ° C, in particular from 50 to 150 ° C. Particular preference is given here to ionic liquids whose anions are selected from the group comprising HSO ₄ ^- , HPO ₄ ^2- , H ₂ PO ₄ ^- and HR ^a PO ₄ ^- ; especially HSO ₄ ^- .

In an embodiment be the preparation of the reaction solution and the degradation in the same temperature.

In In another embodiment, the preparation of the reaction solution and the degradation is carried out at different temperatures.

From Case by case, it is also possible that already during the preparation of the reaction solution a degradation of cellulose takes place. In a special embodiment find the solution and the degradation process takes place in parallel, as it were.

Usually the reaction takes place at ambient pressure. It may be case by case but also be advantageous in case of overpressure to work.

As a rule, the reaction is carried out in air. But it is also possible under inert gas, so for example, under N ₂ , a noble gases, or mixtures thereof, to work.

In dependence from the desired Degree of degradation, the reaction time and the reaction temperature is set.

In an embodiment water is added. In a partial degradation of cellulose are preferably substoichiometric Amounts of water are added or the reaction is stopped.

If the degradation is carried out in the presence of water it is possible the ionic liquid and Pre-mix the water and add the cellulose in this mixture to solve. It is also possible the water to the solution of ionic liquid and cellulose.

If it is desired to convert the cellulose, which is composed on average of x anhydroglucose units, into a cellulose whose number of anhydroglucose units is less than x, the amounts of water used are usually adjusted according to the _{degree of} degradation (n _{anhydroglucose units} / n _water) 1). The larger the quotient n _{anhydroglucose units} / n of _water , the lower will be the average degradation of cellulose under otherwise identical reaction conditions and the same reaction time and the higher the DP of the degraded cellulose (which of course will be smaller than the DP of the cellulose used).

In another embodiment is worked without the addition of water. This is usually the case then Case when the ionic liquid used small amounts Contains water and / or if water adheres to the cellulose used. Of the Water content at usual Cellulose can be up to 10 wt .-%, based on the total weight of used cellulose lie. The above statements apply accordingly.

It there is also the possibility that one or more other solvents to the reaction mixture or the water - as far as this was added - are added. As a solvent come here in question, which is not the solubility of cellulose adversely affect like aprotic dipolar solvents, for example, dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane.

In a particular embodiment contains the reaction mixture is less than 5% by weight, preferably less than 2% by weight, in particular less than 0.1% by weight, of further solvents, based on the total weight of the reaction mixture.

Farther Is it possible to stop the degradation reaction when the desired degree of degradation is reached is by adding appropriate amounts of silylating agent of the formula IV are added, which react with remaining water.

The so obtained solution will now be used in step b) as described above.

In another embodiment, a silylated cellulose having a DS <3 may be subjected to acylation. Acylating agents in the context of the present invention are carboxylic acid derivatives as well Ketene and diketene.

wobei die Reste folgende Bedeutung haben:
R^s, R^s' H, C₁-C₃₀-Alkyl, C₂-C₃₀-Alkenyl, C₂-C₃₀-Alkinyl, C₃-C₁₂-Cycloalkyl, C₅-C₁₂-Cycloalkenyl, Aryl oder Heterocyclyl, wobei diese sieben letztgenannten Reste ggf. substituiert sein können;
T Halogen, Imidazol-1-yl oder O-COR^s'.Carboxylic acid derivatives in the context of the present invention are carboxylic acid derivatives of the formula V

where the radicals have the following meaning:
R ^s , R ^{s' is} H, C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alkynyl, C ₃ -C ₁₂ cycloalkyl, C ₅ -C ₁₂ cycloalkenyl, aryl or Heterocyclyl, where these seven latter radicals may be optionally substituted;
T is halogen, imidazol-1-yl or O-COR ^s' .

wobei die Reste folgende Bedeutung haben:
R^t, R^t', R^u, R^u' Wasserstoff, C₁-C₃₀-Alkyl, C₂-C₃₀-Alkenyl, C₂-C₃₀-Alkinyl, C₃-C₁₂-Cycloalkyl, C₅-C₁₂-Cycloalkenyl, Aryl oder Heterocyclyl, wobei die sieben letztgenannten Reste ggf. substituiert sein können;
oder
R^t und R^u bzw. R^t' und R^u' bilden gemeinsam eine ggf. substituierte -Y_o-(CH₂)_p-, -(CH₂)_q -Y-(CH₂)_r- oder eine -CH=CH-CH=CH- -Kette, wobei
Y O, S, S(=O), S(=O)₂, NH oder NC₁-C₆-Alkyl;
o 0 oder 1;
p 2, 3, 4, 5, 6, 7 oder 8;
q, r 1, 2, 3, 4, 5 oder 6;
bedeuten.Ketenes for the purposes of the present invention (compounds of the formula VI) are ketenes of the formula VIa and diketenes for the purposes of the present invention are diketenes of the formula VIb1 or mixed diketenes of the formula VIb2,

where the radicals have the following meaning:
R ^t , R ^{t '} , R ^u , R ^{u' are} hydrogen, C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, C ₂ -C ₃₀ -alkynyl, C ₃ -C ₁₂ -cycloalkyl, C ₅ - C ₁₂ -cycloalkenyl, aryl or heterocyclyl, where the seven last-mentioned radicals may optionally be substituted;
or
R ^t and R ^u and R ^{t '} and R ^u' together form an optionally substituted -Y _o - (CH ₂ ) _p -, - (CH ₂ ) _q -Y- (CH ₂ ) _r - or a -CH = CH-CH = CH- chain, where
YO, S, S (= O), S (= O) ₂ , NH or NC ₁ -C ₆ alkyl;
o is 0 or 1;
p is 2, 3, 4, 5, 6, 7 or 8;
q, r is 1, 2, 3, 4, 5 or 6;
mean.

As optionally substituted C ₁ -C ₃₀ -alkyl radicals for R ^s , R ^s' , R ^t , R ^{t '} , R ^u or R ^u' are in particular unsubstituted C ₁ -C ₃₀ -alkyl radicals or by functional groups , Aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted C ₁ -C ₃₀ -alkyl radicals,
preferably C ₁ -C ₃₀ -alkyl radicals, such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1 Pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1 -propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl 2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3 , 3-Dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, 2-ethylhexyl, 2,4,4 Trimethylpentyl, 1,1,3,3-tetramethylbutyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tridecyl, 1-tetradecyl, 1-pentadecyl, 1-hexadecyl, 1-heptadecyl, 1 Octadecyl and 1-eicosan-yl, more preferably methyl, ethyl, 1-propyl, 1-butyl, 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl; or
preferably C ₁ -C ₃₀ -alkyl radicals which are substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, methoxycarbonylmethyl, 2-methoxycarbonylethyl , Ethoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2- (butoxycarbonyl) -ethyl, 2-butoxycarbonylpropyl, 1,2-di- (methoxycarbonyl) -ethyl, formyl, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl , 6-hydroxyhexyl, 2-hydroxy-2,2-dimethylethyl, aminomethyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, methylaminomethyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl , 4-methylaminobutyl, 6-methylaminohexyl, dimethylaminomethyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, phenoxymethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6 Phenoxyhexyl, methoxymethyl, 2-methoxyethyl , 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, ethoxymethyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, 2-butoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl , 2-octyloxyethyl, 2-methoxyisopropyl, dimethoxymethyl, diethoxymethyl, 2,2-diethoxymethyl, 2,2-diethoxyethyl, acetyl, propionyl, C _m F _{2 (m-a) + (1-b)} H _{2a + b} with m equal to 1 to 30, 0 ≤ a ≤ m and b = 0 or 1 (for example, CF ₃ , C ₂ F ₅ , CH ₂ CH ₂ -C _(m-2) F _{2 (m-2) +1} , C ₆ F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C ₁₂ F ₂₅ ), chloromethyl, 2-chloroethyl, trichloromethyl, 1,1-dimethyl-2-chloroethyl, methylthiomethyl, ethylthiomethyl, butylthiomethyl, 2-dodecylthioethyl, 2 Phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3,6-dioxa-octyl, 11-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 11- Hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5,10-dioxa-tetradecyl, 5-methoxy 3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 11-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8- dioxa undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-dioxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 11-ethoxy-4,8-dioxa-undecyl, 15- Ethoxy-4,8,12-trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy 5,10-oxa-tetradecyl.

As optionally substituted C ₂ -C ₃₀ alkenyl radicals for R ^s, R ^s' , R ^t , R ^{t '} , R ^u or R ^u' are in particular unsubstituted C ₂ -C ₃₀ alkenyl radicals or by functional groups , Aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted C ₂ -C ₃₀ -alkenyl radicals,
preferably C ₂ -C ₃₀ -alkenyl radicals, such as, for example, vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl or trans-2-butenyl, particularly preferably vinyl or 2-propenyl; or
preferably C ₂ -C ₃₀ -alkenyl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for example, C _m F _{2 (m-a) - (1-b)} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

Optionally substituted C ₂ -C ₃₀ -alkynyl radicals for R ^s , R ^s' , R ^t , R ^{t '} , R ^u or R ^u' are in particular unsubstituted C ₂ -C ₃₀ -alkynyl radicals or by functional groups , Aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted C ₂ -C ₃₀ -alkynyl radicals,
preferably C ₂ -C ₃₀ -alkynyl radicals, such as, for example, ethynyl, 1-propyn-3-yl, 1-propyn-1-yl or 3-methyl-1-propyn-3-yl, particularly preferably ethynyl or 1-propyne -3-yl.

As optionally substituted C ₃ -C ₁₂ -cycloalkyl radicals for R ^s , R ^s' , R ^t , R ^{t '} , R ^u or R ^u' are in particular unsubstituted C ₃ -C ₈ -cycloalkyl radicals or by functional groups , Aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted C ₃ -C ₁₂ -cycloalkyl radicals,
preferably C ₃ -C ₁₂ -cycloalkyl radicals, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl or butylcyclohexyl, and also bicyclic systems such as norbornyl, preferably cyclopentyl or cyclohexyl; or
preferably C ₃ -C ₁₂ -cycloalkyl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for example, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C _m F _{2 (m-a) - (1-b)} H _2a-b with m ≤ 30, 0 ≤ a ≤ m and b = 0 or 1.

As optionally substituted C ₅ -C ₁₂ cycloalkenyl radicals for R ^s , R ^s' , R ^t , R ^{t '} , R ^u or R ^u' are in particular unsubstituted C ₃ -C ₈ cycloalkenyl radicals or by functional groups , Aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted C ₃ -C ₈ -cycloalkenyl radicals,
preferably C ₃ -C ₈ -cycloalkenyl radicals, such as, for example, 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl, and also bicyclic systems such as norbornyl, more preferably 3-cyclopentenyl, 2-cyclohexenyl or 3- cyclohexenyl;
or
preferably C ₃ -C ₈ -cycloalkenyl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as C _n F _{2 (m-a) -3 (1-b )} H _2a-3b with m ≤ 12, 0 ≤ a ≤ m and b = 0 or 1.

As optionally substituted aryl radicals for R ^s , R ^s' , R ^t , R ^{t '} , R ^u or R ^u' are in particular unsubstituted C ₆ -C ₁₂ aryl radicals or by functional groups, aryl, alkyl, aryloxy , Alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted C ₆ -C ₁₂ -aryl radicals,
preferably C ₆ -C ₁₂ -aryl radicals, such as, for example, phenyl, α-naphthyl or β-naphthyl, particularly preferably phenyl;
or
preferably C ₆ -C ₁₂ -aryl radicals which are substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as tolyl, xylyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexylo xyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2-nitrophenyl, 4-nitrophenyl, 2, 4-dinitrophenyl, 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C ₆ F _(5-a) H _a with 0 ≤ a ≤ 5, more preferred 4-tolyl.

Examples of optionally substituted heterocyclyl radicals which may be mentioned are unsubstituted heteroaryl radicals or heteroaryl radicals which are substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles,
preferably 5- or 6-membered heteroaryl radicals which have oxygen, nitrogen and / or sulfur atoms, such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl or benzothiazolyl;
or
preferably 5- or 6-membered heteroaryl radicals which contain oxygen, nitrogen and / or sulfur atoms, such as methylpyridy, dimethylpyridyl, Methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, chloropyridyl, or difluoropyridyl.

If R ^t and R ^u or R ^{t '} and R ^u' together are an optionally substituted -Y _o - (CH ₂ ) _p -, - (CH ₂ ) _q -Y- (CH ₂ ) _r - or a -CH = CH-CH = CH- chain, are preferably a -Y _o - (CH ₂ ) _p -, - (CH ₂ ) _q -Y- (CH ₂ ) _r - or a -CH = CH-CH = CH - chain, especially - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ - or -CH = CH-CH = CH-, in particular - (CH ₂ ) ₅ - or - (CH ₂ ) ₆ - into consideration .
or
a C ₁ -C ₄ alkyl-substituted -Y _o - (CH ₂ ) _p -, - (CH ₂ ) _q -Y- (CH ₂ ) _r - or a C ₁ -C ₄ alkyl-substituted - CH = CH-CH = CH- chain, into consideration.

In an embodiment Carboxylic acid derivatives of the formula V are used in the present invention.

In particular, carboxylic acid derivatives of the formula V are used, where the radicals have the following meanings:
R ^s , R ^{s' are} hydrogen or C ₁ -C ₃₀ alkyl;
T halogen or O-COR ^s' .

Particular preference is given to using carboxylic acid derivatives of the formula V where the radicals have the following meanings:
R ^{s is} hydrogen or C ₁ -C ₁₈ -alkyl, preferably hydrogen or C ₁ -C ₆ -alkyl; particularly preferably methyl, ethyl or butyl;
T halogen, preferably chloride.

Equally particularly preferably, carboxylic acid derivatives of the formula V are used, where the radicals have the following meanings: R ^{s is} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl; T halogen, preferably chloride.

Particular preference is given to using carboxylic acid derivatives of the formula V where the radicals have the following meanings:
R ^s , R ^{s' are} hydrogen or C ₁ -C ₁₈ -alkyl, preferably hydrogen or C ₁ -C ₆ -alkyl; particularly preferably methyl, ethyl or butyl;
T OCOR ^s' .

Extraordinary preference is given to using carboxylic acid derivatives of the formula V in which the radicals R ^s and R ^{s' have} the same meaning ("symmetrical carboxylic anhydrides").

Equally particularly preferably, carboxylic acid derivatives of the formula V are used, the radicals having the following meanings:
R ^{s is} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
T OCOR ^s .

In a further embodiment The present invention uses ketenes of the formula VIa.

In particular, ketenes of the formula Iia are used, where the radicals have the following meanings:
R ^{t is} hydrogen or C ₁ -C ₁₈ -alkyl, preferably hydrogen or C ₁ -C ₆ -alkyl; particularly preferably hydrogen, methyl or ethyl; most preferably hydrogen;
R ^u hydrogen.

Likewise, in particular, ketenes of the formula VIa are used, where the radicals have the following meanings:
R ^{t is} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
R ^u hydrogen.

In a further embodiment The present invention uses diketenes of the formula VIb1.

In particular, diketenes of the formula VIb1 are used, the radicals having the following meanings:
R ^{t is} hydrogen or C ₁ -C ₁₈ -alkyl, preferably hydrogen or C ₁ -C ₆ -alkyl, particularly preferably hydrogen, methyl or ethyl, in particular hydrogen;
R ^u hydrogen.

Likewise particularly preferred are diketenes of the formula VIb1, where the radicals have the following meanings:
R ^{t is} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
R ^u hydrogen.

In a further embodiment The present invention relates to mixed diketenes of the formula VIb2 used.

In particular, mixed diketenes of the formula VIb2 are used, the radicals having the following meanings:
R ^t , R ^{u are} hydrogen or C ₁ -C ₆ -alkyl, preferably hydrogen, methyl or ethyl, in particular hydrogen;
R ^t , R ^{u 'is} hydrogen.

Likewise, in particular, diketenes of the formula VIb2 are used, where the radicals have the following meanings:
R ^t , R ^{u '} 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl
R ^t , R ^{u 'is} hydrogen.

The Acetylation of the silylated cellulose can be analogous to the Expert known methods are performed. It is also possible the reaction of the silylated cellulose in an ionic liquid perform. For this purpose, the silylated cellulose in a, as described above, ionic liquid solved. The concentration of silylated cellulose can in this case in large areas be varied. Usually it is in the range of 0.1 to 50 wt .-%, based on the total weight the solution, preferably at 0.2 to 40 wt .-%, particularly preferably 0.3 to 30 wt .-% and particularly preferably at 0.5 to 20% wt .-%.

This solution process can be carried out at room temperature or under heating, but above the melting or softening temperature of the ionic Liquid, usually at a temperature of 0 to 200 ° C, preferably at 20 to 180 ° C, especially preferably at 50 to 150 ° C. It is also possible the dissolution process by intensive stirring or mixing and by entry of microwave or ultrasonic energy or by speeding up their combination.

To this solution thus obtained Now the acylating agent is given.

The carboxylic acid derivative of the formula V or the ketene of the formula VI can be added in bulk, dissolved in an ionic liquid or in a suitable solvent. Suitable solvents include, for example, ethers, such as diethyl ether, methyl tert-butyl ether, terahydrofuran or dioxane, or ketones, such as dimethyl ketone, or halogenated hydrocarbons, such as dichloromethane, trichloromethane or dichloroethane. The amount of solvent used to dissolve the carboxylic acid derivative of formula V or the ketene of formula VI should be such that no precipitation of the silylated cellulose occurs when adding occurs. As ionic liquid is preferably the one in which the silylated cellulose itself - as described above - is dissolved.

If the carboxylic acid derivative of the formula V or the ketene of the formula VI is gaseous, this may be in the solution the silylated cellulose are gassed in the ionic liquid.

In a particular embodiment becomes the carboxylic acid derivative of the formula V or the ketene of the formula VI in substance.

In another particular embodiment becomes the carboxylic acid derivative of the formula V or the ketene of the formula VI in an ionic liquid solved added, with particular preference the ionic liquid which is also used to solve the cellulose is used.

It there is also the possibility that one or more other solvents be added to the reaction mixture, or with the carboxylic acid derivative of formula V or the ketene of formula VI are supplied. As a solvent come here in such solvents in question, what the solubility do not adversely affect the silylated cellulose, such as aprotic dipolar Solvent, for example, dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane. Furthermore you can also nitrogenous bases, such as pyridine, etc., additionally added become.

In a particular embodiment contains the reaction mixture in addition to the ionic liquid and possibly the solvent, in which the carboxylic acid derivative of the formula V or the ketene of the formula VI is dissolved, less than 5 wt.%, preferably less than 2% by weight, in particular less than 0.1% by weight, Based on the total weight of the Ge mixture, on more solvents and / or additional nitrogenous bases.

In the event that carboxylic acid derivatives of the formula V with T = Hal or OCOR ^s' are used as the acylating agent, it may also be expedient to acylate in the presence of a tertiary amine, such as triethylamine, an aromatic nitrogen base, such as pyridine, or mixtures to do this. The teriary amine, the aromatic nitrogen base or the mixtures thereof are usually used in a stoichiometric ratio. On a case-by-case basis, an excess or a deficit can also be beneficial.

In the event that ketenes of the formula VI are used as the acylating agent, it is also possible to carry out the acylation according to the invention in the presence of a catalyst. Suitable for this purpose are the alkali metal or alkaline earth metal salts of C ₁ -C ₄ -alkanecarboxylic acids or benzoic acid. Examples of these are sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium benzoate or potassium benzoate, preferably sodium acetate. However, it is also possible to use the acids themselves, that is to say the C ₁ -C ₄ -alkanecarboxylic acids or benzoic acid. The catalyst is usually used in amounts of up to 10 mol%, preferably up to 8 mol% based on the ketene of the formula VI.

The Implementation becomes dependent from the ionic liquid used and the carboxylic acid derivative used of the formula V or of the ketene of the formula VI used at a temperature of melting point of the ionic liquid up to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C carried out.

In the case of carboxylic acid derivatives of the formula V or ketenes of the formula VI which are liquid or solid at the reaction temperature, the reaction is usually carried out at ambient pressure. However, it may also be advantageous on a case-by-case basis to work at overpressure, especially when a volatile carboxylic acid derivative of the formula V or ketene of the formula VI is used. As a rule, the reaction is carried out in air. But it is also possible under inert gas, so for example under N ₂ , a noble gas or mixtures thereof, to work.

at Carboxylic acid derivatives of the formula V or ketenes of the formula VI, which are gaseous at the reaction temperature, it may be beneficial to the reaction under the autogenous pressure of Reaction mixture at the desired Reaction temperature to perform or at a pressure higher is, as the autogenous pressure of the reaction system.

However, it may also be advantageous to durchzu the reaction with a carboxylic acid derivative of formula V or a ketene of formula VI, which is gaseous at the reaction temperature, under ambient pressure lead and to use the gaseous carboxylic acid derivative of formula V or the ketene of formula VI in excess.

In dependence from the desired Acylation degree of silylated cellulose is the amount of used Acylating agent - respectively in relation to to the silylated cellulose used - the reaction time and possibly adjusted the reaction temperature.

For example, if it is desired to fully acylate the silylated cellulose (DS 0 <a <3), which is composed on average of u anhydroglucose units, then (3-a) u equivalents of acylating agent are needed. Preferably, the stoichiometric amount of acylating agent (n _{acylating agent} / s _{anhydroglucose units} = 3 - a) or an excess is used, preferably an excess of up to 1000 mol% based on u.

If it is desired to partially acylate the silylated cellulose, which is composed on average of u anhydroglucose units, the amount of acylating agent used is usually adjusted (n _{acylating agent} (s) _{anhydroglucose units} <3-a). The smaller the quotient n _{acylating agent} (s) _{anhydroglucose units} , the lower will be the average degree of substitution of the silylated / acylated cellulose under otherwise identical conditions and the same reaction time.

Farther Is it possible abort the acylation reaction when the desired degree Acylation is achieved by removing the acylated cellulose from the Reaction mixture is separated. This can be done, for example Adding a surplus of water or other suitable solvent in which the acylated / silylated Cellulose not soluble, the ionic liquid but easily soluble is such as a lower alcohol, such as methanol, ethanol, propanol or butanol, or with a ketone, for example diethyl ketone etc., or mixtures thereof, take place. The choice of the suitable solvent is also determined by the respective degree of substitution and the substituents determined the cellulose. Preferably, an excess of water or methanol used.

The Work-up of the reaction mixture is usually carried out by the acylated / silylated Cellulose is precipitated as described above and the acylated / silylated Cellulose is filtered off. But it is also possible separation by centrifugation perform. From the filtrate or the centrifugate can by conventional methods, the ionic liquid be recovered by the volatile components, such. the precipitant, or excess acylating agent (or reaction products and / or hydrolysis products of the acylating agent) etc. are distilled off. The remaining ionic liquid can again in the inventive method be used.

It but it is also possible the reaction mixture in water or in another suitable solvent, in which the acylated / silylated cellulose is insoluble, the ionic liquid but easily soluble is such as a lower alcohol such as methanol, ethanol, propanol or butanol, or a ketone, for example diethyl ketone etc. or mixtures thereof, and depending on the embodiment For example, fibers, films of acylated / silylated cellulose to obtain. The choice of the appropriate Lösusungsmittels is also by the respective degree of substitution and the substituents of the cellulose certainly. The filtrate is worked up as described above.

Farther Is it possible abort the acylation reaction when the desired degree acylation is achieved by cooling the reaction mixture and worked up. The work-up can be described after the above Methods are done.

Of the Termination of the acylation reaction can also be done so that to a given time still existing acylating agent from the reaction mixture by distillation, stripping or extraction with a solvent, that with the ionic liquid forms two phases, is removed.

In another embodiment of the present invention two or more acylating agents used. This can be a Mixture of two (or more) carboxylic acid derivatives of the formula V or Ketenes of the formula VI in analogy to the above procedure be used. But it is also possible first with the first Acylation agent to carry out the reaction to a DS = a '(a <a' <3) and then with a second Acylating the reaction to a DS = b, where a '<b ≤ 3 to perform.

In this embodiment, acylated / silylated celluloses are obtained which contain two (or more rere) carry different acyl radicals (depending on the acylating agent used).

In the case, that the ionic liquid guided in circulation mode becomes, in one embodiment, the ionic liquid purified, for example, from the precipitant, possibly added other solvents, Hydrolysis and degradation products of the acylating agent, etc., and used again. In a further embodiment can the ionic liquid, which up to 15 wt .-%, preferably up to 10 wt .-%, in particular up to 5% by weight of precipitant (s) etc. as described above, be reinstated. This may however be necessary from case to case, for example if the precipitant carries free hydroxy groups, the ionic liquid from still existing precipitant etc., for example, by the remaining precipitant etc. is distilled off, or it is a corresponding excess of acylating agent used.

The Method may be discontinuous, semi-continuous or continuous, carried out become.

In In another embodiment, the cellulose according to the present Invention in an ionic liquid silylated and the resulting silylated cellulose is without isolation directly subjected to the acylation as described above.

The The following examples serve to illustrate the invention.

Preamble:

Avicel PH 101 (microcrystalline cellulose) or tree wolf linters (DP 3250) were over Night at 105 ° C and dried 0.05 mbar.

The ionic liquids were over Night at 120 ° C and 0.05 mbar with stirring dried, except other is stated.

Of the average degree of substitution DS of the silylated cellulose was determined by IR spectroscopic methods, except other indicated.

Abbreviations:

• BMIM

  Ac 1-butyl-3-methylimidazolium acetate

  BMIM

  Benzoate 1-butyl-3-methylimidazolium benzoate

  BMIM

  Cl 1-butyl-3-methylimidazolium chloride

  BMIM

  SCN 1-butyl-3-methylimidazolium thiocyanate

  BMIM

  Prop 1-butyl-3-methylimidazolium propionate

  BMMIM

  Cl 1-butyl-2,3-methylimidazolium chloride

  BzMIM

  Cl 1-Benzyl-3-methylimidazolium chloride

  EMIM

  Ac 1-ethyl-3-methylimidazolium acetate

  EMIM

  DEP 1-ethyl-3-methylimidazolium diethyl

  EMIM

  SCN 1-ethyl-3-methylimidazolium thiocyanate

  HMDS

  hexamethyldisilazane

  NOBA

  N, O-bistrimethylsilylacetamide

  TDMSA

  Thexyldimethylsilylamin

  TMSDA

  -trimethylsilylacetamide

  AGU

  anhydroglucose

  DS

  average degree of substitution

  IL

  ionic liquid

  EA

  Elemental analysis (at Determination of DS)

  NMR

  ¹ H-NMR method (for the determination of DS)

Example 1:

General rule

The ionic liquid (about 10 ml) was introduced into a 100 ml two-necked flask with reflux condenser under dry nitrogen, Avicel PH 101 (about 1.0 g) was added and the mixture was heated to 100 ° C. with stirring. After a clear solution was obtained, first 0.02 g of saccharin was added followed by the HMDS ,

To Stirring for 16 hours at 100 ° C the reaction mixture was cooled and with vigorous stirring in 200 ml of methanol at room temperature. The forming Precipitate was filtered off and washed three times with 20 ml of methanol. The product thus obtained was 14 hours at 60 ° C in vacuo to constant weight dried.

• ^b)Der DS wurde NMR-spektroskopisch bestimmt.

Table 1 below summarizes the results obtained according to this general procedure. Table 1 IL Quantity [ml] HMDS [mmol] n _(AGU) : n _(HMDS) [mol / mol] Yield [% of theory] DS Solubility of the product in toluene THF BMMIM Cl 11 6.8 1: 0.98 81 1.2 + + EMIM SCN 10 6.2 1: 1.01 66 1.0 - - BMIM SCN 10 6.2 1: 0.95 87 0.5 - - BMIM Cl 11 30.9 1: 4.64 51 2.2 + + BMIM Ac 12 30.9 1: 4.61 96 2.9 - - EMIM Ac 11 30.9 1: 4.61 85 2.9 - - BzMIM Cl 12 30.9 1: 4.61 75 2.4 + + BMIM SCN 10 30.9 1: 4.61 74 2.8 + + EMIM SCN 10 30.9 1: 4.61 74 2.7 + + BMMIM Cl 10 31.0 1: 4.63 68 2.8 + + BMIM Cl 10 31.0 1: 5.0 66 2.7 + + BMIM benzoate 10 12.4 1: 2.0 83 2.9 - - BMIM benzoate 10 6.8 1: 1.1 68 2.1 + + BMIM benzoate 10 3.7 1: 0.6 94 0.2 - - BMIM Cl 10 13.6 1: 2.2 82 2.2 + + BMIM Ac 11 14.9 1: 2.3 94 2.9 ^b) BMIM Cl 11 14.9 1: 2.1 82 2.5 ^b) BMIM Prop 11 3.5 1: 0.6 80 1.0 BMIM Prop 11 7.4 1: 1.2 88 2.2 BMIM Prop 11 9.9 1: 1.5 55 3.0 ^b) EMIM DEP 11 3.8 1: 0.6 96 0.9 EMIM DEP 11 6.2 1: 1.1 91 2.3 EMIM DEP 11 9.9 1: 1.54 92 2.6

• ^b) The DS was determined by NMR spectroscopy.

Example 2:

Following the general procedure set forth in Example 1, silyl celluloses were prepared, with the silylating agent being varied. Table 2 below summarizes the results obtained. Table 2 IL Quantity [ml] silylating n _(AGu) : n _(HMDS) [mol / mol] Yield [% of theory] DS BMIM Cl 10 trimethylsilyldiethylamine 1: 3.5 72 2.6 BMIM Ac 10 trimethylsilyldiethylamine 1: 3.8 76 2.9 BMIM Cl 10 NOBA 1: 1.9 83 2.5 BMIM Ac 10 NOBA 1: 1.8 78 2.9 BMIM Cl 10 NOBA 1: 0.6 91 0.5 BMIM Cl 10 NOBA 1: 1.3 74 2.5 BMIM Cl 10 NOBA 1: 0.7 72 1.5

Example 3:

In A 100 mL two-necked flask with reflux condenser was placed under dry Argon 11 ml BMIM Cl, which previously in high vacuum at 100 ° C until Constant weight was dried, initially charged, at 100 ° C 1.17 g Avicel PH 101 added and stirred until a clear solution was obtained. After addition of 0.021 g of saccharin and 2.4 g of HMDS was for another 16 hours at 100 ° C touched, wherein after about 1 hour, the deposition of a solid product the IL started. Subsequently was cooled and the reaction mixture with vigorous stirring in 200 ml of methanol at Room temperature entered. The precipitate was sucked off and washed three times with 20 ml of methanol. The product thus obtained was 14 hours at 60 ° C dried in vacuo to constant weight. One got 2.06 g of a white one Solid (83% of theory), which an average degree of substitution of 2.2 (determined by NMR spectroscopy).

Example 4:

In A 100 mL two-necked flask with reflux condenser was placed under dry Argon 11 ml BMIM Cl, which previously in high vacuum at 120 ° C until Constant weight was dried, initially charged, at 120 ° C 1.02 g Avicel PH 101 added and stirred until a clear solution was obtained. After addition of 0.021 g of saccharin, 2.4 g of HMDS and 20 ml of toluene was used for another 16 hours at 120 ° C touched. After separating the toluene phase, the IL phase was washed 3 times with each 20 ml of toluene extracted. The toluene phases were combined, the solvent removed in vacuo and the residue thus obtained to constant weight dried. This gave 1.66 g of a white solid (83% of theory) with an average degree of substitution of 2.2.

Out the IL phase could be resolved by dilution with 200 ml of water no further product can be isolated.

Example 5:

s1,06 g Avicel PH 101 were dissolved in 12 ml of EMIM Cl at 120 ° C, 2.2 g HMDS and 0.023 g Sacharin was added and stirred for 16 hours at 120 ° C, leaving a solid product was deposited on the IL phase. Then 20 ml of toluene were added, the phases separated and the IL phase three times with 20 ml of toluene extracted. The toluene phases were combined, the solvent removed in vacuo and the residue thus obtained to constant weight dried. 1.83 g of a colorless solid (89% of theory) were obtained. with an average degree of substitution of 2.1.

Out the IL phase could be resolved by dilution with 200 ml of water no further product can be isolated.

Example 6:

2.37 grams of Avicel PH 101 were dissolved in 20 grams of BMIM Cl at 80 ° C, 5.2 grams of HMDS and 0.023 grams of saccharin were added and stirred at 120 ° C for 16 hours to precipitate a solid product on the IL phase. Subsequently, 20 ml of toluene were added, the phases were separated and the IL phase extracted three times with 20 ml of toluene. The toluene phases were combined, the solvent was removed in vacuo and the residue thus obtained was dried to constant weight. This gave 3.6 g of a colorless solid (75% of theory) with an average degree of substitution of 2.3.

Out the IL phase could be resolved by dilution with 200 ml of water no further product can be isolated.

Example 7:

In A 100 mL two-necked flask with reflux condenser was placed under dry Argon 11 ml BMIM Cl, which previously in high vacuum at 100 ° C until Constant weight was dried, submitted, at 100 ° C 0.90 g Avicel PH 101 added and stirred until a clear solution was obtained. After adding 4.0 g of HMDS was added for more 16 hours at 100 ° C touched, wherein after about 1 hour, the deposition of a solid product started on the IL. Subsequently the reaction mixture was cooled and with vigorous stirring in 200 ml of methanol at room temperature. The rainfall was filtered off and washed three times with 20 ml of methanol. The so obtained product was 14 hours at 60 ° C product in vacuo until Constant weight dried. This gave 1.72 g of a white solid (89% of theory) with an average degree of substitution of 2.5 (NMR spectroscopy certainly).

Example 8:

1.02 g Avicel PH 101 were dissolved in 11 g BMIM Cl at 100 ° C, added 2.6 g HMDS and 16 hours at 120 ° C touched, wherein a solid product was deposited on the IL phase. Subsequently, 20 were Toluene was added, the phases separated and the IL phase three times extracted with 20 ml of toluene. The toluene phases were combined, the solvent removed in vacuo and the residue thus obtained to constant weight dried. This gave 1.76 g of a colorless solid (86%). d.Th.) with an average degree of substitution of 2.3.

Out the IL phase could be resolved by dilution with 200 ml of water no further product 5 can be isolated.

Example 9:

General rule

The ionic liquid (about 10 ml) was placed under dry argon in a 100 ml two-necked flask with reflux condenser, heated to 100 ° C., and the biopolymer (about 1.0 g) was added. It is stirred at 100 ° C until a clear solution is formed (about 2 to 4 hours). After a clear solution was obtained, the silylating agent and optionally a catalyst was added , After 16 hours of stirring at 100 ° C, the reaction mixture was cooled and added with vigorous stirring in 200 ml of methanol at room temperature. The precipitate which formed was filtered off with suction and washed three times with 50 ml of methanol each time. The product thus obtained was dried for 14 hours at 60 ° C and 0.05 mbar to constant weight.

• ^d)der DS wurde NMR-spektroskopisch bestimmt
• ^e)der DS wurde per EA bestimmt
• ^f)Zusatz von 0,2 g Saccharin als Katalysator

Table 3 below summarizes the results obtained according to this general procedure. Table 3: IL Quantity [ml] biopolymer Quantity [g] reagent Quantity [g] n _(OH) : n _(reagent) [mol: mol] Yield [% of theory] DS BMIM Cl 11 potato starch 0.917 NOBA 2.5 1: 0.73 66 2.6 ^d) BMIM Cl 11 chitin 0.979 NOBA 3.6 1: 1.84 86 0.9 ^e) BMIM Cl 10 chitosan 0.937 NOBA 3.6 1: 1.52 81 1.4 ^e) BMIM Ac 11 potato starch 1.07 NOBA 2.5 1: 0.62 66 2.7 ^d) BMIM Cl 11 potato starch 1.16 TMSDA ^f) 3.0 1: 0.95 84 2.6 ^d) BMIM Ac 11 potato starch 1.16 TMSDA ^f) 3.2 1: 0.95 66 2.1 BMIM Ac 10 chitin 0.97 TMSDA ^f) 3.2 1: 2.34 82 0.4 ^d) BMIM Cl 11 potato starch 0.943 HMDS ^f) 3.0 1: 0.86 86 2.6 ^d) BMIM Cl 10 chitin 0.281 HMDS ^f) 2.3 1: 5.1 84 0,5 ^e) BMIM Cl 10 chitosan 0.234 HMDS ^f) 2.4 1: 4.97 85 0.4 ^e) BMIM Ac 11 potato starch 1,029 HMDS ^f) 2.2 1: 0.73 79 1.9

• ^d) the DS was determined by NMR spectroscopy
• ^e) the DS was determined by EA
• ^f) Addition of 0.2 g of saccharin as catalyst

Example 10:

General rule

In a 100 ml two-necked flask with reflux condenser, the ionic liquid (about 10 ml) was placed under dry argon, heated to 100 ° C and added AVICEL PH 101 (about 1.0 g). It is stirred at 100 ° C until a clear solution is formed (about 2 to 4 hours). After a clear solution was obtained, the TDMSA and optionally a catalyst was added , After 16 hours of stirring at 100 ° C, the reaction mixture was cooled and added with vigorous stirring in 200 ml of methanol at room temperature. The precipitate which formed was filtered off with suction and washed three times with 50 ml of methanol each time. The product thus obtained was dried for 14 hours at 60 ° C / 0.05 mbar product to constant weight.

• ^h)der DS wurde NMR-spektroskopisch bestimmt
• ⁱ⁾Zusatz von 0,2 g Saccharin als Katalysator

Table 4 below summarizes the results obtained according to this general procedure. Table 4: IL Quantity [ml] TDMSA [mmol] n _(AGU) : n _(TDMSA) [mol: mol] Yield [% of theory] DS ^h) BMIM Cl 11 19.4 1: 3.3 87 0.9 BMIM Cl 11 6.5 1: 1 92 0.4 BMIM Cl 11 11.5 1: 1.9 97 0.7 BMIM Cl 11 18.8 1: 3.1 94 1.1 BMIM Ac 11 19.4 1: 3.5 80 1.3 BMIM Ac 11 7.7 ⁱ⁾ 1: 1.3 72 0.6 BMIM Ac 11 12.7 ⁱ⁾ 1: 2.1 76 1.1 BMIM Prop 11 17.6 1: 2.9 85 1.2 BMIM benzoate 11 18.4 1: 3.0 85 2.1 EMIM DEP 11 19.3 1: 3.4 83 1.9

• ^h) the DS was determined by NMR spectroscopy
• ⁱ⁾ Addition of 0.2 g of saccharin as catalyst

Example 11:

1.0 g of cotton linters were dissolved in 10 ml of BMIM Cl containing 200 ppm of water by stirring for 4 hours at 120 ° C (n _(AGu) : n _(H2O) = 55: 1). After 2 hours of stirring at 150 ° C was cooled to 80 ° C, 6.0 g of HMDS was added and stirred at 80 ° C for 16 hours. The reaction mixture was then stirred into 200 ml of methanol, the precipitate filtered off, washed three times with 20 ml of methanol and dried at 60 ° C and 0.05 mbar to constant weight. The product thus obtained was used in a yield of 84% d. Th. And has a DP of 57 (determined by gel permeation chromatography) and a DS of 2.1 (determined by NMR).

Example 12:

General rule

• A: Nach Abkühlen wurde die Benzolphase abgetrennt, und die IL-Phase zweimal mit je 25 ml Benzol extrahiert. Die vereinigten Benzolphasen wurden gefriergetrocknet.
• B: Nach Abkühlen wurde das Reaktionsgemisch mit 20 ml Cyclohexan versetzt, die obere Phase abgetrennt und gefriergetrocknet.

1.0 g of cotton linters were dissolved in 10 ml of BMIM Cl by stirring at 120 ° C for 4 hours. Then the amount of water indicated in Table 5 was added, heated to 150 ° C and stirred for the time indicated in Table 1 at this temperature. It was then cooled to 80 ° C, 6.0 g of HMDS and 25 ml of benzene and stirred at 80 ° C for 16 hours. The workup was carried out according to the following variants:

• A: After cooling, the benzene phase was separated and the IL phase was extracted twice with 25 ml of benzene each time. The combined benzene phases were freeze-dried.
• B: After cooling, the reaction mixture was mixed with 20 ml of cyclohexane, the upper phase separated and freeze-dried.

• ^j)der DP wurde mittels Gelpermeationschromatographie bestimmt
• ^k)der DS wurde NMR-spektroskopisch bestimmt

Table 5 below summarizes the results obtained according to this general procedure. Table 5: n _(AGU) : n _(H2O) [mol / mol] Amount of water Time at 150 ° C [h] workup Yield [% of theory] DP ^j) DS ^k) 2: 1 0.05 ml (2.9 mmol) 3 A 98 26 2.2 2: 1 0.05 ml (2.9 mmol) 4 A 100 15 2.1 2: 1 0.05 ml (2.9 mmol) 6 A 81 11 2.2 1: 1.8 0.2 ml (11.1 mmol) 15 B 86 1 4.7

• ^j) the DP was determined by gel permeation chromatography
• ^k) the DS was determined by NMR spectroscopy

Example 13:

General rule

In A 100 mL two-necked flask with reflux condenser was placed under dry Nitrogen the ionic liquid (about 10 ml) submitted, Avicel PH 101 (about 1.0 g) was added and under stir heated. Having a clear solution was first added 0.02 g of saccharin and then the Amount of HMDS as indicated in Table 6. After stirring for 16 hours the temperature indicated in Table 6 became the reaction mixture chilled and either with vigorous stirring entered in 200 ml of methanol at room temperature, the forming Filtered off and washed three times with 20 ml of methanol, or extracted with toluene and the toluene phase is concentrated. That so The product obtained was dried for 14 hours to constant weight.

Table 6 below summarizes the results obtained according to this general procedure. Table 6 IL n _(AGU) : n _(HMDS) [mol / mol] Temperature [° C] DS BMIM Cl 1: 1 80 0.2 BMIM Cl 1: 2 80 2.1 BMIM Cl 1: 1 100 1.1 BMIM Cl 1: 4.6 100 2.4 BMIM Cl 1: 1 120 1.0 BMIM Cl 1: 2 120 2.0 BMMIM Cl 1: 2 100 2.3 BMMIM Cl 1: 4.6 120 2.6 BMIM Ac 1: 0.5 80 0.2 BMIM Ac 1: 1 80 0.2 BMIM Ac 1: 2.2 80 2.8 BMIM Ac 1: 2.2 100 2.8 BMIM Ac 1: 1 120 1.1 BMIM Ac 1: 2.5 120 2.7 EMIM Ac 1: 4.6 100 2.8

Example 14:

General rule

• A: Gefriergetrocknung
• B: Extraktion mit einen aromatischen Lösungsmittel

1.0 g of hydrate cellulose was stirred in 10 ml of BMIM Cl containing 200 ppm of water at 120 ° C for 4 hours. It was then heated to 150 ° C and stirred for the time indicated in Table 7 at this temperature. It was then cooled to 80 ° C, 6.0 g of HMDS and stirred at 80 ° C for 16 hours. The workup was carried out according to the following variants:

• A: freeze-drying
• B: extraction with an aromatic solvent

• ^l)der M_w wurde mittels Gelpermeationschromatographie bestimmt
• ^m)der DS wurde NMR-spektroskopisch bestimmt

Table 7 below summarizes the results obtained according to this general procedure. Table 7: Time at 150 ° C [h] workup M _w ^l) DS ^m) 2 A 7750 2.3 15 B 770 3.8

• ^l) the M _w was determined by gel permeation chromatography
• ^m) the DS was determined by NMR spectroscopy

Claims (20)

Process for the silylation of poly-, oligo- or disaccharides, or derivatives thereof, characterized in that one dissolves a poly-, oligo- or disaccharide, or the corresponding derivative, in at least one ionic liquid and reacted with a silylating agent. Method according to claim 1, characterized in that that as poly, oligo- or Disaccharide, or a derivative thereof, a polysaccharide, or a derivative thereof. Method according to claim 2, characterized in that that as polysaccharide, or a derivative thereof, cellulose, or a cellulose derivative. Method according to claim 3, characterized that as polysaccharide, or a derivative thereof, cellulose starts. Process according to Claims 1 to 4, characterized in that the ionic liquid, or mixtures thereof, are chosen from the compounds of the formulas I, [A] + / n [Y] ^n- (I), where n is 1, 2, 3 or 4; [A] ⁺ for a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation; and [Y] ^n- for a mono-, di-, tri- or tetravalent anion; stand; or the compounds of the formula II [A ¹ ] ⁺ [A ² ] ⁺ [Y] ^n- (IIa), where n = 2; [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [Y] ^n- (IIb), where n = 3; or [A ¹ ] ⁺ [A ² ] ⁺ [A ³ ] ⁺ [A ⁴ ] ⁺ [Y] ^{n -} (IIc) wherein n = 4 and wherein [A1] ⁺ , [A2] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ ; and [Y] ^{n- have} the abovementioned meaning. A method according to claim 5, characterized in that [A] ⁺ for a cation selected from the compounds of formulas (IIIa) to (IIIy)

and oligomers containing this structure, wherein • the radical R is hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Radical with 1 to 20 carbon atoms; and • the radicals R ¹ to R ⁹ independently of one another are hydrogen, a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups substituted radical having 1 to 20 carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (III) to a carbon atom (and not to a heteroatom) ge connected, may additionally be halogen or a functional group ; or two adjacent radicals from the series R ¹ to R ⁹ together also represent a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups with 1 to 30 carbon atoms, can stand; wherein when IIIw is III, then R ³ is not hydrogen. Process according to claims 5 or 6, characterized in that [Y] ^n- for an anion is selected from • the group of halides and halogen-containing compounds of the formula: F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₃ ) ₂ N ^- , CF ₃ CO ₂ ^- , CCl ₃ CO ₂ ^- , CN ^- , SCN ^- , OCN ^- • the group of sulfates, sulfites and sulfonates of general Formula: SO ₄ ^2- , HSO ₄ ^- , SO ₃ ^2- , HSO ^3- , R ^a OSO ₃ ^- , R ^a SO ₃ ^- • the group of phosphates of the general formula PO ₄ ^3- , HPO 4 ^2- , H ₂ PO ₄ ^- , R ^a PO ₄ ^2- , HR ^a PO ₄ ^- , R ^a R ^b PO ₄ ^- • the group of phosphonates and phosphinates of the general formula: R ^a HPO ₃ ^- , R ^a R ^b PO ₂ ^- , R ^a R ^b PO ₃ ^- • the group of phosphites of the general formula: PO ₃ ^3- , HPO ₃ ^2- , H ₂ PO ^3- , R ^a PO ₃ ^2- , R ^a HPO ₃ ^- , R ^a R ^b PO ₃ ^- • the group of phosphonites and phosphinites of the general formula: R ^a R ^b PO ₂ ^- , R ^a HPO ₂ ^- , R ^a R ^b PO ^- , R ^a HPO ^- • the group of carboxylic acids of the general formula: R ^a COO ^- • the group of bristles of general formula: BO ₃ ^3- , HBO ₃ ^2- , H ₂ BO ₃ ^- , R ^a R ^b BO ₃ ^- , R ^a HBO ₃ ^- , R ^a BO ₃ ^2- , B (OR ^a ) (OR ^b ) ( OR ^c ) (OR ^d ) ^- , B (HSO ₄ ) ^- , B (R ^a SO ₄ ) ^- • the group of boronates of the general formula: R ^a BO ₂ ^2- , R ^a R ^b BO ^- • the group of Silicates and silicic acid esters of the general formula: SiO ₄ ^4- , HSiO ₄ ^3- , H ₂ SiO ₄ ^2- , H ₃ SiO ₄ ^- , R ^a SiO ₄ ^3- , R ^a R ^b SiO ₄ ^2- , R ^a R ^b R ^c SiO ₄ ^- , HR ^a SiO ₄ ^2- , H ₂ R ^a SiO ₄ ^- , HR ^a R ^b SiO ₄ ^- • the group of the alkyl or aryl silane salts of the general formula: R ^a SiO ₃ ^3- , R ^a R ^b SiO ₂ ^{2 -,} R ^a R ^b R ^c SiO ^-, R ^a R ^b R ^c SiO ₃ ^-, R ^a R ^b R ^c SiO ₂ ^-, R ^a R ^b SiO ₃ ^2- • the group of carboximides, bis (sulfonyl) imides and sulfonylimides of the general formula:

The group of methides of the general formula:

where the radicals R ^a, R ^b, R ^c and R ^d are each independently hydrogen, C _1-30 alkyl, optionally substituted by one or more nonadjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted Imino groups interrupted C ₂ -C ₁₈ alkyl, C ₆ -C ₁₄ aryl, C ₅ -C ₁₂ cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle, wherein two of them together unsaturated, saturated or aromatic, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups interrupted ring, said radicals each additionally by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy , Halogen, heteroatoms and / or heterocycles may be substituted; stands. Process according to claims 5 to 7, characterized in that [A] ^{+ represents} a cation selected from the group of the compounds IIIa, IIIe, IIIf; IIIg, IIIg ', IIIh, IIIi, IIIj, IIIj', IIIk, IIIk ', IIIl, IIIm, IIIm', IIIn or IIIn '. Process according to claims 5 to 8, characterized in that [A] ^{+ is} a cation selected from the group of compounds IIIa, IIIe or IIIf. Process according to Claims 5 to 9, characterized in that [Y] ^{n- represents} an anion selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, of the group comprising SO ₄ ^2- , SO ₃ ^2- , R ^a OSO ₃ ^- and R ^a SO ₃ ^- , and the group containing PO ₄ ^3- and R ^a R ^b PO ₄ ^- stands. Process according to claims 1 to 10, characterized in that the silylating agent is a compound of formula IV

where the radicals have the following meaning: R ^x , R ^y , R ^{z is} C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, C ₂ -C ₃₀ -alkynyl, C ₃ -C ₁₂ -cycloalkyl, C ₅ - C ₁₂ -cycloalkenyl or aryl, where these six radicals may optionally be substituted; X is halogen, NH ₂ , imidazol-1-yl, di- (C ₁ -C ₆ -alkyl) -amine, NH-SiR ^x R ^y R ^z , NH-CO-NH-SiR ^x R ^y R ^z , NHCO- (C ₁ -C ₆ -alkyl), N (C ₁ -C ₆ -alkyl) -CO- (C ₁ -C ₆ -alkyl), N (C ₁ -C ₆ -alkyl) -CO- (C ₁ -) C ₆ haloalkyl), O-SO ₂ - (C ₁ -C ₆ alkyl), O-SO ₂ - (C ₁ -C ₆ haloalkyl), OC (= N-SiR ^x R ^y R ^z ) - ( C ₁ -C ₆ -alkyl) or OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ -haloalkyl); used. A process as claimed in claim 11, wherein the radicals of the silylating agents of the formula IV have the following meanings: R ^x , R ^{y '} , R ^{z is} C ₁ -C ₃₀ -alkyl or aryl, where these radicals may optionally be substituted; X is halogen, imidazol-1-yl, di- (C ₁ -C ₆ -alkyl) -amine, NH-SiR ^u R ^v R ^w , OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ alkyl) or OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₆ haloalkyl). A process as claimed in claim 12, wherein the radicals of the silylating agents of the formula IV have the following meanings: R ^x , R ^{y '} , R ^z', C ₁ -C ₆ -alkyl or phenyl; X is chlorine, di (C ₁ -C ₄ alkyl) amine, NH-SiR ^x R ^y R ^z , OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₄ alkyl) or OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₄ haloalkyl). A process according to claim 13, wherein the radicals of the silylating agents of the formula IV have the following meaning: R ^x , R ^{y '} , R ^{z' is} C ₁ -C ₆ -alkyl; X is di- (C ₁ -C ₄ -alkyl) -amine, NH-SiR ^x R ^y R ^z , OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₄ -alkyl) or OC (= N-SiR ^x R ^y R ^z ) - (C ₁ -C ₄ haloalkyl). Process according to claims 1 to 14, characterized that the concentration of poly, oligo- or disaccharide, or one Derivatives thereof, in ionic liquid in a range of 0.1 to 50 wt .-% based on the total weight of the solution. Process according to claims 1 to 15, characterized that the reaction at a temperature from the melting point of the ionic liquid up to 200 ° C carried out becomes. Process according to claims 1 to 16, characterized that the silylation of the polysaccharide by addition of a Solvent, in which the silylated polysaccharide is insoluble, quenches. Process for the silylation of poly, oligo- or Disaccharides, or derivatives thereof, characterized in that a poly- or oligosaccharide, or the corresponding derivative, in at least one ionic liquid triggers and in Step A) with at least one acid, optionally with the addition of Water, (step A1), or if necessary with the addition of water, at increased Temperature (step A2), treated and in Step B) that way obtained poly-, oligo or disaccharide, or derivative thereof, the DP is lower than that of the poly- or oligosaccharide used, with a silylating agent, according to claims 1 to 16 implemented. Process for the acylation of silylated poly, Oligo- or disaccharides, or derivatives thereof, characterized that in a first step a poly-, oligo- or disaccharide, or the corresponding derivative, in at least one ionic liquid triggers and with a silylating agent according to claims 1 to 18, and then acylated. The method of claim 20, wherein both the reaction of the poly, oligo- or Disaccharide, or a derivative thereof, with the silylating agent as well as the subsequent one Acylation in an ionic liquid, as in the claims 5 to 10 described performed become.