EP1994060A1

EP1994060A1 - Method for breaking down cellulose

Info

Publication number: EP1994060A1
Application number: EP07726534A
Authority: EP
Inventors: Klemens Massonne; Giovanni D'andola; Veit Stegmann; Werner Mormann; Markus Wezstein; Wei Leng; Stephan Freyer
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-03-08
Filing date: 2007-02-28
Publication date: 2008-11-26
Also published as: AU2007222456A1; WO2007101812A1; KR20080110608A; JP2009529075A; BRPI0708584A2; US20090020112A1; CA2642866A1

Abstract

The invention relates to a method for breaking down cellulose by dissolving the cellulose in an ionic liquid and treating it at elevated temperatures, optionally in the presence of water.

Description

Process for the degradation of cellulose

The present invention describes a process for the degradation of cellulose by dissolving the cellulose in an ionic liquid and treating it at elevated temperature, optionally in the presence of water.

Cellulose is the most important renewable raw material and represents an important starting material for, for example, the textile, paper and nonwoven industries. It also serves as a raw material for derivatives and modifications of cellulose, to which cellulose ethers, such as, for example, Methylcellulose and carboxymethylcellulose, cellulose esters based on organic acids, e.g. Cellulose acetate, cellulose butyrate, and cellulose esters based on inorganic acids, e.g. Cellulose nitrate, and others count. These derivatives and modifications find a variety of applications, for example in the food, construction and paint industries.

Cellulose is characterized by insolubility, especially in common solvents of organic chemistry. In general, N-methyl-morpholine-N-oxide, anhydrous hydrazine, binary mixtures such as methylamine / dimethyl sulfoxide, or ternary mixtures such as ethylenediamine / SO 2 / dimethyl sulfoxide are used as solvent today. However, it is also possible to use saline systems, e.g. LiCl / dimethylacetamide, LiCl / N-methylpyrrolidone, potassium thiocyanate / dimethyl sulfoxide, etc.

Rogers et al. have recently reported (J. Am. Chem. Soc., 124, 4974 (2002)) that cellulose is oxidized in ionic liquids, such as e.g. [1-butyl-3-methyl-imidazolium] chloride is soluble.

Usually, cellulose is characterized by the average degree of polymerization (DP). The DP of cellulose depends on its origin; so the DP of raw cotton can be up to 12,000. Usually, cotton linters have a DP of 800 to 1800 and in wood pulp it is in the range of 600 to 1200. For many applications, however, it is desirable to use cellulose having a DP which is lower than the above, and it is also desirable to have the proportion to reduce polymers with high chain length.

For the degradation of cellulose, various methods are known which can be divided into four groups - the mechanical degradation, the chemical degradation, the degradation by the action of radiation and the thermal degradation (D. Klemm et al., Comprehensive Cellulose Chemistry, Vol , Pp. 83-127, Wiley Verlag, 1998). In mechanical degradation, such as in dry or wet grinding, it is disadvantageous that the DP of the cellulose is reduced only to a small extent.

As chemical degradation methods, the acidic, the alkaline and the oxidative degradation, in addition to the enzymatic known.

In acidic heterogeneous degradation, for example, the cellulose is suspended in dilute mineral acid and treated at elevated temperature. In this method it is found that the DP of the cellulose (degraded cellulose) obtained after the work-up does not fall under the so-called "level-off DP" (LOPD). The LODP appears to be related to the size of the crystalline regions of the cellulose employed. It is dependent on the cellulose used, but also on the reaction medium, if, for example, solvents, such as dimethyl sulfoxide, water, alcohols or methyl ethyl ketone are additionally added. In this method, the yield of degraded cellulose is low, because the amorphous regions or the accessible regions of the cellulose are completely hydrolyzed.

Furthermore, it is also possible to subject cellulose in a homogeneous system to an acidic degradation. In this case, cellulose is dissolved, for example, in a mixture of LiCl / dimethylformamide and treated with an acid. In this method, the preparation of the solution is very complicated, the work-up complicated and low the yield of degraded cellulose.

In the alkaline degradation of cellulose, glucose is gradually split off at the so-called reducing terminus of the cellulose. This leads to low yields of degraded cellulose.

The oxidative degradation of cellulose is usually carried out with oxygen. As a preliminary step, it usually involves the formation of individual anhydroglucose units, which react further to form unstable intermediates and ultimately lead to a chain break. The control of this reaction is usually difficult.

When degraded by radiation, cellulose can be treated with high-energy radiation, such as X-radiation. Here, the DP of the cellulose is lowered very quickly. However, chemical modification of the cellulose also occurs by forming a high number of carboxylic acid or keto functions. On the other hand, if less energy-rich radiation is used, such as UV / visible light, it is necessary to use photosensitizers. And here, too, there is a modification of the cellulose by formation of keto Functional, or if oxygen is present during the irradiation, to peroxide formation.

An uncontrolled degradation takes place in the thermal treatment and also the cellulose is modified, in particular dehydrocelluloses can be formed.

The abovementioned methods therefore have various disadvantages and there is therefore a need for a simplified process for the degradation of cellulose, which takes place without modification of the polymer and in high yields.

A process has now been found for degrading cellulose by dissolving cellulose in an ionic liquid and treating this solution at elevated temperatures, optionally in the presence of water.

Ionic liquids in the sense of the present invention are preferred

(A) Salts of the general formula (I)

[A]; [Yf- (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] ^π "is a one-, two- or more -, tri- or tetravalent anion stands;

(B) mixed salts of the general formulas (II)

[A ¹ J ⁺ [A ² J ⁺ [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 - (Mc), where n = 4 and

where [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ^{+ are} independently selected from the groups mentioned for [A] ⁺ and [Y] ⁿ "is the meaning mentioned under (A) has.

Preferably, the ionic liquids have a melting point of less than 180 ° C. More preferably, the melting point is in a range of -50 ° C to 150 ° C, more preferably in the range of -20 ° C to 120 ° C, and most preferably below 100 ° C.

Compounds which are suitable for forming the cation [A] ⁺ of ionic liquids are known, for example, from DE 102 02 838 A1. So can such connections Oxygen, phosphorus, sulfur or in particular nitrogen atoms, for example at least one nitrogen atom, preferably 1 to 10 nitrogen atoms, particularly preferably 1 to 5, very particularly preferably 1 to 3 and in particular 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 where the nitrogen atom is the carrier of the positive charge in the cation of the ionic liquid, in the synthesis of the ionic liquids a cation can first be generated by quaternization on the nitrogen atom of, for example, an amine or nitrogen heterocycle. The quaternization can be carried out by alkylation of the nitrogen atom. Depending on the alkylating reagent used, salts with different anions are obtained. In cases where it is not possible to form the desired anion already during quaternization, this can be done in a further synthesis step. Starting from, for example, an ammonium halide, the halide can be reacted with a Lewis acid to form a complex anion from halide and Lewis acid. Alternatively, replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt with precipitation of the metal halide formed, via an ion exchanger or by displacement of the halide ion by a strong acid (with liberation of the hydrohalic acid). Suitable methods are, for example, in Angew. Chem. 2000, 12, pp. 3926-3945 and the literature cited therein.

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

Preference is given to those compounds which contain at least one five- to six-membered heterocycle, in particular a five-membered heterocycle, which has at least one nitrogen atom and, if appropriate, an oxygen or sulfur atom. Also particularly preferred are those compounds containing at least one 5- to 6-membered heterocycle having one, two or three nitrogen atoms and one sulfur or one oxygen atom, most preferably those having two nitrogen atoms. Further preferred are aromatic heterocycles. Particularly preferred compounds are those which have a molecular weight below 1000 g / mol, very particularly preferably below 500 g / mol and in particular below 350 g / mol.

Furthermore, preference is given to those cations which are selected from the compounds of the formulas (IIIa) to (IIIw),

Ia) (MIb) (MIc)

(MId) (MIe) (MIf)

Ciig> (mg ¹ ) (MIh)

(NU) (MIj ')

(MIm) (MIm ') (MIn)

(MIp) (MIq) (MIq ')

(HIq ") (Me) (MIr ')

(MIr ") (MIs) (With)

(MIu) (MIv) (MIw)

and oligomers containing these structures.

Further suitable cations are compounds of the general formula (IMx) and (MIy)

R ² R ²

₃ 1 -H ₁ I + ₁

R-P-R S-R

I I R R

(MIx) (MIy)

and oligomers containing this structure.

In the above formulas (IMa) to (IMy) stand

• the radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups and having 1 to 20 carbon atoms; and • the radicals R ¹ to R ⁹ independently of one another represent hydrogen, a sulfo

Group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or ar-aliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical or 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), may additionally 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 Residue with 1 to 30 carbon atoms.

As hetero atoms, in the definition of the radicals R and R ¹ to R ^{9, 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-, -SO2-, -NR'-, -N =, -PR'-, -PR'3 and -SiRV, where the radicals R 'is the remainder of the carbon-containing residue. The radicals R ¹ to R ⁹ are, in the cases in which these are attached in the above formulas (III) to a carbon atom (and not to a heteroatom), 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. Suitable examples are -OH (hydroxy), = 0 (especially as carbonyl group), -NH 2 (amino), -NHR ', -NR ₂ ', = NH (imino), = NR ', -COOH (carboxy), - CONH ₂ (carboxamide), -SO3H (sulfo) and -CN (cyano). Functional groups and heteroatoms may 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 (Ci-C4-alkyl) amino, Ci-C4-alkyloxycarbonyl or Ci-C4-alkyloxy. The radicals R 'are the remaining part of the carbon-containing radical.

Halogens are fluorine, chlorine, bromine and iodine. The radical R preferably stands for

• C 1 -C 20 -alkyl which is unsubstituted or branched, unsubstituted or monosubstituted to hydroxyl, halogen, phenyl, cyano, C 1 -C 6 -alkoxycarbonyl and / or SO 3 H 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, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) - et hyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;

Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C 1 -C 5 -alkyl end group, such as 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 θ) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^{B is} preferably hydrogen, methyl or ethyl and m is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6 Dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 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-Ci-Cδ-alkyl-amino, such as N, N-dimethylamino and N ₁ N-diethylamino.

The radical R particularly preferably represents unbranched and unsubstituted C 1 -C 6 -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 also CH ₃ O- (CH ₂ CH ₂ O) _m -CH ₂ CH2 and _CH3 CH2θ- (CH2CH2θ) _m -CH ₂ CH 2 with m = 0 to. 3

The radicals R ¹ to R ⁹ are preferably each independently • hydrogen;

• halogen;

• a functional group;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups cis-alkyl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups cis alkenyl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-cycloalkyl;

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-cycloalkenyl; or

• an optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle; or

two adjacent radicals together for

An unsaturated, saturated or aromatic, if appropriate by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or

Heterocycles substituted and optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups ring.

Optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles d-cis-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, cyclohexylmethyl, 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-D 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-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3 Methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 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) + (ib) H 2 a + b with m equal to 1 to 30, 0 <a <m and b = 0 or 1 (for example CF3, C2F5, CH2CH2-C ( _m -2) F2 (m-2) + i, C ₆ Fi ₃ , C ₈ Fi ₇ , C10F21, Ci ₂ 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, butylthio-methyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl , 8-hydroxy-3,6-dioxo-octyl, 11-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 1-hydroxy-4,8-dioxa-undecyl, 15-hydroxy-4,8,12-trioxa-pentadecyl, 9-hydroxy-5-oxo-nonyl, 14-hydroxy-5,10-dioxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy 3,6-dioxo-octyl, 1-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1-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-oxato-tetradecyl.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and / or substituted by one or a plurality of oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino interrupted C2-Ci8-alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _m F2 (ma) - (ib) H2a-b with in <30, 0 <a <m and b = 0 or 1.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C6-Ci2-aryl is preferably phenyl, ToIyI, XyIyI, α-naphthyl, ß-naphthyl, 4-diphenylyl, Chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, 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-dimethylamino-phenyl, 4-acetylphenyl, methoxyethylphenyl, ethoxymethylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl or C6F (5- _a ) H _a with 0 <a <5.

C 5 -C 12 -cycloalkyl optionally substituted by 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) - (ib) 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.

When optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C5-Ci2-cycloalkenyl is preferably 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclo hexadienyl or C _n F2 _(m -a) -3 (ib) H2a-3b where m <30, 0 <a <m and b = 0 or the first

An optionally substituted by 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 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 several 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-Ci-C4-alkyl 1-aza-1, 3-propenylene, 1,4-butan-1, 3-dienylene, 1-az-1, 4-buta-1,3-dienylene or 2-aza-1,4-buta-1, 3-dienylene.

If the abovementioned radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups, the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the remainder, preferably not more than 4 and very particularly preferably not more than 3.

If the abovementioned radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.

Particularly preferably, the radicals R ¹ to R ⁹ are each independently

• hydrogen;

• straight-chain or branched, unsubstituted or monosubstituted to polysubstituted by hydroxyl, halogen, phenyl, cyano, C 1 -C 6 -alkoxycarbonyl and / or SO 3 H substituted C 1 -C 20 -alkyl having in total 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, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl,

Undecylfluoroisopentyl, 6-hydroxyhexyl and propylsulfonic acid;

Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C 1 to C 1 alkyl as end group, such as 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 is} preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 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.

Most preferably, the radicals R ¹ to R ⁹ are each independently hydrogen or Ci-Cis-alkyl, such as methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, phenyl for 2-hydroxyethyl, 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 as well as for CH3O-

(CH ₂ CH2θ) _m -CH ₂ CH 2 and CH ₃ CH2θ- (CH2CH2θ) _m -CH ₂ CH 2 with m = 0 to. 3

Very particularly preferred pyridinium ions (Ulla) are those 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} carboxy or 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 are} 1, 4-buta-1, 3-dienylene and the remaining 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. Particularly preferred pyridinium ions (IIIa) which may be mentioned 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-yl methyl-pyridinium, 1- (1-butyl) -2-methyl-3-ethyl-pyridinium, 1- (1-hexyl) -2-methyl-3-ethyl-pyridinium and 1- (1-oct yl) -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-ethyl-pyridinium.

Very particularly preferred pyridazinium ions (MIb) 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.

Very particularly preferred pyrimidinium ions (MIc) 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.

Very particularly preferred pyrazinium ions (MId) 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.

Very particular preference is given to imidazolium ions (Nie) such as those in which

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

Very particularly preferred imidazolium ions (MIe) which may be mentioned are 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-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 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-methyl imidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3- methyl imidazolium, 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 and 1- (prop-1-en-3-yl) -3-methylimidazolium.

Very particularly preferred pyrazolium ions (MIf), (MIg) or (MIg ') are those in which

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

Very particular preference is given as Pyrazoliumionen (IMh) such, in which

Are • R ¹ to R ⁴ are independently hydrogen or methyl. Very particular preference is given to using as 1-pyrazolinium (Uli) those in which

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

Very particularly preferably used as 2-pyrazolinium (IMj) or (MIj ') such, in which

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

Very particular preference is given as 3-pyrazolinium (MIk) or (IMk ') such, 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.

Very particularly preferred imidazolinium ions (IUI) 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.

Very particularly preferred as Imidazoliniumionen (Ulm) or (MIm ') are 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.

Very particular preference is given to using as imidazolinium ions (IMn) or (MIn ') 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.

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

• R ^{1 is} hydrogen, methyl, ethyl or phenyl and R ² and R ^{3 are} independently hydrogen or methyl. Very particular preference is given to using as 1,2,4-triazolium ions (NIq), (HIq ') or (MIq ") those in which

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

Very particular preference is given to using as 1,3,3-triazolium ions (Mir), (IMr ') or (MIr ") those 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.

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

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

With very particular preference one uses as imidazolidinium ions (mit) 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.

Very particular preference is given as ammonium ions (MIu) such, in which

• R ¹ to R ^{3 are} independently of each other Ci-Cis-alkyl; or

• R ¹ and R ² together are 1, 5-pentylene or 3-oxa-1, 5-pentylene and R ^{3 is} Ci-Cis-alkyl, 2-hydroxyethyl or 2-cyanoethyl.

As very particularly preferred ammonium ions (IMu) may be mentioned methyl tri (1-butyl) -ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.

Examples of the tertiary amines of which the quaternary ammonium ions of the general formula (IMu) are derived by quaternization with the radicals R mentioned are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl hexylamine, 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-isopropyl-butylamine, di-isopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, di-isopropyl-2-ethylhexyl amine, di-n-butylethylamine, di-n-butyl-n-propylamine, di-n-butyl-n-pentylamine, di-n-butylhexylamine, di-n-butyloctylamine, di-n-butyl (2-methyl) ethylhexyl) amine, Nn-butylpyrrolidine, N-sec-butylpyrrodidine, N-tert-butylpyrrolidine, Nn-pentylpyrrolidine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-di-n-butylcyclohexylamine, Nn -Propylpiperidine, N-isopropylpiperidine, Nn-butylpiperidine, N-sec-butylpiperidine, N-tert-butylpiperidine, Nn-pentylpiperidine, Nn-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, Nn-pentylmorpholine , N-benzyl-N-ethylaniline, N-benzyl-Nn-propylaniline, N-benzyl-N-iso-propylaniline, N-benzyl-Nn-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 tertiary amines (MIu) are di-iso-propylethylamine, diethyl-tert-butylamine, di-iso-propylbutylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.

Particularly 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.

Very particularly preferred as guanidinium ions (MIv) are those in which

• R ¹ to R ⁵ are methyl.

As a very particularly preferred guanidinium ion (MIv) may be mentioned N, N, N ', N', N ", N" - hexamethylguanidinium.

Very particularly preferred as cholinium ions (MIw) are those in which

• R ¹ and R ^{2 are} independently methyl, ethyl, 1-butyl or 1-octyl and R ^{3 is} hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ ;

• 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 hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ ; 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 hydrogen, methyl, ethyl, acetyl, -SO ₂ OH or -PO (OH) ₂ are. Particularly preferred cholinium ions (MIw) are those in which R ^{3 is} selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 1 1-methoxy 3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1-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-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-oxo nonyl or 14-ethoxy-5,10-oxato-tetradecyl.

Very particularly preferred phosphonium ions (IMx) are those in which

• R ¹ to R ^{3 are} independently C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.

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

Particular preference is given to 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-ethyl-pyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium, 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1 - ( 1-dodecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-tetradecyl) -2-methyl-3-ethyl-pyridinium, 1- (1-hexadecyl) -2-methyl-3-ethyl-pyri dinium, 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-methyl-imidazolium , 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-dimethylimidazolium, 1- (1-hexyl) -2 , 3-dimethylimidazolium and 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.

As anions, in principle, all anions can be used.

The anion [Y] ⁿ - 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 SOs) ₂ N-, CF ₃ CO ₂ -, CCI 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 ³ OSO ₃ -, R ³ SO ₃ -

The group of phosphates of the general formula PO ₄ ^{3 "} , HPO ₄ ^2" , H ₂ PO ₄ -, R ³ PO ₄ ^{2 "} , HR ³ PO ₄ -, R ³ R ^b PO ₄ -

The group of phosphonates and phosphinates of the general formula: R ³ H PO ₃ -, R ³ R ^b PO ₂ -, R ³ R ^b PO ₃ -

The group of phosphites of the general formula: PO ₃ ^{3 "} , HPO ₃ ^2" , H ₂ PO ₃ -, R ³ PO ₃ ^{2 "} , R ³ HPO ₃ -, R ³ R ^b PO ₃ -

The group of phosphonites and phosphinites of the general formula: R ³ R ^b PO ₂ -, R ³ HPO ₂ -, R ³ R ^b PO-, R ³ HPO ^"

• the group of carboxylic acids of the general formula: R ³ COO-

The group of borates of the general formula:

BO ₃ ^{3 "} , HBO ₃ ^2" , H ₂ BO ₃ -, R ³ R ^b BO ₃ -, R ³ HBO ₃ -, R ³ BO ₃ ^{2 "} , B (0R ³ ) (0R ^b ) (0R ^c ) (0R ^d ) ^" , B (HSO ₄ ) ^" , B (R ³ SO ₄ ) -

The group of the boronates of the general formula: R ³ BO ₂ ² -, R ³ 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 ³ SiO ₄ ^{3 "} , R ³ R ^b Si0 ₄ ^2" , R ³ R ^b R 1 SiO ₄ -, HR ³ SiO ₄ ^{2 "} ,

H ₂ R ³ SiO ₄ ^" , HR ³ R ^b SiO ₄ - The group of the alkyl or aryl silane salts of the general formula: R ³ SiO ₃ ^{3 "} , R ^a R ^b Si0 ₂ ² -, R ^a R ^b R ^c SiC-, R ^a R ^b R ^c Si0 ₃ -, R ^a R ^b R ^c Si0 ₂ -, R ^a R ^b Si0 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:

SO ₂ -R ³

R ^b -O ₂ S ^' SO, -R ^C

In this formula, R ^a , R ^b , R ^c and R ^d independently of one another are each hydrogen, C ₁ -C 30 -alkyl, if appropriate by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted Te imino groups interrupted C2-Ci8-alkyl, C6-Ci4-aryl, C5-Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, wherein two of them together an unsaturated, saturated or aromatic , optionally can form a ring interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups, where the radicals mentioned are each additionally denoted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles may be substituted.

In which are optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted Ci-cis-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, heptadyl, 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 Dimethyl 2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, A-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, A-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, A-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 groups interrupted C2-Ci8-alkyl, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6- dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 1-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5 oxa-nonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxa-octyl, 1-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-dioxaoctyl, 1-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 1-ethoxy-4,8-dioxaundecyl, 15- Ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxato-tetradecyl.

If two radicals form a ring, these radicals can be taken together, for example, as fused building block 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.

The number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited, or is automatically limited by the size of the remainder or of the ring building block. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferably not more than 3. Furthermore, at least one, preferably at least two, carbon atoms (e) are generally present between two heteroatoms.

Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino. The term "functional groups" is to be understood as meaning, for example, the following: carboxy, carboxamide, hydroxy, di- (C 1 -C ₄ -alkyl) -amino, C 1 -C ₄ -alkyloxy-carbonyl, cyano or C 1 -C ₄ -alkoxy C 1 -C ₄ -alkyl methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

Optionally C6-C4-aryl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles are, for example, phenyl, ToIyI, XyIyI, α-naphthyl, β-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl nyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylsaphthyl, 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 C5-C12-cycloalkyl which is substituted by 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.

A five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle is, for example, furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzthiazolyl, 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 carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates, in particular from the group of halides and halogen-containing compounds, the group of carboxylic acids, the Group containing SO ₄ ^{2 "} , SO ₃ ^2" , R ³ OSO ₃ ^" and R ³ SO ₃ -, and the group containing PO ₄ ^3" and R ³ R ^b PO ₄ -.

Preferred anions are chloride, bromide, iodide, SCN, OCN, CN, acetate, CrC ₄ alkyl sulfates, R ³ -C00 ^" , R ³ SO ₃ -, R ³ R ^b PO ₄ -, methanesulfonate, tosylate or CrC ₄ - Dialkyl phosphates. Particularly preferred anions are Ch, 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 -

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-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-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- dimethyl imidazolium, 1,4-dimethyl imidazolium, 1,3,4-trimethyl imidazolium, 1,4-dimethyl-3-ethyl imidazolium, 1,4-dimethyl-3-butyl imida Zolium, 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 +} 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 -,

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 ³ 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-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-tetradec ^ -S-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) -S-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1 Hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -S-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-di - Methylimidazolium, 1, 4-dimethylimidazolium, 1, 3,4-trimethylimidazolium, 1, 4-dimethyl-3-ethylimidazolium, 1, 4-dimethyl-3-butylimidazoliu m, 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 process according to the invention, an ionic liquid of the formula I is used 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 it is possible to use an ionic liquid of the formula II or a mixture of ionic liquids of the formula II, preferably an ionic liquid of the formula II is used.

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

For the degradation of cellulose according to the invention, celluloses from a wide variety of sources can be used, e.g. cotton, flax, ramie, straw, bacteria etc., or wood or bagasse, in the cellulose-enriched form.

However, the process according to the invention can be used not only for the degradation of cellulose but generally for the cleavage or degradation of poly-, oligo- and disaccharides, as well as derivatives thereof. As examples of polysaccharides are besides cellulose and hemicellulose, starch, glycogen, dextran and tunicin. Also included are the polycondensates of D-fructose, such as inulin, as well as chitin and alginic acid. Sucrose is an example of a disaccharide. Suitable cellulose derivatives include cellulose ethers, such as methylcellulose and carboxymethylcellulose, cellulose esters, such as cellulose acetate, cellulose butyrate, and cellulose senitrate. The corresponding explanations apply accordingly.

In the process according to the invention, a solution of cellulose in ionic liquid is prepared. The concentration of cellulose can be varied within wide ranges. Usually, it is in the range of 0.1 to 50 wt .-%, based on the total weight of the solution, preferably 0.2 to 40 wt .-%, particularly preferably 0.3 to 30 wt .-% and particularly preferably at 0.5 to 20% by weight.

This dissolution 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 150 ° C, preferably at 20 to 150 ° C, particularly preferably at 50 to 150 ° C. , But it is also possible to accelerate the dissolution process by intensive stirring or mixing and by entry of microwave or ultrasonic energy or by combining them.

The degradation is carried out depending on the ionic liquid used usually at a temperature of melting point of the ionic liquid from 0 to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C.

If ionic liquids are used which have acidic functions, then it is also possible to lower the reaction temperature. 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 ³ PO ₄ -, in particular HSO ₄ -. Reactions in these ionic liquids are preferably included a temperature of 0 to 150 ° C, preferably from 20 to 150 ° C, in particular from 50 to 150 ⁰ C.

If ionic liquids are used which have no acidic functions, then the reaction is usually carried out from 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 ³ OSO ₃ ^" and R ³ SO ₃ -, And the group containing PO ₄ ^{3 "} and R ³ R ⁰ PO ₄ -. Preferred anions here are chloride, bromide, iodide, SCN, OCN, CN, acetate, C 1 -C ₄ alkyl sulfates, R ^a -COC-, R ³ SO ₃ ^" , R ^a R ^b PO ₄ -, methanesulphonate, tosylate or C 1 -C ₄ dialkylphosphates, and especially preferred 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 -

In one embodiment, the preparation of the reaction solution and the degradation are carried out at the same temperature.

In a further embodiment, the preparation of the reaction solution and the degradation are carried out at different temperatures.

It is also possible on a case-by-case basis that degradation of the cellulose takes place already during the preparation of the reaction solution. In a special embodiment, the dissolution and the degradation process take place more or less in parallel.

Usually, the reaction is carried out at ambient pressure. It may also be advantageous from case to case to work at overpressure.

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, CO ₂ , or Gemi- see thereof to work.

Depending on the desired degree of degradation, the reaction time and the reaction temperature are adjusted.

In one embodiment, water is added. Through the use of an excess of water based on the anhydroglucose units of the cellulose, complete degradation as far as glucose can be achieved. In case of partial degradation of the cellulose, substoichiometric amounts of water are preferably added or the reaction is stopped.

When the degradation is carried out in the presence of water, it is possible to premix the ionic liquid and the water and dissolve the cellulose in this mixture. But it is also possible to add the water to the solution of ionic liquid and cellulose.

For example, if it is desired to completely degrade the cellulose, which is composed on average of x anhydroglucose units, to glucose, x equiv. Of water is needed. Preferably, the stoichiometric amount of water (nAnhydrogiucoseeιnheιten / n _W ater = 1) or an excess is in this case sets einge-. However, the excess of water must not be so high that the solubility of the cellulose is no longer guaranteed. It can be a surplus be used of at least 3 mol%, but not more than 3000 mol% of water based on x.

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, then the amounts of water used are usually adjusted accordingly (n-anhydrogglucose / water ^> 1 ). The larger the quotient nAnhydrogiu _∞ seeinheiten / nwasser, the lower will be under otherwise the same reaction conditions and the same reaction time, the average degradation of celulose and the higher the DP of the degraded cellulose (which will of course be smaller than the DP of the cellulose used) ,

In another embodiment, working without the addition of water. This is usually the case when the ionic liquid used contains small amounts of water and / or if water adheres to the cellulose used. The proportion of water in conventional cellulose can be up to 10% by weight, based on the total weight of the cellulose used. The above statements apply accordingly.

There is also the possibility that one or more other solvents are added to the reaction mixture or the water - as far as it has been added. 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, the reaction mixture contains less than 5 wt .-%, preferably less than 2 wt .-%, in particular less than 0.1 wt .-% of other solvents, based on the total weight of the reaction mixture.

Furthermore, it is possible to stop the degradation reaction when the desired degree of degradation is achieved by separating the cellulose from the reaction mixture. This can be achieved, for example, by adding an excess of water, usually at least 20% by weight, based on the cellulose solution or other suitable solvent in which the degraded cellulose is not soluble, e.g. a lower alcohol, such as methanol, ethanol, propanol or butanol, or with a ketone, for example acetone, etc., or mixtures thereof. Preferably, an excess of water or methanol is used.

The workup of the reaction mixture is usually carried out by the cellulose is precipitated as described above and the cellulose is filtered off. The ionic liquid can be recovered from the filtrate by customary methods. by distilling off the readily volatile components, such as the precipitant, the water. The remaining ionic liquid can be reused in the process according to the invention.

Due to the statistical degradation of cellulose, the ionic liquid to be regenerated contains only a small amount of glucose or its oligomers. Any existing amounts of these compounds can be separated by extraction with a solvent or by adding a precipitant from the ionic liquid.

It is also possible to stop the degradation reaction when the desired degree of degradation is achieved by precipitating the cellulose from the reaction mixture without first cooling the reaction mixture.

It is also possible that the reaction mixture is dissolved in water or in another suitable solvent in which the degraded cellulose is insoluble, such as e.g. a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, for example acetone, etc., or mixtures thereof, initiate and, depending on the embodiment, for example, fibers, films, etc. obtained from degraded cellulose. The filtrate is worked up as described above.

In the event that reaction conditions are chosen so that the cellulose is completely degraded, the corresponding glucose can be separated from the ionic liquid by conventional methods, such as by precipitation with ethanol.

In the event that the ionic liquid is circulated, the ionic liquid may contain up to 15% by weight, preferably up to 10% by weight, in particular up to 5% by weight of precipitant (s) as described above , contain.

The process can be carried out batchwise, semicontinuously or continuously.

The following examples serve to illustrate the invention.

Preamble:

Cotton linters (hereinafter called Linters) and Avicel PH 101 (microcrystalline cellulose) were dried overnight at 80 ° C and 0.05 mbar and 105 ° C and 0.1 mbar.

The ionic liquids were dried overnight at 120 ° C and 0.1 to 0.05 mbar with stirring. The average degree of polymerization DP of the used (where necessary) and the degraded cellulose was determined in each case by measuring the viscosity in Cuen solution.

Abbreviations:

EMIM HSO ₄ 1-Ethyl-3-methylimidazolium Hydrogen sulfate

BMIM Ac 1-butyl-3-methylimidazolium acetate

BMIM Cl 1-butyl-3-methylimidazolium chloride

BMMIM Cl 1-butyl-2,3-dimethylimidazolium chloride DP Average degree of polymerization

AGE anhydroglucose unit

Example 1 - Complete degradation of cellulose in EMIM HSO ₄ at 100 ° C

0.5 g of dried linters in 20.0 g of EMIM HSO _{4 were} stirred at 120 ° C. in a 50 ml protective gas flask with magnetic stirrer bar until a clear solution resulted. After cooling to 100 ° C, 0.05 g of water was added. (The ratio of AGE to water was 1: 1). The reaction mixture was stirred at 100 ° C for 16 h; then one part of the mixture was precipitated in twenty times the amount of water and another in twenty times the amount of methanol. In both cases, no precipitate formed, in Gelchromatogramm only low molecular weight components were found, which corresponds to a complete degradation of cellulose.

Example 2 - Degradation of cellulose in BMIM Cl at 95 ° C / 3 h

In a 50 ml inert gas flask with magnetic stir bar at 120 ° C 0.5 g dried linters were stirred in 20.0 g BMIM Cl. After 3 h, a clear solution was obtained. The reaction mixture was then sonicated for 3 h in the ultrasonic bath (Bandelin electronic Sonorex Super RK 106, bath temperature 95 ° C); Thereafter, the cellulose was precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 80 ° C and 0.1 mbar overnight. The yield of degraded cellulose was 0.485 g (97%). The DP of the cellulose thus obtained was 380. The DP of the employed Linter 3252.

Example 3 - Degradation of cellulose in BMIM Cl at 95 ° C / 4h

In a 50 ml inert gas flask with magnetic stir bar at 120 ° C 0.5 g dried linters were stirred in 20.0 g BMIM Cl. After 3 h, a clear solution was obtained. The reaction mixture was then incubated for 4 h in an ultrasound bath (Bandelin-electic). ronic Sonorex Super RK 106; Bath temperature 95 ° C) sonicated; then the cellulose was precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 80 ° C and 0.1 mbar overnight. The yield of degraded cellulose was 0.490 g (98%). The DP of the cellulose thus obtained was 225. The DP of the employed linter was 3252.

Example 4 - Degradation of cellulose in BMIM Cl at 120 ° C

In a 50 ml inert gas flask with magnetic stir bar at 120 ° C 0.5 g dried linters were stirred in 20.0 g BMIM Cl. After 3 h, a clear solution was obtained. The reaction mixture was then stirred for 16 h at 120 ° C bath temperature; Thereafter, the cellulose was precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 80 ° C and 0.1 mbar overnight. The yield of degraded cellulose was 0.495 g (99%). The DP of the cellulose thus obtained was 548. The DP of the employed linter was 3252.

Example 5 - Thermal degradation of cellulose in BMIM Cl at 130 ° C

In a 50 ml inert gas flask with magnetic stir bar at 120 ° C 0.5 g dried linters were stirred in 20.0 g BMIM Cl. After 3 hours, a clear solution was obtained. The reaction mixture was then stirred for 16 h at 130 ° C bath temperature; Thereafter, the cellulose was precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 80 ° C and 0.1 mbar overnight. The yield of degraded cellulose was 0.485 g (97%). The DP of the cellulose thus obtained was 396. The DP of the employed linter was 3252.

Example 6 - Degradation of cellulose in BMIM Cl at 150 ° C

0.5 g of dried Avicel PH 101 in 10.0 g of BMIM Cl were stirred at 120 ° C. in a 50 ml protective gas flask with magnetic stirrer bar. After 3 h, a clear solution was obtained. The reaction mixture was then stirred for 2 h at 150 ° C bath temperature; Thereafter, the cellulose was precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 80 ° C and 0.1 mbar overnight. The yield of degraded cellulose was 0.490 g (98%). The DP of the cellulose thus obtained was 51. The DP of Avicel PH 101 was 463.

Example 7 - Degradation of cellulose in BMMIM Cl at 150 ° C 0.5 g dried Avicel PH 101 in 10.0 g BMMIM Cl were stirred at 120 ° C. in a 50 ml protective gas flask with magnetic stirrer bar. After 3 h, a clear solution was obtained. The reaction mixture was then stirred for 2 h at 150 ° C bath temperature; Thereafter, the cellulose was precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 80 ° C and 0.1 mbar overnight. The yield of degraded cellulose was 0.475 g (95%). The DP of the cellulose thus obtained was 62. The DP of Avicel PH 101 was 463.

Example 8 - Degradation of cellulose in BMIM Cl at 150 ° C

In a 50 ml inert gas flask with magnetic stir bar at 120 ° C 0.5 g dried linters were stirred in 10 g BMIM Cl. After 3 h, a clear solution was obtained. The reaction mixture was then stirred for 2 h at 150 ° C bath temperature; Thereafter, the cellulose was precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 80 ° C and 0.1 mbar overnight. The yield of degraded cellulose was 0.475 g (95%). The DP of the cellulose thus obtained was 98. The DP of the employed linter was 3252.

Example 9 - Degradation of cellulose in BMIM Cl at 150 ° C - Influence of the reaction time

0.5 g of dried Avicel PH 101 in 20.0 g of BMIM Cl was stirred for 12 h at 120 ° C. in a 50 ml protective gas flask with magnetic stirrer bar. Then the clear reaction mixture was stirred at 150 ° C bath temperature. After the times t, which are listed in Table 1, an aliquot was removed in each case, the cellulose precipitated in the twenty-fold amount of methanol, filtered, washed with methanol and dried at 80 ° C and 0.1 mbar overnight. The yield of degraded cellulose and its DP are shown in Table 1.

Table 1 :

There was no precipitate on precipitation with methanol, indicating complete degradation of the cellulose. Example 10 - Degradation of cellulose in BMIM Cl at 150 ° C - Influence of the reaction time

0.5 g of dried linters in 20.0 g of BMIM Cl were stirred for 12 h at 120 ° C. in a 50 ml protective gas flask with magnetic stirrer bar. Then the clear reaction mixture was stirred at 150 ° C bath temperature. After the times t, which are listed in Table 2, each an aliquot was removed, the cellulose precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 80 ° C and 0.1 mbar overnight. The yield of degraded cellulose and its DP are shown in Table 2.

Table 2:

Example 11 - Degradation of cellulose in BMIM Ac at 120 ° C - Influence of the reaction time

0.5 g of dried linters were dissolved in 20.0 g of BMIM Ac at 120 ° C and after the times t, which are listed in Table 3, an aliquot was removed in each case, the cellulose precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 60 ° C and 0.05 mbar. The DPs of the degraded cellulose are shown in Table 3.

Table 3:

Example 12 - Degradation of cellulose in BMIM Cl at 120 ° C - Influence of the reaction time

0.5 g of dried linters were dissolved in 20.0 g of BMIM Cl at 120 ° C., and after the times t, which are listed in Table 4, in each case an aliquot was added. taken, the cellulose precipitated in the twenty-fold amount of methanol, filtered, washed with methanol and dried at 60 ° C and 0.05 mbar. The DPs of the degraded cellulose, which were determined by gel permeation chromatography, are shown in Table 4.

Table 4:

Example 13 - Degradation of cellulose in BMIM Ac at 100 ° C - Influence of the reaction time

1.0 g of dried Avicel PH 101 was dissolved in 20.0 g of BMIM Ac at 100 ° C., and after the times t, which are listed in Table 5, an aliquot was taken in each case, the cellulose precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 60 ° C and 0.05 mbar. The DPs of the degraded cellulose are shown in Table 5.

Table 5:

Claims

claims

1. A process for the degradation of poly-, oligo- or disaccharides, or derivatives thereof, characterized in that one dissolves the poly-, oligo- or disaccharide, o- the corresponding derivative, in at least one ionic liquid and, optionally under Add water, treated at elevated temperature.

2. The method according to claim 1, characterized in that one uses as polylactic, oligo- or disaccharide, or a derivative thereof, a polysaccharide, or a derivative thereof.

3. The method according to claim 2, characterized in that one uses as polysaccharide, or a derivative thereof, cellulose, or a cellulose derivative.

4. The method according to claim 3, characterized in that one uses as polysaccharide, or a derivative thereof, cellulose.

5. Process according to claims 1 to 4, characterized in that the ionic liquid, or mixtures thereof, are selected from the compounds of the formulas I,

[A]; [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] ^p - for a mono-, di-, tri- or tetravalent anion; stand;

or

the compounds of the formula II

[A ¹ J ⁺ [A ² J ⁺ [Y] ⁿ - (IIa) where n = 2;

where [A ¹ ] ⁺ , [A ² ] ⁺ , [A ³ ] ⁺ and [A ⁴ ] ⁺ independently of one another are those mentioned for [A] ⁺

Groups are selected; and [Y] ⁿ - have the abovementioned meaning.

6. The method according to claim 5, characterized in that [A] ⁺ for a cation selected from the compounds of the formulas (IIIa) to (MIy)

Ia) (MIb) (MIc)

(UId) (MIe) (MIf)

Ciig> (mg ¹ ) (MIh)

(INJ) (MIj ')

(MIm) (MIm ') In)

(MIn ') lo) (MIo')

(MIp) (MIq) (MIq ')

(MIq ") (Mir) (MIr ')

(MIr ") (MIs) (With)

(MIu) Iv) (MIw)

R ^z R ^z

3 ' ⁺ 1 ^{1 +} 1

R-PR ¹ SR ¹ RR

Ix) (MIy)

and oligomers containing this structure, wherein

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 independently of one another represent 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 having 1 to 20 carbon atoms, wherein the radicals R ¹ to R ⁹ , which in the abovementioned formulas (IM) are bonded to a carbon atom (and not to a heteroatom), may additionally also stand for halogen or a functional group; or two adjacent radicals from the series R ¹ to R ^{9 taken} 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 Rest with 1 to 30 carbon atoms, can stand.

Process according to claims 5 or 6, characterized in that [Y] ^n- selected from an anion

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 SOs) ₂ N-, CF ₃ CO ₂ - , CCI 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 ³ OSO ₃ -, R ³ SO ₃ -

The group of carboxylic acids of the general formula:

R ³ COO ^"

The group of borates of the general formula: BO ₃ ^{3 "} , HBO ₃ ^2" , H ₂ BO ₃ -, R ³ R ^b BO ₃ -, R ³ HBO ₃ -, R ³ BO ₃ ^{2 "} , B (0R ³ ) (0R ^b ) (0R ^c ) (0R ^d ) ^" , B (HSO ₄ ) ^" , B (R ³ SO ₄ ) ^"

The group of boronates of the general formula: R ³ BO ₂ ^{2 "} , R ³ 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 ³ SiO ₄ ^{3 "} , R ³ R ^b Si0 ₄ ^2" , R ³ R ^b R ^ SiO ₄ -, HR ³ - SiO ₄ ² -, H ₂ R ³ SiO ₄ -, HR ³ R ^b SiO ₄ - The group of the alkyl or aryl silane salts of the general formula: R ³ SiO ₃ ^{3 "} , R ^a R ^b Si0 ₂ ² -, R ^a R ^b R ^c SiC-, R ^a R ^b R ^c Si0 ₃ -, R ^a R ^b R ^c Si0 ₂ -, R ^a R ^b Si0 ₃ ^{2 "}

The group of methides of the general formula:

SO ₂ -R ³

R ^b -O ₂ S SO ₂ -R ^C

wherein the radicals R ^a , R ^b , R ^c and R ^d are each independently hydrogen, Ci-C ₃ o-alkyl, optionally by one or more non-adjacent

Oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino interrupted C2-Ci8-alkyl, C6-Ci ₄ -aryl, Cs-Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or Heterocycle containing sulfur atoms, wherein two of them together can 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 may be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles;

stands.

8. Process according to claims 5 to 7, characterized in that [A] ⁺ for a cation selected from the group of the compounds IMa, Nie, MIf; IMg, IMg ',

MIh, Uli, MIj, MIj ', MIk, IMk', IUI, Ulm, Ulm ', IMn or IMn' stands.

9. Process according to claims 5 to 8, characterized in that [A] ^{+ represents} a cation selected from the group of the compounds IMa, IMe or IMf.

10. Process according to claims 5 to 9, characterized in that [Y] ⁿ - for an anion selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group containing SO ₄ ^{2 "} , SO3 ^2" , R ³ OSO ₃ - and R ³ SO ₃ -, as well as the group containing PO ₄ ^{3 "} and R ³ R ^b PO ₄ -, stands.

1 1. A process according to claims 5 to 9, characterized in that [Y] ⁿ -for an anion selected from the group consisting of HSO ₄ -, HPO ₄ ^{2 "} , HaPO ₄ - and HR ³ PO ₄ - stands-.

12. The method according to claims 1 to 1 1, characterized in that the

Concentration of poly, oligo- or disaccharide, or a derivative thereof, in ionic liquid in a range of 0.1 to 50 wt .-% based on the total weight of the solution.

13. Process according to claims 1 to 12, characterized in that water is added.

14. The method according to claims 1 to 12, characterized in that it is carried out without the addition of water.

15. Process according to claims 1 to 14, characterized in that the hydrolysis is carried out at a temperature of from 0 to 200 ° C.

16. The method according to claims 1 to 15, characterized in that the quenching by the addition of a solvent in which the degradation products of the polysaccharide are not soluble, quenching.