EP1994059A1 - Method for breaking down cellulose in solution - Google Patents

Abstract

The invention relates to a method for breaking down cellulose in solution by dissolving the cellulose in an ionic liquid and treating it with an acid, optionally while adding water.

Description

Process for breaking down cellulose in solution

The present invention describes a process for the degradation of cellulose by dissolving the cellulose in an ionic liquid and treating it with an acid, optionally with the addition 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 - mechanical degradation, thermal degradation, degradation by the action of radiation and chemical degradation (D. Klemm et al., Comprehensive Cellulose Chemistry, Vol. 1 , Pp. 83-127, Wiley Verlag, 1998).

In mechanical degradation, such as in dry or wet grinding, it is disadvantageous that the DP reduces the cellulose only to a small extent becomes. An uncontrolled degradation takes place in the thermal treatment and also the cellulose is modified, in particular dehydrocelluloses can be formed. 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 the formation of keto functions, or if oxygen is present during the irradiation, to peroxide formation.

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

A process has now been found for the controlled degradation of cellulose by dissolving cellulose in an ionic liquid and treating it with an acid, optionally with the addition of water.

Ionic liquids in the sense of the present invention are preferred

(A) Salts of the general formula (I)

[Ai; [Y] ⁿ - (I),

where n is 1, 2, 3 or 4, [A] ^{+ is} a quaternary ammonium cation

Oxonium cation, a sulfonium cation or a phosphonium cation and [Y] ⁿ "is a mono-, di-, tri- or tetravalent anion;

(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 selected} independently of one another from the groups mentioned for [A] ⁺ and [Y] ^π "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. 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, of which then, in equilibrium, a proton or an alkyl group can be transferred to the anion to form 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),

Ciig> (mg ¹ ) (MIh)

(MIi) (INJ) (MIj ')

(MIk) (MIk ') (im)

(Ulm) (MIm ') (MIn)

(MIn ') (MIo) (MIo')

(MIp) (MIq) (MIq ')

R

(MIq ") Ir) Ir ')

(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, 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 aromatic aliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms, where the radicals R ¹ to R ⁹ , which in the abovementioned formulas (III) to a carbon atom (and not to a heteroatom) may additionally be also halogen or a functional group; or

two adjacent radicals from the series R ¹ to R ⁹ together also for a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or by 1 to 5 heteroatoms or functional

Groups interrupted or substituted radical having 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-, -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 '(imino), -COOH (carboxy ), -CONH ₂ (carboxamide), -SO 3 H (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 remainder of the carbon-containing radical.

Halogens are fluorine, chlorine, bromine and iodine.

The radical R preferably stands for

• unbranched or branched, unsubstituted or monosubstituted to hydroxyl, halogen, phenyl, cyano, C 1 -C 6 -alkoxycarbonyl and / or SO 3 H- C 1 -C 20 -alkyl substituted with 1 to 20 carbon atoms in total, 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 -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 -C 5 -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 O- 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 especially methyl, ethyl, 1-butyl and 1-octyl, and for CH3O- _(CH2 CH2θ) _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.

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 C5-C12-cycloalkenyl substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halo, heteroatoms and / or heterocycles; 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, 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 substituted or unsubstituted Imino groups broken 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-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-dioxolane-2 yl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydr oxypropyl, A-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, A-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) H2a + 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, C ₂ F _25), chloromethyl, 2-chloroethyl, trichloromethyl, 1, 1-dimethyl-2-chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2- iso-propoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, 2-methoxyisopropyl, 2- (meth oxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 5-hydroxy-3-oxa-pentyl, 8-hydroxy-3 , 6-dioxo-octyl, 1 1-hydroxy-3,6,9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, 1 1-hydroxy-4,8-di-oxa-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, 1-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, 1 1-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, 1-ethoxy-4,8-dioxa-undecyl, 15-ethoxy-4,8,12- trioxa-pentadecyl, 9-ethoxy-5-oxa-nonyl or 14-ethoxy-5,10-oxa-tetra-decyl.

In the case of optionally interrupted by 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 C2- Cis-alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or C _m F 2 (ma) - (ib) H 2a-b with im <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, halo, 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 im <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 in the <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-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.

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 radical, 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;

• 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) - 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 θ) _m -CH ₂ CH ₂ CH ₂ CH ₂ - with R ^A and R ^B preferably hydrogen, 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-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 ₁ N-di-Ci-Cδ alkyl-amino, such as N, N-dimethylamino and N ₁ N-diethylamino.

Most preferably, the radicals R ¹ to R ^{9 are} independently hydrogen or Ci-Ci8-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 and for CH ₃ O- (CH ₂ CH ₂ O) _{m is} -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.

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 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.

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-methylpyridinium, 1 - (1-Butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2-methyl-3-ethylpyridinium and 1- (1-octyl) -2-methyl-3- ethyl-pyridinium, 1- (1-dodecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethyl-pyridinium and 1- (1-hexadecyl) - 2-methyl-3-ethyl-pyτidinium.

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 particularly preferred as Imidazoliumionen (Never) are 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-H exadecyl) -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-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3 ethylimidazolium, 3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,1,5-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 hydrogen or methyl.

Very particular preference is given to using as 3-pyrazolinium ions (MIk) or (IMk ') 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.

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 (MIp) 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 (MIq), (MIq ') 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 of one another 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.

With very particular preference, the ammonium ions (MIu) used are those 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 from which the quaternary ammonium ions of the general formula (IMu) are derived by quaternization with the abovementioned radicals R 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-isopropyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpentylamine, di-iso-propylhexylamine, di-isopropyloctylamine, diisopropyl-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-ethylhexyl) amine, Nn-butylpyrrolidine, N-sec-butylpyrrodidine, N-tert-butyl 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 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- 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-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-tιϊoxa-pentadecyl, 9-ethoxy-5-oxa-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 the imidazolinium and imidazolium 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 -D odecyl) -2-methyl-3-ethylpyridinium, 1- (1-tetradecyl) -2-methyl-3-ethylpyridinium, 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-dimethylimidazolium, 1- (1-hexyl) -2,3 dimethyl imidazolium and 1- (1-octyl) -2,3-dimethylimidazolium, 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-tetramethylimidaz olium, 1, 4,5-trimethyl-3-ethyl imidazolium, 1, 4,5-trimethyl-3-butylimidazolium, 1, 4,5-trimethyl-3-octylimidazolium and 1 - (Pro-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 P0-, 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 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 ³ R ^b SiO ₂ ² , R ³ R ^b R 1 SiO ³ , R ³ R ^b R 1, SiO ₃ , R ³ R ^b R ^ Si0 ₂ -, R ³ 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 ₂ -R ^C

Herein, R ^a, R ^b, R ^c and R ^d are each independently hydrogen, Ci- C3o-alkyl, optionally substituted by one or more nonadjacent oxygen and / or sulfur atoms and / or one or more substituted or the unsubstituted imino groups te 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.

Therein, 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, 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-butoxy-propyl, 2-octyloxyethyl, chloromethyl, trichloromethyl, trifluoromethyl, 1, 1-dimethyl-2-chloroethyl, 2-methoxy-isopropyl, 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, 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 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-oxatetradecyl.

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 CrC ₄ -alkoxy. In this case, Ci to C4-alkyl is 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, 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 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) -S-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-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) -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-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 imidazolium, 1,4-dimethyl-3-octyl imidazolium, 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 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. In the process according to the invention, the acids used are inorganic acids, organic acids or mixtures thereof.

Examples of inorganic acids are hydrohalic acids, such as HF, HCl, HBr or Hl, perhalogenic acids, such as HCIO ₄ , halogen acids, such as HCIO3, sulfur-containing acids, such as H2SO4, polysulfuric acid or H2SO3, nitrogen-containing acids, such as HNO3, or phosphorus-containing Acids, such as H3PO4, polyphosphoric acid or H3PO3 Preferably hydrogen halide acids, such as HCl or HBr, H2SO4, HNθ3 θder H3PO4 used, in particular HCl, H ₂ SO ₄ or H ₃ PO ₄ .

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-resp. 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 Ci-Cδ-haloalkanecarboxylic acids, e.g. 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 8 -haloalkanesulfonic acids, such as trifluoromethanesulfonic acid,

Aromatic sulfonic acids, for example arylsulfonic acids, such as benzenesulfonic acid or 4-methylphenylsulfonic acid.

As organic acids, preference is given to C 1 -C 6 -alkanecarboxylic acids, for example acetic acid or propionic acid, halogenated carboxylic acids, for example C 6 -haloalkanecarboxylic acids, for example 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 used. Preferably, acetic acid, chlorofluoroacetic acid, trifluoroacetic acid, perfluoropropionic acid, methanesulfonic acid, trifluoromethanesulfonic acid or 4-methyl-phenylsulfonic acid are used.

In a particular embodiment of the invention are used as the acid sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid or 4-methylphenyl sulfonic acid. If 4-methylphenylsulfonic acid monohydrate is used, there is already one equivalent of water present.

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

In a further particular embodiment, ionic liquids and acids are used whose anions are not identical.

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, in addition to cellulose and hemicellulose, starch, glycogen, dextran and tunicin may be mentioned. Likewise, these include the polycondensates of D-fructose, such as inulin, and u.a. Chitin, and alginic acid. Sucrose is an example of a disaccharide. As cellulose derivatives, i.a. Cellulose ethers, such as methylcellulose and carboxymethylcellulose, cellulose esters, such as cellulose acetate, cellulose butyrate and cellulose senitrate. The corresponding explanations apply analogously.

In the process according to the invention, a solution of cellulose in ionic liquid is prepared. The concentration of cellulose can be varied within a wide range. It is usually in the range from 0.1 to 50% by weight, based on the total weight of the solution, preferably from 0.2 to 40% by weight, in particular It is preferably from 0.3 to 30% by weight, and more preferably from 0.5 to 20% by weight.

This dissolution process can be carried out at room temperature or with 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., particularly preferably at 50 to 150 ° C. However, it is also possible to accelerate the dissolution process by intensive stirring or mixing as well as by introduction of microwave or ultrasonic energy or by a combination thereof.

To this solution thus obtained, the acid and optionally water is added. The addition of water may be necessary if the water adhering to the cellulose used is insufficient to reach the desired degree of degradation. In general, the proportion of water in conventional cellulose in the range of 5 to 10 wt .-%, based on the total weight of the cellulose used (cellulose per se + adherent water). By using an excess of water and acid based on the anhydroglucose units of cellulose, complete degradation down to glucose is also possible. In order to achieve partial degradation, substoichiometric amounts of water and acid are added or the reaction is stopped.

In another embodiment, the ionic liquid, acid and possibly water are premixed and the cellulose is dissolved in this mixture.

There is also the possibility that one or more further solvents are added to the reaction mixture or are 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, 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.

The hydrolysis is usually carried out at a temperature from the melting point of the ionic liquid to 200 ° C., preferably from 20 to 180 ° C., in particular from 50 to 150 ° C., depending on the ionic liquid used and the acid used. Usually, the reaction is carried out at ambient pressure. However, it may also be advantageous on a case-by-case basis to work at overpressure, especially when 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 N2, to work a noble gas, CO2 or a mixture thereof.

Usually, the reaction time is in a range of 1 to 24 hours.

Depending on the desired degree of degradation, the amount of acid used, the water to be added if necessary, in each case in relation to the cellulose used, the reaction time and optionally the reaction temperature is set.

For example, if it is desired to completely degrade the cellulose, which is composed on average of x anhydroglucose units, to glucose, x equivalents of water are needed. Preferably, in this case, the stoichiometric amount of water (nAnhydrogiu∞seeιnheιten / nsaure = 1) or an excess is used, preferably an excess of> 3 mol% based on x. The acid can be used here in catalytic amounts, preferably in the range from 1 to 50 mol% based on x. However, it is also possible to increase the proportion of acid up to the stoichiometric ratio (with respect to x) or in excess.

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 smaller than x, then the amounts of water used and acid used are usually adjusted accordingly (n-anhydroglucose units / n _s acid> 1). The larger the quotient nAnhydrogiu _∞ times / acidity, the lower will be the average degradation of cellulose under otherwise identical reaction conditions and the same reaction time. The larger the quotient nAnhydrogiuΣseemheiten / nwasser, the lower will be under otherwise the same reaction conditions and the same reaction time, the average degradation of cellulose.

Furthermore, it is possible to stop the hydrolysis reaction when the desired degree of degradation is achieved by separating the cellulose from the reaction mixture. This can be done, for example, by cooling the reaction mixture and then adding an excess of water or other suitable solvent in which the degraded cellulose is insoluble, such as 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. It is also possible to stop the hydrolysis 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 another suitable solvent in which the degraded cellulose is insoluble, 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.

It is also possible to stop the hydrolysis reaction when the desired degree of degradation is achieved by trapping the acid with a base. Suitable bases include both inorganic bases, e.g. Alkali hydroxides, carbonates, hydrogen carbonates, but also organic bases such as e.g. Amines which are used in stoichiometric ratio to the acid or in excess. In a further embodiment, a hydroxide can be used as the base, which is characterized in that its cation corresponds to that of the ionic liquid 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. From the filtrate, the ionic liquid can be recovered by conventional methods by dissolving the volatile components, e.g. the precipitating agent, any added water and if volatile acids such as e.g. Organic acids were used, these, or possibly further solvent are distilled off. The remaining ionic liquid can be reused in the process according to the invention.

However, the acid can also, if it is worked up without neutralization, remain after removal of the solvent in the ionic liquid and the mixture (if necessary after addition of water) can be used again for the cellulose degradation.

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.

In the event that reaction conditions are chosen so that the cellulose is completely degraded, the corresponding glucose can be separated by conventional methods, such as precipitation with ethanol from the ionic liquid. 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 (hereafter Linters) or Avicel PH 101 (microcrystalline cellulose) were dried overnight at 80 ° C and 0.05 mbar.

The ionic liquids were dried overnight at 120 ° C and 0.05 mbar with stirring. The ionic liquids then contain about 200 ppm of water.

All examples with controlled water content were carried out in an atmosphere of anhydrous argon.

The average degree of polymerization DP of the (used as far as necessary) and of the degraded cellulose was determined by measuring the viscosity in each case.

Solution determined.

Abbreviations:

BMIM Cl 1-butyl-3-methylimidazolium chloride

EMIM Cl 1-ethyl-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 BMIM Cl by trifluoroacetic acid at 100 ⁰ C

In a 50 ml inert gas flask with magnetic stir bar at 120 ° C 0.5 g of dried linters in 20.0 g BMIM Cl were stirred until a clear solution. After cooling to 100 ° C, 0.1 g of trifluoroacetic acid and 0.05 g of water were added. (The ratio of AGE to acid was 3.5: 1, that of AGE to water was 1: 1.) The reaction mixture was stirred for 16 h at 100 ° C, then one part of the mixture was added twenty times the amount of water, another in the twenty times Amount of methanol precipitated. 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 - Complete degradation of cellulose in BMIM Cl by trifluoroacetic acid at 120 ⁰ C

0.5 g of dried linters in 20.0 g of BMIM Cl were stirred at 120 ° C. in a 50 ml protective gas flask with magnetic stirring bar until a clear solution was formed. To this clear solution was added 0.1 g of trifluoroacetic acid and 0.05 g of water. (The ratio of AGE to acid was 3.5: 1, that of AGE to water was 1: 1.) The reaction mixture was stirred for 4 h at 120 ° C; then one part of the mixture was precipitated in twenty times the amount of water, another part in twenty times the amount of methanol. In both cases, no precipitate formed; in the

Gelchromatogramm only low molecular weight components were found, which corresponds to a complete degradation of cellulose.

Example 3 - Partial degradation of cellulose in BMIM Cl by trifluoroacetic acid at 100 ⁰ C

In a 50 ml inert gas flask with magnetic stir bar 0.5 g of dried linters were stirred in 19.5 g BMIM Cl at 120 ° C until a clear solution was formed. After cooling to 100 ° C, 2.85 mg of trifluoroacetic acid dissolved in 0.5 g of BMIM Cl was added to the clear solution. (The ratio of AGE to acid was 125: 1.) The reaction mixture was stirred at 100 ° C for 16 h; Thereafter, the reaction mixture was precipitated in twenty times the amount of methanol. The precipitate was filtered off, washed with methanol and dried at 80 ° C and 1 mbar overnight. The yield of cellulose was 0.47 g (94%). The DP of the cellulose thus obtained was 171. The DP of the employed Linter 3252.

Example 4 - Complete degradation of cellulose in BMIM Cl by p-toluenesulfonic acid monohydrate at 100 ° C

0.5 g of dried Avicel PH 101 in 10.0 g of BMIM Cl were stirred at 120 ° C. in a 25 ml protective gas flask with magnetic stirrer bar until a clear solution resulted. After cooling to 100 ° C, 0.586 g of p-toluenesulfonic acid monohydrate was added to the clear solution. (The ratio of AGE to acid was 1: 1, that of AGE to water also 1: 1). The reaction mixture was stirred for 2 h at 100 ° C; then one part of the mixture was added in twenty times the amount of water, another rer in 20 times the amount of methanol precipitated. In both cases, no precipitate formed, in Gelchromatogramm only low molecular weight components were found, which corresponds to a complete degradation of cellulose.

Example 5 - Full degradation of cellulose in BMIM Cl by p-toluenesulfonic acid at 100 ⁰ C

0.5 g of dried Avicel PH 101 in 10.0 g of BMIM Cl were stirred at 120 ° C. in a 25 ml protective gas flask with magnetic stirring bar until a clear solution was formed. After cooling to 100 ° C, 0.531 g of anhydrous p-toluenesulfonic acid was added to the clear solution. (The ratio of AGE to acid was 1: 1.) The reaction mixture was stirred at 100 ° C for 2 h; then one part of the mixture was precipitated in twenty times the amount of water, another part in twenty times the amount of methanol. In both cases, no precipitation formed, in the

Gelchromatogramm only low molecular weight components were found, which corresponds to a complete degradation of cellulose.

Example 6 - Partial degradation of cellulose in BMIM Cl by p-toluenesulfonic acid monohydrate at 100 ° C

In a 25 ml inert gas flask with magnetic stir bar 0.5 g of dried linters were stirred in 9.5 g BMIM Cl at 120 ° C until a clear solution was formed. After cooling to 100 ° C, 5.86 mg of p-toluenesulfonic acid monohydrate dissolved in 0.5 g of BMIM Cl were added to the clear solution. (The ratio of AGE to acid was 100: 1, that of AGE to water was also 100: 1). The reaction mixture was stirred at 100 ° C for 6 hours, after which the mixture was precipitated in twenty times the amount of methanol. The precipitate was filtered off, washed with methanol and dried at 80 ° C and 1 mbar overnight. The yield of cellulose was 0.485 g (97%). The DP of the cellulose thus obtained was 187. The DP of the employed linter was 3252.

Example 7 - Complete degradation of cellulose in BMIM Cl by phosphoric acid at 100 ⁰ C

0.5 g of dried Avicel PH 101 in 10.0 g of BMIM Cl were stirred at 120 ° C. in a 25 ml protective gas flask with magnetic stirrer bar until a clear solution resulted. After cooling to 100 ° C, 0.5 g of 60 wt. % Phosphoric acid. (The ratio of AGE to acid was 1: 1, that of AGE to water 1: 3.6). The reaction mixture was stirred for 6 h at 100 ° C; after that For example, 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 8 - Complete degradation of cellulose in EMIM Cl by trifluoroacetic acid at 120 ^° C.

0.5 g of dried linters in 20.0 g of EMIM Cl were stirred at 120 ° C. in a 50 ml protective gas flask with magnetic stirrer bar until a clear solution was formed. To this clear solution was added 0.1 g of trifluoroacetic acid and 0.05 g of water. (The ratio of AGE to acid was 3.5: 1, that of AGE to water was 1: 1.) The reaction mixture was stirred for 4 h at 120 ° C; then one part of the mixture was precipitated in twenty times the amount of water, another part in twenty times the amount of methanol. In both cases, no precipitate formed; Gelchromatogramm only low molecular weight components were found, which corresponds to a complete degradation of the cellulose.

Example 9 - Partial degradation of cellulose in BMMIM Cl by trifluoroacetic acid at 100 ⁰ C

In a 50 ml inert gas flask with magnetic stirring bar, 0.5 g of dried linters were stirred in 19.5 g BMMIM Cl at 120 ° C. until a clear solution was formed. After cooling to 100 ° C, 2.85 mg of trifluoroacetic acid dissolved in 0.5 g of BMMIM Cl was added to the clear solution. (The ratio of AGE to acid was 125: 1.) The reaction mixture was stirred at 100 ° C for 16 h; Thereafter, the reaction mixture was precipitated in twenty times the amount of methanol. The precipitate was filtered off, washed with methanol and dried at 80 ° C and 1 mbar overnight. The yield of cellulose was 0.48 g (97%). The DP of the cellulose thus obtained was 180. The DP of the used Linter 3252.

Example 10 - Partial degradation of cellulose in BMIM Cl by trifluoroacetic acid at 100 ⁰ C

In a 50 ml inert gas flask with magnetic stir bar at 120 ° C 0.5 g of dried linters in 20.0 g BMIM Cl were stirred until a clear solution. After cooling to 100 ° C, 0.1 g of trifluoroacetic acid and 0.05 g of water were added. (The ratio of AGE to acid was 3.5: 1, that of AGE to water was 1: 1. The reaction mixture was stirred at 100 ° C. for 3 h, after which the reaction mixture was stirred. Mixed in 20 times the amount of methanol precipitated. The precipitate was filtered off, washed with methanol and dried at 80 ° C and 1 mbar overnight. The yield of cellulose was 0.46 g (92%). The DP of the cellulose thus obtained was 211. The DP of the used Linter 3252.

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 with at least one acid , optionally with the addition of water, treated.

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;

[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 ] ⁺ 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 ') (MIn)

(MIn ') lo) (MIo')

(MIp) (MIq) (MIq ')

(HIq ") (Me) (MIr ')

(MIr ") (MIs) (With)

(MIu) Iv) (MIw)

R ^z R ^z

3 ' ⁺ 1 ^{1 +} 1

R ³ - 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 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 A radical having 1 to 20 carbon atoms, where the radicals R ¹ to R ⁹ which in the abovementioned formulas (III) are attached to a carbon atom (and not to a heteroatom) may additionally be halogen or a functional group; or

two adjacent radicals from the series R ¹ to R ⁹ together also for 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 radical or substituted 1 to 30 carbon atoms, can stand.

7. Process according to claims 5 or 6, characterized in that [Y] ⁿ "is 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 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 HPO 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 P0-, 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 boronates of the general formula:

R ³ BO ₂ ² -, R ³ R ^b B0- 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 ^c Si0 ₄ -, HR ³ - SiO ₄ ² -, H ₂ R ³ SiO ₄ -, HR ^a R ^b Si0 ₄ -

The group of the alkyl or aryl silane salts of the general formula:

R ³ SiO ₃ ^{3 "} , R ³ R ^b Si0 ₂ ² -, R ³ R ^b R ^c Si0 ^" , R ³ R ^b R ^c Si0 ₃ -, R ³ R ^b R ^c Si0 ₂ -, R ³ 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 is} -O ₂ S SO ₂ -R ^C ;

wherein the radicals R ³ , R ^b , R ^c and R ^d are each independently hydrogen, Ci-C ₃ o-alkyl, optionally substituted 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 8 -alkyl, C ₆ -C 14 -aryl, Cs

Ci ₂ -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 by one or more oxygen and / or sulfur atoms and / or a or a plurality of unsubstituted or substituted imino groups can form an interrupted ring, where the radicals mentioned can each additionally 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, MIe, IMf; IMg, IMg, MIh, Uli, MIj, MIj, MIk, IMk, IUI, Ulm, Ulm, IMn or IMn.

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

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 1 to 10, characterized in that an inorganic acid, an organic acid or mixtures thereof are used as the acid.

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 is.

13. The method according to claims 1 to 12, characterized in that the degradation is carried out at a temperature from the melting point of the ionic liquid to 200 ° C.

14. The method according to claims 1 to 13, characterized in that the quenching by the addition of a solvent in which the degradation products of the polysaccharide are not soluble, quenching.

15. The method according to claims 1 to 14, characterized in that the quenching by the addition of base degradation.