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WO2008119770A1 - Procédé pour modifier la structure d'un matériau cellulosique par traitement au moyen d'un liquide ionique - Google Patents

Procédé pour modifier la structure d'un matériau cellulosique par traitement au moyen d'un liquide ionique Download PDF

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Publication number
WO2008119770A1
WO2008119770A1 PCT/EP2008/053759 EP2008053759W WO2008119770A1 WO 2008119770 A1 WO2008119770 A1 WO 2008119770A1 EP 2008053759 W EP2008053759 W EP 2008053759W WO 2008119770 A1 WO2008119770 A1 WO 2008119770A1
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alkyl
group
methyl
paper
cellulosic material
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German (de)
English (en)
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WO2008119770A9 (fr
Inventor
Matthias Maase
Uwe Vagt
Wolfgang Gaschler
Oliver Koch
Hubertus KRÖNER
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

Definitions

  • the present invention relates to a method of modifying the structure of a cellulosic material by contacting it with a liquid treatment medium comprising at least one ionic liquid.
  • Wood pulp derived from wood which is predominantly obtained by mechanical means, serves as fibrous material for the production of paper and paper-like products, such as cardboard and cardboard.
  • Made of wood or other fiber materials by digestion pulp containing a very high proportion of cellulose, the z.
  • Cellulose is also the most important constituent of fiber raw materials, especially cotton, for the textile industry.
  • Cellulose is a generally highly crystalline biopolymer of B-anhydroglucopyranose with long chains of sugar units linked by ⁇ -1,4-glycosidic linkages.
  • the individual polymer chains are interconnected by inter- and intramolecular hydrogen bonds and Van der Wals interactions.
  • the structure of unmodified clusters is further characterized by a high proportion of crystalline regions. With this structure, certain application properties are associated, which are still in need of improvement due to the extremely diverse applications of cellulose materials. So it may be z. For example, it may be desirable to vary mechanical properties of the material such as strength or porosity, optical properties such as color or gloss, and / or surface properties such as roughness, grip, or air resistance.
  • BMIMCI 1-butyl-3-methylimidazolium chloride
  • AMIMCI 1-allyl-3-methylimidazolium chloride
  • WO 03/029329 teaches to dissolve cellulose for its further processing in an ionic liquid which may essentially contain no water and no nitrogenous bases.
  • WO 2004/084627 describes a process for the preparation of regenerated cellulose capsules with an active ingredient using an ionic liquid as a solvent.
  • WO 2005/017001 describes a method for dissolving a lignocellulosic material with an ionic liquid under microwave irradiation and / or pressure and in the absence of water.
  • the cations of the ionic liquid correspond to those mentioned in WO 2004/084627.
  • WO 2005/017252 describes a method for treating a lignocellulosic material with an ionic liquid, for. B. for delignification.
  • DE 102005017733 describes solutions containing cellulose, an ionic liquid as solvent and 6 to 30 wt .-% of a nitrogen-containing base, based on the total weight of the solution.
  • DE 10 2005 017 715 describes solutions containing cellulose and an ionic liquid, wherein the ionic liquid is based on cations which have at least one atom selected from nitrogen, oxygen, sulfur and phosphorus and which is present in protonated form.
  • the invention therefore provides a method of modifying the structure of a cellulosic material by contacting it with a liquid treatment medium comprising at least one ionic liquid, wherein the bulk of the cellulosic material is not converted to a solubilized state.
  • a liquid treatment medium comprising at least one ionic liquid
  • the amounts of ionic liquid used are significantly lower than in a complete solution of the cellulosic material, thus reducing the cost of recovery or the ionic liquid used may remain in the modified cellulosic material.
  • the inventive method is particularly suitable for modifying the properties of paper and paper-like products or of cellulose starting materials for the production of paper and paper-like products.
  • the resulting products are z. B. by increased strength, reduced porosity and / or lower air resistance.
  • modification of the structure is to be understood broadly in the context of the present invention and in principle refers to any structural change associated with the change of at least one physical property of the cellulosic material.
  • Typical physical properties that undergo a change in a modification of the structure according to the inventive method are the so-called material properties, which can generally be described qualitatively by so-called material parameters.
  • Typical material properties are:
  • the method according to the invention serves to modify the structure of paper or of a cellulose material, which is subsequently used for papermaking.
  • Typical characteristics for paper that may change with a modification of the structure are the following:
  • the basis weight can be determined according to DIN ISO 536. It results from the quotient of mass and area of a sample and is given in [g / m 2 ].
  • the thickness is usually defined by the measuring instrument used. According to DIN 53105, part 1 z.
  • the meter must have two plane-parallel plates of 200 mm 2 each, which act at 100 kPa on the sample. The distance between the plates is then the paper thickness.
  • breaking strength, elongation at break and width-related breaking force are determined. From the breaking force F B , the breaking length R can be derived, knowing the width b of the test strip and its area-related mass niA:
  • the tear length R results in m.
  • tear length R is understood in paper, the length of the strip, in which the strip, suspended on one side, tearing off by its own weight at the suspension point.
  • the breaking strength index I From the mean values of the measured width-related breaking force and the area-related mass, the breaking strength index I.
  • ⁇ is the degree of fill and B is the elongation at break ⁇
  • the degree of perfection can be calculated from the force-strain diagram by dividing the area under the curve by the area that results when constructing a rectangle between the zero and the break point.
  • the humidity has an influence on the measured values. Correctly according to DIN, the samples should be brought to 65% moisture before this test. It is also possible to measure the humidity and to correct the measured values with empirically determined correction factors from tables. 10. Air resistance
  • Air resistance is the resistance that a sheet of paper opposes to the passage of air when there is a pressure differential between the boundaries of the sample.
  • the air resistance measurement can be done in a Gurley Method densitometer by measuring, for a given volume of air, the time it takes to pass through a sample of given dimensions under standard conditions of pressure, pressure difference, temperature and relative humidity.
  • the treatment of the cellulosic material with a liquid treatment medium is carried out under such conditions that the bulk of the cellulosic material is not converted to a solubilized state.
  • main amount is meant that at least 30 wt .-%, preferably at least 50 wt .-% of the cellulose material used for the treatment is not converted into the solubilized state.
  • at least 75% by weight, especially at least 90% by weight, of the cellulosic material is not converted to a solubilized state.
  • the term "solubilization" in the context of the invention refers to the conversion into a liquid state and in this case comprises the generation of solutions of the cellulose material as well as the conversion into a different solubilized state. If a cellulosic material is converted into a solubilized state, the individual polymer molecules do not necessarily have to be completely surrounded by a solvate shell. It is essential that the polymer changes to a liquid state as a result of the solubilization.
  • Carrying out the treatment at a low treatment temperature preferably upstream of at most 100 0 C, particularly preferably of at most 70 0 C, in particular of at most 50 0 C;
  • ionic liquids refer to organic salts which are already liquid at temperatures below 180 ° C.
  • the ionic liquids have a melting point of less than 180 0 C.
  • the melting point is in the range from -50 0 C to 150 0 C, more preferably in the range from -20 0 C to 120 0 C and more preferably below 100 0 C.
  • Cations and anions are present in the ionic liquid.
  • a proton or an alkyl radical can be transferred to the anion, resulting in two neutral molecules.
  • the ionic liquids used according to the invention have polyatomic, d. H. polyatomic anions, with two or more than two atoms on.
  • alkyl includes straight-chain or branched alkyl. It is preferably straight-chain or branched C 1 -C 30 -alkyl, in particular C 1 -C -alkyl, and very particularly preferably C 1 -C 12 -alkyl.
  • alkyl groups are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 1-methyl-butyl, tert-pentyl, neopentyl, n-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, n
  • alkyl also includes alkyl radicals whose carbon chain is replaced by one or more nonadjacent heteroatoms or heteroatom-containing groups which are preferably selected from -O-, -S-, -NR a -, -PR a -, -SiR a R aa and / or -SO2- can be interrupted.
  • R a is preferably hydrogen, alkyl, cycloalkyl, hetero cycloalkyl, aryl or hetaryl.
  • R aa is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, or aryl.
  • alkyl radicals whose carbon chains may be interrupted by one or two nonadjacent heteroatoms -O- are the following:
  • alkyl radicals whose carbon chains may be interrupted by three or more than three nonadjacent heteroatoms -O- are also oligo- and polyoxyalkylenes, ie compounds having repeating units which are preferably selected from (CH 2 CH 2 O) ⁇ i, (CH (CH 3 ) CH 2 O) ⁇ 2 and ((CH 2 ) 4 ⁇ ) x3 , where x1, x2 and x3 independently of one another are an integer from 3 to 100, preferably from 3 to 80. The sum of x1, x2 and x3 is an integer from 3 to 300, especially 3 to 100.
  • polyoxyalkylenes having two or three different repeating units the order is arbitrary, ie it may be random, alternating or block-shaped Repeat units act.
  • these are 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 4,8,12-trioxatridecyl (1-methoxy-4,8-dioxa-undecyl), 4 , 8.12-Trioxatetradecyl,
  • alkyl radicals whose carbon chains by one or more, for. B. 1, 2, 3, 4 or more than 4, non-adjacent heteroatoms -S- may be interrupted are the following:
  • Butylthiomethyl 2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-butylthio-ethyl, 2-dodecylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-propylthiopropyl,
  • 3-butylthiopropyl 4-methylthiobutyl, 4-ethylthiobutyl, 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithio-octyl, 4,8-dithia-nonyl, 3,7-dithio-octyl, 3, 7-di-thia-nonyl, 2- and 4-butylthiobutyl, 4,8-dithia-decyl, 3,6,9-trithia-decyl, 3,6,9-trithia-undecyl, 3,6,9-trithia dodecyl, 3,6,9,12-tetrathia-tridecyl and 3,6,9,12-tetrathia-tetradecyl.
  • alkyl radicals whose carbon chains are interrupted by one or two non-adjacent heteroatom-containing groups -NR a - are the following: 2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 3-methylaminopropyl, 2- and 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and 4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl, 6-methylaminohexyl, 6- Dimethylaminohexyl, 6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl and 3,6-dimethyl-3,6-diazaoctyl.
  • alkyl radicals whose carbon chains may be interrupted by three or more than three non-adjacent heteroatom-containing groups -NR a - are also oligo- and polyalkyleneimines.
  • the comments made above for the polyoxyalkylenes apply analogously to polyalkyleneimines, wherein the oxygen atom is replaced in each case by a group NR a , in which R a is preferably hydrogen or C 1 -C 4 -alkyl.
  • Examples of these are 9-methyl-3,6,9-triazadecyl, 3,6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl, 3,6,9-trimethyl-3,6 , 9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyl, 3,6,9,12-tetramethyl-3,6,9,12-tetraazatridecyl, and the like.
  • alkyl radicals whose carbon chains by one or more, for. B. 1 or 2 non-adjacent groups -SO2- are interrupted, are 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl, 2-isopropylsulfonylethyl, 2-Butylsulfonylethyl, 2-methylsulfonylpropyl, 3-methylsulfonylpropyl, 2-ethylsulfonyl propyl, 3rd Ethylsulfonylpropyl, 2-propylsulfonylpropyl, 3-propylsulfonylpropyl, 2-butylsulfonylpropyl, 3-butylsulfonylpropyl, 2-methylsulfonylbutyl, 4-methylsulfonylbutyl, 2-ethylsulfonyl
  • alkyl also includes substituted alkyl radicals.
  • Cycloalkyl, cycloalkyloxy, polycycloalkyl, polycycloalkyloxy, heterocycloalkyl, aryl and hetaryl substituents of the alkyl groups may themselves be unsubstituted or substituted; suitable substituents are those mentioned below for these groups.
  • alkyl also apply in principle to the alkyl moieties in alkoxy, alkylamino, dialkylamino, alkylthio (alkylsulfanyl), alkylsulfinyl, alkylsulfonyl, etc.
  • Suitable substituted alkyl radicals are the following:
  • Alkyl substituted by carboxy such as. Carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 7-carboxyheptyl, 8-carboxyctyl, 9-carboxynonyl, 10-carboxydecyl, 12-carboxydodecyl and 14-carboxytetradecyl;
  • Alkyl which is substituted by SO3H such as. Sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 7-sulfoheptyl, 8-sulfooctyl, 9-sulfononyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl;
  • Alkyl which is substituted by carboxylate such as. Alkoxycarbonylalkyl, e.g. Methoxycarbonylmethyl, ethoxycarbonylmethyl, n-butoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-methoxycarbonylpropyl, 2-ethoxycarbonylpropyl, 2- (n-butoxycarbonyl) propyl, 2- (4-n-butoxycarbonyl) propyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 3- (n-butoxycarbonyl) propyl, 3- (4-n-butoxycarbonyl) propyl, aminocarbonylalkyl, e.g.
  • Alkyl substituted by hydroxy such as. 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 2-hydroxy-2,2-dimethylethyl,
  • Alkyl which is substituted by amino such as. 2-aminoethyl, 2-aminopropyl,
  • Alkyl which is substituted by cyano such as. 2-cyanoethyl, 3-cyanopropyl, 3-cyanobutyl and 4-cyanobutyl;
  • Alkyl which is substituted by nitro such as. 2-nitroethyl, 2- and 3-nitropropyl and 2-, 3- and 4-nitrobutyl and the like.
  • Alkyl which is substituted by amino such as. 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl and the like.
  • Alkyl substituted by cycloalkyl such as. Cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl and the like.
  • Alkyl which is substituted by 0 (oxo group), such as. 2-oxopropyl, 2-oxobutyl, 3-oxobutyl, 1-methyl-2-oxopropyl, 2-oxopentyl, 3-oxopentyl, 1-methyl-2-oxobutyl, 1-methyl-3-oxobutyl, 2-oxohexyl, 3-oxohexyl, 4-oxohexyl, 2-oxoheptyl, 3-oxoheptyl, 4-oxoheptyl, 4-oxoheptyl and the like.
  • Alkyl which is substituted by S (thioxo), such as.
  • S (thioxo) such as.
  • 2-thioxopropyl 2-thioxopropyl
  • Alkoxy is an alkyl group bonded via an oxygen atom.
  • alkoxy are: methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1, 1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 , 1-Dimethylpropoxy, 1, 2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy , 1, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2,2-trimethylpropoxy, 1 -Ethyl-1-methylpropoxy or 1-ethyl-2
  • Alkylthio (alkylsulfanyl) is an alkyl group bonded via a sulfur atom. Examples of alkylthio are methylthio, ethylthio, propylthio, butylthio, pentylthio and hexylthio.
  • Alkylsulfinyl for a via an S ( O) group bonded alkyl group.
  • Aryl-substituted alkyl radicals (“arylalkyl”) have at least one, as defined below, unsubstituted or substituted aryl group. Suitable substituents on the aryl group are the following. In this case, the alkyl group in "arylalkyl” may bear at least one further substituent as defined above and / or by one or more nonadjacent heteroatoms or heteroatom-containing groups which are selected from -O-, -S-, -NR a - , and / or SO 2 - be under- broke.
  • Arylalkyl is preferably phenyl-Ci-Cio-alkyl, particularly preferably phenyl-Ci-C 4 -alkyl, z.
  • benzyl 1-phenethyl, 2-phenethyl, 1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut-1 -yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl , 1- (phen-meth) -eth-1-yl, 1- (phen-methyl) -1- (methyl) -eth-1-yl or - (phen-methyl) -1- (methyl) -prop-1-yl; preferably for benzyl and 2-phenethyl.
  • alkenyl in the context of the present invention comprises straight-chain and branched alkenyl groups which, depending on the chain length, may carry one or more double bonds (eg 1, 2, 3, 4 or more than 4). Preference is given to C 2 -Cis, particularly preferably C 2 -C 2 -alkenyl groups.
  • alkenyl also includes substituted alkenyl groups containing one or more (e.g., 1, 2, 3, 4, 5, or more than 5) substituents can carry. Suitable substituents are, for. B.
  • alkenyl also includes alkenyl radicals whose carbon chain may be interrupted by one or more nonadjacent heteroatoms or heteroatom-containing groups, which are preferably selected from -O-, -S-, -NR a - and / or -SO 2 -.
  • Alkenyl is then for example ethenyl (vinyl), 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,
  • cycloalkyl in the context of the present invention comprises unsubstituted as well as substituted monocyclic saturated hydrocarbon groups having generally 3 to 12 carbon ring members, preferably C3-C12-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentyl , Cyclodecyl, cycloundecyl or cyclododecyl, in particular C5-Ci2-cycloalkyl.
  • C3-C12-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentyl , Cyclodecyl, cycloundecyl or cyclododecyl, in particular C5-C
  • Suitable substituents are as a rule selected for alkyl, the substituents mentioned above for the alkyl groups, alkoxy and also alkylthio.
  • Substituted cycloalkyl groups may have one or more (for example 1, 2, 3, 4, 5 or more than 5) substituents, where in the case of halogen the cycloalkyl radical is partially or completely substituted by halogen.
  • cycloalkyl groups are cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, chloropentyl, dichloropentyl, dimethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3 and 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3 and 4-tert-butylcyclohexyl, chlorhexyl, dimethylcyclohexyl, diethylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butoxycyclohexyl, methylthiocyclohexyl, chlorocyclohexyl,
  • Cycloalkyloxy is an oxygen-bonded cycloalkyl group as defined above.
  • cycloalkenyl includes unsubstituted and substituted, mono- or di-unsaturated hydrocarbon groups having 3 to 5 to 8 to 12, preferably 5 to 12 carbon ring members such as cyclopent-1-en-1-yl, cyclopent-2-en-1 -yl, cyclopent-3-en-1-yl, cyclohex-1-en-1-yl, cyclohex-2-en-1-yl, cyclohex-3-en-1-yl, cyclohexa-2,5-diene -1-yl and the like. Suitable substituents are those previously mentioned for cycloalkyl.
  • Cycloalkenyloxy is an oxygen-bonded cycloalkenyl group as defined above.
  • polycyclyl in the context of the present invention in the broadest sense compounds containing at least two rings, regardless of how these rings are linked. These may be carbocyclic and / or heterocyclic rings.
  • the rings can be saturated or unsaturated.
  • the rings can be linked via single or double bonds ("polynuclear compounds"), linked by annulation (“fused ring systems") or bridged ("bridged ring systems", “cage compounds”).
  • Preferred polycyclic compounds are bridged ring systems and fused ring systems.
  • Condensed ring systems may be fused (fused) aromatic, hydroaromatic and cyclic compounds by annulation. Condensed ring systems consist of two, three or more than three rings.
  • each ring has one edge or two atoms in common with each adjacent ring, and a peri-annulation in which one carbon atom belongs to more than two rings.
  • Preferred among the fused ring systems are ortho-fused ring systems.
  • Bridged ring systems in the context of the present invention include those which do not belong to the polynuclear ring systems and not to the fused ring systems and in which at least two ring atoms belong to at least two different rings.
  • bicycloalkyl encompasses bicyclic hydrocarbon radicals having preferably 5 to 10 C atoms, such as bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl, bicyclo [2.2.1] hept-7-yl, bicyclo [2.2.2] oct-1-yl, bicyclo [2.2.2] oct-2-yl, bicyclo [3.3.0] octyl, bicyclo [4.4.0] decyl and the like.
  • bicycloalkenyl includes monounsaturated, bicyclic hydrocarbon radicals preferably having 5 to 10 carbon atoms, such as bicyclo [2.2.1] hept-2-en-1-yl.
  • aryl in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted.
  • Aryl is usually for hydrocarbon radicals having 6 to 10, to 14, to 18, preferably 6 to 10 carbon ring members.
  • Aryl is preferably unsubstituted or substituted phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, etc., and particularly preferably phenyl or naphthyl.
  • Substituted aryls may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the number and size of their ring systems.
  • Aryl is particularly preferably phenyl, which in the case of a substitution can generally carry 1, 2, 3, 4 or 5, preferably 1, 2 or 3, substituents.
  • Aryl which carries one or more radicals is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6- Trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl , 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-,
  • substituted aryl wherein two substituents attached to adjacent carbon atoms of the aryl ring form a fused ring or fused ring system are indenyl and fluorenyl.
  • aryloxy in the context of the present invention stands for aryl bound via an oxygen atom.
  • arylthio in the context of the present invention stands for aryl bound via a sulfur atom.
  • heterocycloalkyl in the context of the present invention comprises non-aromatic, unsaturated or fully saturated, cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms by heteroatoms selected from oxygen , Nitrogen, sulfur and a group -NR a - are replaced and which is unsubstituted or substituted by one or more, for example, 1, 2, 3, 4, 5 or 6, C 1 -C 6 -alkyl groups.
  • heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothienyl, dihydrothienyl, tetrahydrofuranyl, dihydrofuranyl, Tetrahydropyranyl, 1, 2-oxazolin-5-yl, 1, 3-oxazolin-2-yl and dioxanyl called.
  • Nitrogen-containing heterocycloalkyl can in principle be bound both via a carbon atom and via a nitrogen atom.
  • heteroaryl in the context of the present invention comprises unsubstituted or substituted, heteroaromatic, mononuclear or polynuclear groups having generally 5 to 14 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms one, two, three or four heteroatoms selected from O, N, -NR a and S are substituted, such as furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzofuranyl, benzthiazolyl, benzimidazolyl, pyridyl, quinolinyl, acridinyl , Pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl
  • the substituents are as a rule selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxyl, carboxyl, halogen and cyano.
  • 5- to 7-membered nitrogen-containing heterocycloalkyl or heteroaryl radicals which optionally contain further heteroatoms are, for example, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, pyridinyl, pyridazinyl, pyrimidinyl, Pyrazinyl, triazinyl, piperidinyl, piperazinyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, indolyl, quinolinyl, isoquinolinyl or quinaldinyl, which may
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Carboxylate and sulfonate in the context of this invention preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic ester or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function.
  • these include z.
  • esters with Ci-C4-alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
  • acyl in the context of the present invention represents alkanoyl, hetaroyl or aroyl groups having generally 1 to 11, preferably 2 to 8, carbon atoms, for example the formyl, acetyl, propanoyl, butanoyl, pentanoyl , Hexanoyl, heptanoyl, 2-ethylhexanoyl, 2-propylheptanoyl, benzoyl or naphthoyl group.
  • the radicals E 1 and E 2 , E 3 and E 4 , E 5 and E 6 are independently selected from hydrogen, alkyl, cycloalkyl and aryl.
  • the groups NE 1 E 2 , NE 3 E 4 and NE 5 E 6 are preferably N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylamino, N, N-di-n -butylamino, N, N-di-tert-butylamino, N, N-dicyclohexylamino or N, N-diphenylamino.
  • Preferred ionic liquids are
  • n 1, 2, 3 or 4
  • [A] + is a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation
  • [Y] n ' is a polyatomic, mono-, di-, tri- or tetravalent anion or mixtures of these anions;
  • [A 1 J + , [A 2 ] + , [A 3 J + and [A 4 J + are independently selected from the groups mentioned for [A] + and [Y] "- the meaning mentioned under (A) owns; or
  • [A 1 ] + , [A 2 ] + and [A 3 ] + are independently selected from the groups named for [A] + , [Y] "- has the meaning given under (A) and [M 1 ] + , [M 2 ] + , [M 3 ] + monovalent metal cations, [M 4 P + divalent metal cations and [M 5 J 3+ trivalent metal cations.
  • the metal cations [M 1 ] + , [M 2 J + , [M 3 J + , [M 4 J 2+ and [M 5 J 3+ ] mentioned in formulas (III.a) to (III.j) are They are generally metal cations of the 1st, 2nd, 6th, 7th, 8th, 9th, 10th, 11th, 12th, 13th and 14th group of the periodic table.
  • Suitable metal cations are, for example, Li + , Na + , K + , Cs + , Mg 2+ , Ca 2+ , Ba 2+ , Cr 3+ , Fe 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2 + , Ag + , Zn 2+ and Al 3+ .
  • Suitable compounds which are suitable for forming the cation [A] + of ionic liquids are, for. B. in DE 102 02 838 A1. These compounds preferably contain at least one heteroatom, such as. B. 1 to 10 heteroatoms, which are preferably selected from nitrogen, oxygen, phosphorus and sulfur atoms. Preference is given to compounds which have at least one nitrogen atom and, if appropriate, at least one further heteroatom other than nitrogen. contain atom. Preference is given to compounds which contain at least one nitrogen atom, particularly preferably 1 to 10 nitrogen atoms, in particular 1 to 5 nitrogen atoms, very particularly preferably 1 to 3 nitrogen atoms and especially 1 or 2 nitrogen atoms. The latter nitrogen compounds may contain other heteroatoms such as oxygen, sulfur or phosphorus atoms.
  • heteroatom such as. B. 1 to 10 heteroatoms, which are preferably selected from nitrogen, oxygen, phosphorus and sulfur atoms.
  • the nitrogen atom is z. B. a suitable carrier of the positive charge in the cation of the ionic liquid.
  • 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 protonation of the nitrogen atom.
  • salts with different anions are obtained. In cases where it is not possible to form the desired anion already during the quaternization, this can be done in a further synthesis step.
  • the halide can be reacted with a Lewis acid to form a complex anion from halide and Lewis acid.
  • a Lewis acid to form a complex anion from halide and Lewis acid.
  • replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt with precipitation of the resulting Metallha- logenids, via an ion exchanger or by displacement of the halide ion by a strong acid (to release the hydrohalic acid). Suitable methods are, for example, in Angew. Chem. 2000, 112, p. 3926-3945 and the literature cited therein.
  • 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 optionally an oxygen or sulfur atom
  • aromatic heterocycles are particularly preferred.
  • Particularly preferred compounds are those which have a molar mass of less than 1000 g / mol, very particularly preferably less than 600 g / mol and in particular less than 400 g / mol.
  • Preferred cations are selected from the compounds of the formulas (IV.a) to (IV.z),
  • R is hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, polycyclyl, heterocycloalkyl, aryl or heteroaryl;
  • Radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 which are bonded to a ring carbon atom, independently of one another, represent hydrogen, a sulfo group, COOH, carboxylate, sulfonate , Acyl, alkoxycarbonyl, cyano, halogen, hydroxyl, SH, nitro,
  • NE 1 E 2 alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, cycloalkyl, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, polycyclyl, polycycloxy, heterocycloalkyl, aryl, aryloxy or heteroaryl, where E 1 and E 2 independently of one another represent hydrogen , Alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
  • Radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 which are bonded to a ring heteroatom, for hydrogen, SO 3 H, NE 1 E 2 , alkyl, alkoxy , Alkenyl, cycloalkyl, cycloalkenyl, polycyclyl, heterocycloalkyl, aryl or heteroaryl, where E 1 and E 2 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or
  • two adjacent radicals R 1 to R 9 together with the ring atoms to which they are attached may stand for at least one fused, saturated, unsaturated or aromatic ring or a ring system having 1 to 30 carbon atoms, the ring or the ring system 1 to 5 may have non-adjacent heteroatoms or heteroatom-containing groups and wherein the ring or the ring system may be unsubstituted or substituted,
  • R 1 and R 3 or R 3 and R 5 may also together be the bond moiety of a double bond between the ring atoms which carry these radicals,
  • radicals carboxylate, sulfonate, acyl, alkoxycarbonyl, halogen, NE 1 E 2 , alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, cycloalkyl, cycloalkyloxy, cycloalkenyl, cycloalkenyloxy, polycyclyl, polycycloxy , Heterocycloalkyl, aryl, aryloxy or heteroaryl is referred to the introductory statements made in full.
  • Radicals R 1 to R 9 which are bonded to a carbon atom in the abovementioned formulas (IV) and have a heteroatom or a heteroatom-containing group can also be bonded to the carbon atom directly via a heteroatom.
  • the radical R preferably stands for
  • C 1 to C 18 alkyl such as 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, 1 Heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl,
  • Ci-Cis-alkyl especially hydroxy-Ci-Cis-alkyl, such as. 2-hydroxyethyl or 6-hydroxyhexyl; Phenyl-Ci-cis-alkyl, such as. Benzyl,
  • Cyano-Ci-Cis-alkyl such as.
  • Ci-C ⁇ -alkoxy-Ci-Cis alkyl such as.
  • B. 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl or 2- (n-Butoxy-carbonyl) -ethyl
  • C 1 -C 6 -fluoroalkyl such as trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl, undecylfluoroisopentyl
  • Sulfo-Ci-cis alkyl such as.
  • 3-sulfopropyl such as.
  • Hydroxyethyloxyalkyl radicals of oligo- and polyalkylene glycols such as polyethylene glycols and polypropylene glycols and their oligomers having 2 to 100 units and a hydrogen or a C 1 -C 5 -alkyl as an end group, such as R A O- (CH R B -CH 2 -O ) n-CH R B -CH 2 - with R A and R B is preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxa-butyl,
  • the radical R particularly preferably represents linear C 1 - to C 18 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-decyl, 1 Dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, most preferably methyl, ethyl, 1-butyl and 1-octyl and CH 3 O- (CH 2 CH 2 O) n -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.
  • radicals R 1 to R 9 are preferably each independently
  • C 1 -C 18 -alkyl which is unsubstituted or, as defined above, is substituted and / or, as defined above, may be interrupted by at least one heteroatom or a heteroatom-containing group;
  • C 2 -C -alkenyl which is unsubstituted or, as defined above, is substituted and / or, as defined above, may be interrupted by at least one heteroatom;
  • Heterocycloalkyl having 5 or 6 ring atoms, wherein the ring next to carbon ring members 1, 2 or 3 heteroatom or heteroatom-containing groups which are selected from oxygen, nitrogen, sulfur and NR a , and which is unsubstituted or, as defined above, is substituted ;
  • Heteroaryl having 5 to 10 ring atoms, wherein the ring in addition to carbon ring having 1, 2 or 3 heteroatoms or heteroatom-containing groups which are selected from oxygen, nitrogen, sulfur and NR a , and which is unsubstituted or, as defined above, is substituted ,
  • R 1 to R 9 are alkoxy
  • R 1 to R 9 are preferably methoxy or ethoxy or R A O- (CH 2 CH 2 CH 2 CH 2 O) n -CH 2 CH 2 CH 2 CH 2 O.
  • R A and R B preferably hydrogen, methyl or ethyl and n preferably 0 to 3.
  • R 1 to R 9 are acyl
  • R 1 to R 9 are preferably formyl and C 1 -C 4 -alkylcarbonyl, in particular formyl or acetyl.
  • R 1 to R 9 are C 1 -C 6 -alkyl
  • R 1 to R 9 are preferably unsubstituted C 1 -C 18 -alkyl, such as 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-9-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-p
  • C 1 -C 18 -haloalkyl especially C 1 -C 18 -fluoroalkyl, for example trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonofluoroisobutyl, undecylfluoropentyl, undecylisopentyl, C 6 F 13, CsFi 7 , C 10 F 21, C 12 F 25, especially Cis-chloroalkyl such as chloromethyl, 2-chloroethyl, trichloromethyl, 1, 1-dimethyl-2-chloroethyl;
  • Amino-Ci-Ci8-alkyl such as 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, Ci-C6-alkylamino-Ci-Ci8-alkyl, such as 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl; Di- (C 1 -C 6 -alkyl) C 1 -C 4 -alkyl, such as 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, cyano-C 1 -C 18 -alkyl, such as 2-cyanoethyl, 2-cyanopropyl, C 1 -C 10
  • Phenoxy-C 1 -C 6 -alkyl such as 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl;
  • Phenylthio-C 1 -C 18 -alkyl such as 2-phenylthioethyl
  • R 1 to R 9 are C 2 -C alkenyl
  • R 1 to R 9 are preferably C 2 -C 6 -alkenyl, such as vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2- Butenyl or C2-Ci8 alkenyl which is partially or completely substituted by fluorine.
  • R 1 to R 9 are C ⁇ -Cio-aryl
  • R 1 to R 9 are preferably phenyl or naphthyl, wherein phenyl or naphthyl is unsubstituted or mono-, di-, tri- or tetra-substituted, wherein the substituents independently of one another by halogen, C 1 -C 5 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylsulfanyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl,
  • Ci-C ⁇ -alkylcarbonyl, amino, Ci-C ⁇ -alkylamino, di- (Ci-C6-dialkyl) amino and nitro are selected, such as phenyl, methylphenyl (ToIyI), dimethylphenyl (XyIyI), such as. For example, 2,6-dimethylphenyl, trimethylphenyl, such as. B.
  • R 1 to R 9 are C 5 -C 12 -cycloalkyl
  • R 1 to R 9 are preferably unsubstituted cycloalkyl, such as cyclopentyl or cyclohexyl;
  • C 5 -C 12 -cycloalkyl which is monosubstituted or disubstituted, wherein the substituents are independently selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylsulfanyl or chlorine, eg. Butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl;
  • R 1 to R 9 are polycyclyl, R 1 to R 9 are preferably C 5 -C 12 -cycloalkyl, such as norbornyl or C 5 -C 12 -cyclo-alkenyl, such as norbornenyl.
  • R 1 to R 9 are C5-Ci2-cycloalkenyl
  • R 1 to R 9 are preferably unsubstituted cycloalkenyl, such as cyclopent-2-en-1-yl, cyclopent-3-en-1-yl, cyclohex-2 -en-1-yl, cyclohex-1-en-1-yl, cyclohexa-2,5-dien-1-yl or partially or fully fluorinated cycloalkenyl.
  • R 1 to R 9 are heterocycloalkyl having 5 or 6 ring atoms
  • R 1 to R 9 are preferably 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 2-methyl-1, 3-dioxolan-2-yl, 4-methyl-1,3-dioxolan-2-yl.
  • R 1 to R 9 are heteroaryl
  • R 1 to R 9 are preferably furyl, thienyl, pyrryl, pyridyl, indolyl, benzoxazolyl, benzimidazolyl, benzthiazolyl.
  • hetaryl carries 1, 2 or 3 substituents which are independently selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and halogen, for example dimethylpyridyl, methylquinolyl, dimethylmethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
  • radicals R 1 to R 9 are each independently
  • Ci-Cis-alkyl such as 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,
  • N, N-di-C 1 -C 6 -alkylamino such as N, N-dimethylamino and N, N-diethylamino.
  • the radicals R 1 to R 9 are each independently hydrogen; Ci-Ci ⁇ -alkyl, such as methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl; phenyl; 2-hydroxyethyl; 2-cyanoethyl; 2- (alkoxycarbonyl) ethyl such as 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl or 2- (n-butoxycarbonyl) ethyl; N, N- (C 1 -C 4 -dialkyl) amino, such as N, N-dimethylamino or N, N-diethylamino; Chlorine and for residues of oligoalkylene glycol, such as CH 3 O- (CH 2 CH 2 O) n -CH 2 CH 2 - or CH 3 CH 2 O- (CH 2 CH 2 O) n -CH 2 CH 2
  • 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;
  • 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 R 1 , R 2 , R 4 and R 5 are hydrogen;
  • 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 (IVa) are pyridinium, 2-methylpyridinium, 2-ethylpyridinium, 5-ethyl-2-methylpyridinium and 2-methyl-3-ethylpyridinium and 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, t- (1-hexadecyl) -pyridinium, 1, 2-dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1 - (1
  • Particularly preferred pyridazinium ions (IVb) are those in which the radicals 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 stand.
  • Particularly preferred pyrimidinium ions (IVc) 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, and R 2 and R 4 is methyl and R 3 is hydrogen.
  • 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 and R 2 and R 4 are methyl and R 3 is
  • R 1 to R 4 are methyl or
  • R 1 to R 4 are hydrogen.
  • Particularly preferred imidazolium ions (IVe) are those in which R 1 is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl and R 2 to R 4 are independently hydrogen, methyl or Ethyl stand.
  • imidazolium ions are 1-methylimidazolium, 1-ethylimidazolium, 1- (1-propyl) -imidazolium, 1- (1-allyl) -imidazolium, 1- (1-butyl) -imidazolium, 1 - (1 - Octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) -imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl 3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) 3-eth
  • Particularly preferred pyrazolium ions (IVf), (IVg) or (IVg ') are those in which
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl.
  • Particularly preferred pyrazolium ions (IVh) are those in which R 1 to R 4 independently of one another are hydrogen or methyl.
  • pyrazolium ions are called pyrazolium and 1, 4-dimethylpyrazolium Particular preference is given in the inventive method as
  • R 1 to R 6 are independently hydrogen or methyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 6 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 to R 6 are independently hydrogen or methyl.
  • imidazolinium ions (IV I) are those in which
  • R 1 and R 2 are independently hydrogen, methyl, ethyl, 1-butyl or phenyl and R 3 and R 4 are independently hydrogen, methyl or ethyl and R 5 and R 6 are independently hydrogen or methyl.
  • imidazolinium ions (IVm) or (IVm ') 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.
  • imidazolinium ions (IVn) or (IVn ') are 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.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
  • Particularly preferred pyrrolidinium ions are those in which R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 9 independently of one another are hydrogen or methyl.
  • Particularly preferred imidazolidinium ions are those in which R 1 and R 4 independently of one another represent hydrogen, methyl, ethyl or phenyl and R 2 , R 3 and R 5 to R 8 are independently hydrogen or methyl.
  • ammonium ions those in which R 1 to R 3 independently of one another are C 1 -C 6 -alkyl, or R 1 and R 2 together represent 1, 5-pentylene or 3-oxa-1, 5 -pentylene and R 3 is selected from Ci-Cis-alkyl, 2-hydroxyethyl or 2-cyanoethyl.
  • tertiary amines of which the quaternary ammonium ions of the general formula (IVu) are derived by quaternization with the radical R mentioned are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethylhexylamine, Diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2-ethylhexyl ) -amine, diisopropylethylamine, di-isopropyl-n-propylamine, di-isopropyl-butylamine, diisopropylpentylamine, di-iso-propyl
  • Preferred tertiary amines 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.
  • R 1 to R 5 are methyl.
  • An especially preferred guanidinium ion (IVv) is N, N, N ', N', N ", N" -hexamethylguanidinium.
  • cholinium ions those in which R 1 and R 2 independently of one another are methyl, ethyl, 1-butyl or 1-octyl, and
  • R 3 is hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 , or
  • R 1 is methyl, ethyl, 1-butyl or 1-octyl
  • R 2 is -CH 2 -CH 2 -OR 4 -;
  • R 3 and R 4 independently of one another represent hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 , or R 1 represents -CH 2 -CH 2 -OR 4 group, R 2 represents 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 stand.
  • Particularly preferred cholinium ions (IVw) are those in which R 3 is selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl,
  • cations (IV.x.1) selected from cations of
  • Particularly preferred phosphonium ions (IVy) are those in which R 1 to R 3 independently of one another are C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl, or phenyl which is unsubstituted or 1, 2, 3, 4 or 5 substituents, which are selected independently of one another from C 1 -C 6 -alkyl, carboxylate, sulfonate, COOH and SO 3 H.
  • Particularly preferred sulfonium ions are those in which R 1 and R 2, independently of one another, are C 1 -C 6 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.
  • the imidazolium ions, imidazolinium ions, pyridinium ions, pyrazolinium ions and pyrazolium ions are preferred. Trains t. Particularly preferred are the imidazolium ions and cations of DBU and DBN.
  • polyatomic anions in principle, all polyatomic anions, d. H. Polyatomic anions (anions with two or more than two atoms), can be used.
  • the anion [Y] n - the ionic liquid is for example selected from
  • radicals R c , R d , R e and R f are preferably each independently
  • Alkyl preferably Ci-C3o-alkyl, particularly preferably Ci-Cis-alkyl, which is unsubstituted, or as defined above, is substituted, and / or, as defined above, may be interrupted by at least one heteroatom or heteroatom-containing group;
  • Aryl preferably C ⁇ -C-u-Arvl, particularly preferably C ⁇ -Cio-aryl, which is unsubstituted, or as defined above, is substituted;
  • Cycloalkyl preferably C5-C12 cycloalkyl which is unsubstituted or substituted as defined above;
  • Heterocycloalkyl preferably heterocycloalkyl having 5 or 6 ring atoms, wherein the ring in addition to carbon ring atoms 1, 2 or 3 heteroatoms or heteroatom-containing groups which is unsubstituted, or as defined above, is substituted;
  • Heteroaryl preferably heteroaryl having 5 to 10 ring atoms, wherein the ring in addition to carbon ring atoms 1, 2 or 3 heteroatom or heteroatom-containing groups which are selected from oxygen, nitrogen, sulfur and NR a , which is unsubstituted, or as defined above, is substituted ;
  • anions which have a plurality of radicals R c to R f in each case two of these radicals together with the part of the anion to which they are attached represent at least one saturated, unsaturated or aromatic ring or a ring system having 1 to 12 carbon atoms may be wherein the ring or the ring system may have 1 to 5 non-adjacent heteroatoms or heteroatom-containing groups, which are preferably selected from oxygen, nitrogen, sulfur and NR a , and wherein the ring or the ring system is unsubstituted or may be substituted.
  • C 1 -C 30 -alkyls in particular C 1 -C 6 -alkyls, C 6 -C 14 -aryls, in particular C 6 -C 10 -cyclo, C 5 -C 12 -cycloalkyls, heterocycloalkyls having 5 or 6 ring atoms and heteroaryls having 5 or 6 Ring atoms is referred to the statements made at the outset.
  • Ci-C 8 alkyl, C 6 -C 2 aryl, C 5 -C 2 cycloalkyl, heterocycloalkyl with 5 or 6 ring atoms and heteroaryl with 5 or 6 ring atoms also referred to the statements made at the outset to substituents.
  • radicals R c to R f is optionally substituted C 1 -C 6 -alkyl, then it is preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, Heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) ethyl
  • At least one of the radicals R c to R f is interrupted by one or more non-adjacent heteroatoms or heteroatom-containing interrupted Ci-cis-alkyl, it is preferably 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxa 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,
  • radicals R c to R f form a ring
  • these radicals can be used 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-Ci-C4-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 heteroatoms or heteroatom-containing groups of the radicals R c to R f is basically not critical and is usually limited only by the size of the respective residue or 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 are generally present between two heteroatoms.
  • Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
  • Preferred functional groups of the radicals R c to R f are carboxy, carboxamide, hydroxy, di- (C 1 -C 4 -alkyl) amino, C 1 -C 4 -alkyloxycarbonyl, cyano or C 1 -C 4 -alkoxy.
  • Alkyl of different radicals R c to R f may also be mono- or polysubstituted by Ci-C 4 -alkyl, preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • At least one of the radicals R c to R f is optionally substituted C 6 -C 12 aryl, then it is preferably phenyl, methylphenyl (ToIyI), XyIyI, ⁇ -naphthyl, ⁇ -naphthyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, Dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso -propylphenyl, tert -butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphen
  • C 5 -C 12 -cycloalkyl it preferably stands for 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.
  • radicals R c to R f are an optionally substituted five- or six-membered heterocycle, it preferably represents furyl, thienyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, Dimethylpyridyl, methylquinolyl, dimethylpyryl, methoxifuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • the substituents are preferably selected independently of one another are alkyl, alkoxy, alkylsulfanyl, cycloalkyl, cycloalkoxy, polycyclyl, heterocycloalkyl, aryl, aryloxy, arylthio and heteroaryl.
  • Preferred anions are, for example, selected from the group of pseudohalides and halogen-containing compounds, the group of carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates.
  • Preferred anions are formate, acetate, propionate, butyrate, lactate, saccharinate, carbonate, bicarbonate, sulfate, sulfite, C 1 -C 4 -alkyl sulfates, methanesulfonate, tosylate, trifluoroacetate, C 1 -C 4 -dialkyl phosphates and hydrogen sulfate.
  • Particularly preferred anions are HCOO-, CH 3 COO-, CH 3 CH 2 COO-, dimethyl phosphate, diethyl phosphate, carbonate, bicarbonate, sulfate, sulfite, tosylate, CH 3 SO 3 - or CH 3 OSO 3 -.
  • Cations and anions are present in the ionic liquid.
  • a proton or an alkyl radical is transferred from the cation to the anion. This creates two neutral molecules.
  • the treatment medium used to modify the cellulosic material may comprise, in addition to at least one ionic liquid, at least one further solvent which is not an ionic liquid.
  • the content of the treatment agent to further solvent is preferably in a range of 5 to 95 wt .-%, particularly preferably 10 to 80 wt .-%, in particular 15 to 60 wt .-%, based on the total weight of the treatment medium used.
  • the liquid treatment medium comprises at least one further solvent
  • this is preferably at least partially miscible with the ionic liquid.
  • the ionic liquid and the further solvent are completely miscible.
  • a liquid treatment medium which comprises at least one further solvent in which the solubility of the cellulosic material is lower under normal conditions (23 ° C., 1 atm.) Than in the ionic liquid.
  • solvent used is preferably a solvent or solvent mixture (precipitant) which is selected from water, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, diols and polyols, such as Ethanediol, propanediol and glycol, amino alcohols such as ethanolamine, diethanolamine and triethanolamine, aromatic solvents, eg. Benzene, toluene, ethylbenzene or xylenes, halogenated solvents, e.g.
  • solvent or solvent mixture selected from water, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, diols and polyols, such as Ethanediol, propanediol and glycol, amino alcohols such as ethanolamine, diethanolamine
  • dichloromethane chloroform, carbon tetrachloride, dichloroethane or chlorobenzene
  • aliphatic solvent eg. Pentane, hexane, heptane, octane, ligroin, petroleum ether, cyclohexane and decalin
  • ethers e.g. For example, tetrahydrofuran, diethyl ether, methyl tert-butyl ether and diethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, esters, eg. Ethyl acetate, and mixtures thereof.
  • the further solvent is selected from water, water-miscible organic solvents and mixtures thereof.
  • Preferred water-miscible organic solvents are the abovementioned alcohols, in particular methanol and / or ethanol.
  • a water-containing medium is used as further solvent.
  • Suitable hydrous media are water and mixtures of water and at least one water-miscible precipitant thereof.
  • Especially preferred is water.
  • an organic solvent is used as a further solvent. Preference is given to the abovementioned alcohols, in particular methanol and / or ethanol.
  • the cellulose material used in the modification process according to the invention preferably has a cellulose content of at least 35% by weight, more preferably of at least 50% by weight. It goes without saying that the cellulosic material used according to the invention contains cellulose which can still undergo a structural change under treatment with at least one ionic liquid. Preferably, therefore, it is a non-pretreated with at least one ionic liquid cellulose.
  • the cellulosic material is preferably selected from cellulose, cellulosic natural materials, wood pulps, pulps, paper and paper-like products, cellulosic textiles and textile components, of which various cellulosic materials and combinations thereof.
  • any known form of cellulose can be used, for. B. from the cellulose materials mentioned below cellulose, regenerated cellulose, bacterial cellulose, etc.
  • Suitable cellulosic natural substances are, for.
  • lignocellulosic materials such as wood, including cellulose-containing natural fiber materials.
  • Under wood pulp fiber materials are wholly or predominantly made by mechanical means of wood, as they are known for. B. as a paper pulp (pulp) can be used. This includes z. B.
  • Pulp wood pulp, brown wood pulp, refiner pulp and wood pulp with chemical pretreatment, such as chemical pulp and chemical refiner pulp.
  • Pulp is understood to mean a fine-fiber mass with a high proportion of cellulose which results from the pulping of wood or other fiber materials. Pulp can z.
  • the pulps obtained by various pulping process such as sulfite pulp, sulfate pulp, soda, nitric, etc., pulp of various provenances, such as Softwood pulp, hardwood pulp, straw pulp, etc.
  • pulps characterized by different degrees of refinement such as unbleached, bleached or bleached pulps.
  • Specific pulp information may, for. B. evidence of the provenance and the digestion process in itself, such. B.
  • paper and paper-like products are also suitable for use in the process according to the invention.
  • the term paper is broadly understood and generally refers to a two-dimensional, essentially cellulosic fibers predominantly of vegetable origin material, which is formed by dewatering a pulp slurry and subsequent compaction and drying of the resulting fiber felt. Paper generally has a basis weight of up to 225 g / m 2 .
  • the basis weight of paperboard is more than 225 g / m 2 .
  • Cardboard refers to a sheet material consisting of paper stock, which lies in its properties between paper and cardboard. Also, the weight per unit area of cardboard reaches into the area of the papers as well as into the cardboard. Cardboard is stiffer than paper and is generally made from higher quality materials than cardboard. Textiles and textile components are also suitable for use in the process according to the invention.
  • the term textiles encompasses fibers for textile use, textiles (ie semi-finished and finished products made of fibers such as yarn or fabric) and finished textile goods (such as textile clothing, etc.). Textiles are generally made of fibers and are much more extended in two dimensions than in a third.
  • Textile surfaces are generally referred to as fabrics and can be z. B. by weaving, knitting, knitting, fulling and solidifying to nonwoven fabric.
  • the cellulosic material is selected from wood, pulps, pulps, paper, paperboard, cardboard, and combinations thereof.
  • the cellulosic material is paper or a paper-like product or cellulosic material which serves as a starting material for the production of paper and paper-like products.
  • the process according to the invention particularly preferably at most 150 0 C and in particular at most 120 0 C. comprises treating the CeIIuIo- sematerials with at least one ionic liquid, as defined above, at a temperature not exceeding 200 0 C, the treatment is preferably carried out at a temperature of at least 20 ° C., more preferably at least 25 ° C.
  • a preferred temperature range is 25 to 120 ° C .; a particularly preferred temperature range is 60 to 100 ° C.
  • the heating can be indirect or direct, preferably indirect. For direct heating, a hot, compatible with the ionic liquid used heat transfer fluid can be used. The indirect heating can be done with customary devices such. B. by heat exchangers, heat baths or microwave irradiation.
  • the pressure in the treatment of the cellulosic material with at least one ionic liquid is generally in a range of 0.1 bar to 100 bar, preferably 1 bar to 10 bar. In a special version, working at ambient pressure.
  • the duration of treatment of the cellulosic material with the ionic liquid is generally 0.5 minutes to 24 hours, preferably 1 to 300 minutes, especially 10 to 100 minutes. By choosing an appropriate, not too long duration of the treatment, it can be prevented that an undesirably large amount of the cellulosic material is converted into a solubilized state.
  • liquid treatment medium after modification may be used partially or completely waived. In a preferred embodiment, however, the liquid treatment medium is at least partially separated from it after the modification of the cellulosic material.
  • the separation into a fraction containing the modified cellulose material and a liquid fraction containing the treatment agent takes place, for. B. by filtration.
  • the filtration can be carried out under cellulosic side increased or expired sided reduced pressure.
  • the separation can be carried out by centrifugation. Usual centrifugation are z. See, for example, G. Hultsch, H. Wilkesmann, "Filtering Centrifuges," DB Purchas, Solid-Liquid Separation, Upland Press, Croydon 1977, pp. 493-559; and H.
  • the modified cellulosic material is preferably subjected to an additional treatment for the removal of ionic liquid still present following the separation of the treatment medium.
  • the cellulosic material may for example be subjected to a wash with a liquid washing medium.
  • Suitable washing media are those in which the ionic liquid dissolves well and cellulose or only in small amounts.
  • Preferred washing media are the additional solvents described above.
  • the washing medium is particularly preferably selected from water and mixtures of water and at least one water-miscible solvent thereof. Water is particularly preferably used as the washing medium.
  • a liquid treatment medium is used to modify the cellulosic material, which contains at least one other solvent in addition to at least one ionic liquid and / or if the cellulosic material is subjected to a treatment with a liquid washing medium to remove any remaining ionic liquid, a liquid composition is obtained contains ionic liquid and a different solvent.
  • This liquid composition is preferably subjected to separation into a fraction containing essentially the ionic liquid (I L1) and a fraction substantially containing the solvent (F1). This separation is usually carried out by evaporation of the precipitant, for. B. by distillation. Suitable separation devices are the customary distillation columns and evaporators, such as. B.
  • Fraction (F1) containing generally at least 80 wt .-%, particularly preferably at least 90 wt .-%, in particular at least 93 wt .-% of the ionic liquid used in the treatment of the cellulosic starting material can be recovered.
  • the fraction essentially containing the ionic liquid (I L1) is preferably used again for modifying the cellulosic starting material.
  • the fraction essentially containing the solvent can be used again as an additional solvent of the treatment medium used for modifying the cellulose material or as a washing medium.
  • the cellulosic material is subjected to grinding before, during and / or after being brought into contact with the liquid treatment medium.
  • the grinding of the cellulosic material takes place in the presence of the liquid treatment medium.
  • the grinding can be done in a suitable device, for example using a refiner.
  • a refiner is a device for mechanically working fibers between rotating grinders at a controlled distance.
  • the usually disk-shaped grinding devices can, for. B. be equipped with knives or Basaltlavamahl Sciencesn.
  • the determination of the degree of grinding can be made after a rough distinction in the grinding states “long and red”, “short and red”, “long and greasy” and “short and greasy”.
  • the exact determination of the freeness can be carried out in a known manner with a MahlgradprüfICI Schopper-Riegler.
  • the difference in freeness of the cellulose material is preferably at least 1 0 SR weight, more preferably at least 10 0 SR.
  • Another object of the invention is a process for the production of paper or a paper-like product, in which one a) providing a cellulose-containing starting material and bringing it into contact with a liquid treatment medium comprising at least one ionic liquid, wherein the bulk of the cellulosic material is not converted into a solubilized state,
  • the cellulose starting material provided in step a) is a material suitable for the production of paper and paper-like products, as is known to those skilled in the art, for example.
  • B. under the name pulp is known.
  • the pulps are subdivided into two groups: primary pulps, ie raw materials that are used for the first time in production, and secondary pulps, ie recycled materials, which are reused in the production process after use.
  • primary fiber materials can be z. B. emanating from groundwood, brown wood pulp, refiner wood pulp, wood pulp with chemical pretreatment, etc. When pulping wood, wood pulp or other fiber materials pulp falls with high cellulose content.
  • step a) For the preparation of the cellulose starting material in step a) are the customary, known to the expert pulping process, such as soda, sulfite, sulfate and Organozellvon, etc. Sulphate pulp is compared to sulfite pulp long-fiber and tear-resistant, so it is mainly for the Production of high white writing and printing papers used. Sulfite pulp finds predominantly use in the production of soft tissue papers. To remove residual lignin and other impurities, the cellulosic material may be subjected to further work-up. Restlignin and other undesirable substances may, for. For example, when bleaching is removed, chemical whitening removes discoloration.
  • Pulps obtained from bleaching with chlorine dioxide are also known as EC F-Ze 11 substances (elementary chlorides). ne free). Other suitable bleaching agents are, for. As oxygen, ozone, peroxoacetic acid, hydrogen peroxide, etc.
  • the resulting pulp is referred to as TCF (totally chlorine free).
  • Paper made from ECF pulps is called low in chlorine (there are still chlorine compounds).
  • TCF pulp generally has lower fiber strength than chlorine-bleached or ECF pulp.
  • Mainly made of wood pulp paper is called woody or medium fine. Since lignin, resins, fats and tannins remain in the pulp, they are of lesser quality than wood-free papers.
  • the bleached pulp is usually dewatered.
  • waste paper is used to provide the cellulosic starting material, this is generally first subjected to a work-up. This usually includes a mechanical processing of the so-called rags by sorting and cleaning in the Haderndrescher. Subsequently, the rags are heated, generally with addition of base (such as CaO, Ca (OH) 2, Na 2 CO 3, K 2 CO 3). Dyes are destroyed, saponified fats and dirt is dissolved. During several hours of cooking, the fabric of the rags loosens and they can then easily pulp into pulp, sorted by grades, bale pressed waste paper with a lot of water crushed and mechanically dissolved.
  • Another suitable device for processing waste paper is the so-called pulper, a chest with rotating propeller.
  • waste paper is crushed with a lot of water and mechanically dissolved. This protects the fibers of the waste paper.
  • the contaminated, pumpable pulp enters the pulper in a cylinder and is defibrated by a rotor. Then the coarsely dissolved substance is forced through a sieve. Due to the centrifugal force coarse impurities are deposited. At the cylinder axis, the light dirt collects. Other foreign substances such as waxes and printing inks are dissolved in special equipment. This includes the chemical treatment for deinking (deinking) of waste paper.
  • the type of grinding essentially determines the property of the paper. In principle, a distinction can be made between a quick grinding and a greasy grinding. Another distinction is made according to the length of the fibers.
  • the fibers are only cut in different lengths and the fiber structure is retained.
  • redcurrant grind For a short reddish grind: z. B. Extinguishing, filter and hygiene papers; For long, redcurrant grind: z. B. printing papers. In greasy grinding (short or long), the fibers are squeezed and crushed.
  • the separation is carried out by filtration.
  • the separated treatment medium is preferably used again in step a).
  • Suitable further components for the production of paper and paper-like products are sizing agents, fillers, dyes and auxiliaries.
  • Cellulosic material and other components are diluted with water and then fed to the manufacture of paper or a paper-like material (eg cardboard, board).
  • the production of paper takes place on paper machines, which usually comprise the following components:
  • the headbox spreads the highly diluted stock evenly across the entire width of the wire section.
  • the paper components are applied so that a homogeneous fiber composite is formed.
  • Through the wire of the wire section there is a strong dewatering, while the fibers deposit next to each other and each other on the screen and form a sheet.
  • the sieve structure is incorporated into the nonwoven fabric. To make the structure the same on both sides of the paper, there are twin-wire machines that extract water both up and down. Some papers receive a watermark at the end of the wire section by the draftsman.
  • the further dewatering of the wet fiber fleece takes place by the pressure of roller pairs.
  • the pressing process causes a compression of the paper structure and the strength is increased.
  • Drying section and reeling The paper web runs like a slalom through the steam-heated drying cylinders and the remaining water is evaporated from the paper in a way that protects the fibers.
  • the paper can be additionally surface-glued. To optimize the sheet thickness, the paper is passed through a roller calender and then rolled up.
  • Finishing takes place in the coating machine, where coating color is applied in excess to the base paper. A doctor blade ensures the correct coating weight and an optimal distribution of the coating color.
  • the invention also provides the cellulosic materials obtainable by the processes described above, especially paper or paper-like products.
  • EMI-DEP 1-ethyl-3-methylimidazolium diethyl phosphate
  • Wood pulp (Schopper-Riegler value 83.5 SR) and spruce pulp (31, 5 SR) are used as cellulosic material.
  • the pulp had a dry content of 30%, it was subjected to disintegration by ZM V / 4/61 at 70000 min-. 1
  • the cellulosic material was subjected to grinding with a Jokro mill with six refineries according to DIN 54 360-04 with 15 min grinding time each with deionized water. Subsequently, laboratory sheets were produced according to DIN EN ISO 5269 / 2-00 and the SR value was measured.
  • the sheets obtained by the soaking process described above were washed in the Rapid-Köthen sheet former. To this was added 2 l of water to the leaf, aspirated and the process then repeated once. Subsequently, the washed sheet was 10 min in Rapid-Kothen T Rockner at 93 0 C under vacuum getrock- net.

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Abstract

L'invention concerne un procédé pour modifier la structure d'un matériau cellulosique, consistant à mettre ce matériau cellulosique en contact avec un agent de traitement liquide comprenant au moins un liquide ionique.
PCT/EP2008/053759 2007-03-30 2008-03-28 Procédé pour modifier la structure d'un matériau cellulosique par traitement au moyen d'un liquide ionique Ceased WO2008119770A1 (fr)

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WO2011027223A1 (fr) * 2009-09-01 2011-03-10 Paul O'connor Prétraitement d'un matériau de biomasse solide contenant de la cellulose au moyen d'un milieu liquide ionique
US7919631B2 (en) 2007-02-14 2011-04-05 Eastman Chemical Company Production of ionic liquids
WO2011114004A1 (fr) 2010-03-18 2011-09-22 University Of Helsinki Procédé pour la fibrillation de matière lignocellulosique, fibres et leur utilisation
US8158777B2 (en) 2008-02-13 2012-04-17 Eastman Chemical Company Cellulose esters and their production in halogenated ionic liquids
US8188267B2 (en) 2008-02-13 2012-05-29 Eastman Chemical Company Treatment of cellulose esters
DE102010061485A1 (de) 2010-12-22 2012-06-28 Chemetall Gmbh Elektroden für Lithium-Batterien
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US8324376B2 (en) 2008-06-17 2012-12-04 Wisconsin Alumni Research Foundation Chemical transformation of lignocellulosic biomass into fuels and chemicals
US8354525B2 (en) 2008-02-13 2013-01-15 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom
US8652261B2 (en) 2009-09-01 2014-02-18 Kior, Inc. Process for dissolving cellulose-containing biomass material in an ionic liquid medium
US8722878B2 (en) 2009-07-01 2014-05-13 Wisconsin Alumni Research Foundation Biomass hydrolysis
US8729253B2 (en) 2011-04-13 2014-05-20 Eastman Chemical Company Cellulose ester optical films
WO2014207100A1 (fr) * 2013-06-27 2014-12-31 Basf Se Procédé de couchage du papier à la cellulose à l'aide d'une solution contenant de la cellulose
US9777074B2 (en) 2008-02-13 2017-10-03 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom
US9834516B2 (en) 2007-02-14 2017-12-05 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom
US10174129B2 (en) 2007-02-14 2019-01-08 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom
CN114846204A (zh) * 2019-12-23 2022-08-02 芬宝公司 纤维素纤维的分散体和生产其的方法
WO2023109738A1 (fr) * 2021-12-15 2023-06-22 兴宇汽车零部件股份有限公司 Particules hybrides de liquide ionique hyper-ramifié/cnf, tpv ignifuge expansé microporeux et procédé de préparation associé

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