EP2035460A1 - Procédé de silylation de cellulose - Google Patents

Procédé de silylation de cellulose

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Publication number
EP2035460A1
EP2035460A1 EP07730232A EP07730232A EP2035460A1 EP 2035460 A1 EP2035460 A1 EP 2035460A1 EP 07730232 A EP07730232 A EP 07730232A EP 07730232 A EP07730232 A EP 07730232A EP 2035460 A1 EP2035460 A1 EP 2035460A1
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EP
European Patent Office
Prior art keywords
alkyl
radicals
group
methyl
cellulose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP07730232A
Other languages
German (de)
English (en)
Inventor
Klemens Massonne
Veit Stegmann
Giovanni D'andola
Werner Mormann
Markus Wezstein
Wei Leng
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Universitaet Siegen
Original Assignee
BASF SE
Universitaet Siegen
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE200610029306 external-priority patent/DE102006029306A1/de
Priority claimed from DE200610032569 external-priority patent/DE102006032569A1/de
Priority claimed from DE200610042890 external-priority patent/DE102006042890A1/de
Priority claimed from DE200610054233 external-priority patent/DE102006054233A1/de
Application filed by BASF SE, Universitaet Siegen filed Critical BASF SE
Publication of EP2035460A1 publication Critical patent/EP2035460A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof

Definitions

  • the present invention describes a process for the silylation of cellulose by reacting cellulose with a silylating agent in an ionic liquid.
  • 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, e.g. 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, silylated celluloses, e.g. Trimethylcellulose, and others count.
  • cellulose ethers e.g. Methylcellulose and carboxymethylcellulose
  • cellulose esters based on organic acids e.g. Cellulose acetate, cellulose butyrate
  • cellulose esters based on inorganic acids e.g. Cellulose nitrate
  • silylated celluloses e.g. Trimethylcellulose, and others count.
  • cellulose silylating agent such as trialkylchlorosilanes such as trimethylchlorosilane, hexamethyldisilazane or N 1 O-bis (trimethylsilyl) acetamide used
  • auxiliary base such as pyridine
  • the cellulose must be activated in an upstream step.
  • the cellulose is pretreated with ammonia, an alkylamine or mixtures thereof. To these heterogeneous systems thus obtained is then added the silylating agent and the silylation is carried out.
  • reaction mixture is initially heterogeneous, runs through a homogeneous phase and is usually heterogeneous again at high DS values (W. Mormann, Cellulose 10, 271 (2003) and Lieratur cited therein). This phenomenon makes a technical implementation practically impossible.
  • silylations of cellulose in dimethylacetamide / LiCl mixtures are described. These are silylations in a homogeneous phase - however, an upstream activation is necessary in order to obtain a homogeneous phase. This makes the process very expensive (W. Schempp et al., Das Textil, 38, 607 (1984)).
  • 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 one, two or more -, tri- or tetravalent anion stands 15
  • 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. 30
  • the ionic liquids of the invention are organic compounds, i. in that at least one cation or anion of the ionic liquid contains an organic radical.
  • 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
  • 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.
  • a cation 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.
  • salts with different anions are obtained.
  • 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.
  • 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 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.
  • aromatic heterocycles are particularly preferred.
  • 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.
  • 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;
  • radicals R 1 to R 9 independently of one another represent hydrogen, a sulfo
  • 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
  • the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable.
  • the radicals R 1 to R 9 may in the cases in which they are bonded in the abovementioned formulas (III) to a carbon atom (and not to a heteroatom) also be bonded directly via the heteroatom.
  • Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom and which do not react with silylating reagents.
  • O in particular as carbonyl group
  • -NR 2 ', NR', -CONH 2 (carboxamide), and -CN (cyano).
  • Fractional 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-C 4 -AlkVl) - amino, Ci-C4-alkyloxycarbonyl or Ci-C4-alkyloxy.
  • the R 'radicals are the remainder of the carbon-containing radical.
  • Halogens are fluorine, chlorine, bromine and iodine.
  • the radical R preferably stands for
  • Halogen, phenyl, cyano and / or C 1 -C 6 -alkoxycarbonyl-substituted C 1 -C 18 -alkyl having a total of 1 to 20 carbon atoms such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl 1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2- Methyl 1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl 3-pentyl, 4-methyl-2
  • Glycols, butylene glycols and their oligomers having from 1 to 100 units, all of the above groups having an ⁇ -C ⁇ -alkyl radical as end group, that is to say, for example, R A O- (CHR B -CH 2 -O) m -CHR B -CH 2 - or R A O- (CH 2 CH 2 CH 2 CH 2 O) m -CH 2 CH 2 CH 2 CH 2 - with R A and R B preferably methyl or ethyl and m preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3, 6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;
  • N, N-di-Ci-C ⁇ -alkyl-amino such as N, N-dimethylamino and N 1 N-diethylamino.
  • the radical R particularly preferably represents unbranched and unsubstituted C 1 -C 18 -alkyl, such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 1-propen-3-yl, in particular methyl, ethyl, 1-butyl and 1-octyl, and also CH 3 O- (CH 2 CH 2 COm-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.
  • C 1 -C 18 -alkyl such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl,
  • radicals R 1 to R 9 are preferably each independently
  • a suitable functional group optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups - Ci ⁇ -alkyl;
  • C 2 interrupted by suitable functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups -
  • aryl optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, Alky- loxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl;
  • C5-C12-cycloalkyl substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles;
  • C5-C12-cycloalkenyl substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles; or
  • an unsaturated, saturated or aromatic optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more sub- substituted or unsubstituted imino groups interrupted ring.
  • Ci-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-
  • aryl is, it is preferably phenyl, tolyl, xylyl, ⁇ -naphthyl, ß-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethyl phenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl
  • C 5 -C 12 -cycloalkyl which is optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyl-loxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl , Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C m F 2 ( m -a) - (ib) H 2a-b with im ⁇ 30, 0
  • An optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl , Pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
  • Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally by one or more oxygen and / or sulfur atoms and / or or a plurality of substituted or unsubstituted imino groups interrupted ring, it is preferably 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3 -propylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propenylene, 3-oxa-1, 5-pentylene, 1-aza-1, 3-propenylene, 1-Ci-C4-alkyl 1-aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1-aza-1, 4-buta-1, 3-dienylene or 2-aza-1, 4-buta-1 , 3-dienylene.
  • 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.
  • radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.
  • radicals R 1 to R 9 are each independently
  • Halogen, phenyl, cyano and / or C 1 -C 6 -alkoxycarbonyl-substituted C 1 -C 20 -alkyl having in total 1 to 20 carbon atoms such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2 butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-
  • Glycols, butylene glycols and their oligomers having from 1 to 100 units, wherein all the above groups carry a Ci-Cs-alkyl radical as an end group, so for example R A O- (CHR B -CH 2 -O) m -CHR B -CH 2 - or R A O- (CH 2 CH 2 CH 2 CH 2 O) m -CH 2 CH 2 CH 2 CH 2 - with R A and R B preferably, methyl or ethyl and n preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-
  • N N-di- (Ci-C6-alkyl) amino, such as N, N-dimethylamino and N 1 N-diethylamino;
  • R 3 is not hydrogen
  • the radicals R 1 to R 9 are each independently hydrogen or Ci-Cis-alkyl, such as methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, phenyl , for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N-diethylamino, for chlorine and for CH 3 O- (CH 2 CH 2 O) m -CH 2 CH 2 - and CH 3 CH 2 O- (CH 2 CH 2 CVCH 2 CH 2 - with m equal to 0 to 3.
  • Ci-Cis-alkyl such as methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl
  • radicals R 1 to R 5 are 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 carboxamide and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen; or
  • R 1 and R 2 or R 2 and R 3 are 1, 4-buta-1, 3-dienylene and the remaining R 1 , R 2 , R 4 and R 5 are hydrogen;
  • R 1 to R 5 are hydrogen
  • radicals R 1 to R 5 are methyl or ethyl and the remaining radicals R 1 to R 5 are hydrogen.
  • pyridinium ions (IIIa) there may be mentioned 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,
  • MIb very particularly preferred pyridazinium ions
  • R 1 to R 4 are hydrogen
  • radicals R 1 to R 4 are methyl or ethyl and the remaining radicals R 1 to R 4 are hydrogen.
  • MIc very particularly preferred pyrimidinium ions
  • 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.
  • MId very particularly preferred pyrazinium ions
  • 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
  • R 1 to R 4 are methyl hydrogen.
  • Imidazoliumionen are those in which • R 2 to R 4 are independently hydrogen; preferably R 2 to R 4 independently of one another are hydrogen, and R and R 1 independently of one another are C 1 -C 4 -alkyl or allyl.
  • MIe imidazolium ions
  • R 3 and R 4 are independently hydrogen; preferably R 3 and R 4 independently of one another are hydrogen, and R, R 1 and R 2 independently of one another are C 1 -C 4 -alkyl or allyl; in particular R 3 and R 4 preferably each independently hydrogen, R and R 1 are independently -C 4 - alkyl, and R 2 are Ci-C 4 alkyl or allyl.
  • MIe imidazolium ions
  • R 1 is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 1-propen-3-yl or 2-cyanoethyl
  • R 2 to R 4 are independently hydrogen , Methyl or ethyl.
  • MIe Very particularly preferred imidazolium ions 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)
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl.
  • R 1 to R 4 are independently hydrogen or methyl.
  • R 1 to R 6 are hydrogen or methyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 6 are independently hydrogen or methyl.
  • MIk 3-pyrazolinium
  • IMk ' 3-pyrazolinium
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 to R 6 are independently hydrogen or methyl.
  • IUI imidazolinium ions
  • 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.
  • 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.
  • IMn imidazolinium ions
  • MIn ' imidazolinium ions
  • R 1 to R 3 are independently hydrogen, methyl or ethyl and R 4 to R 6 are independently hydrogen or methyl.
  • MIo thiazolium ions
  • MIo ' thiazolium ions
  • MIp oxazolium ions
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are independently hydrogen or methyl.
  • MIq 1,2,4-triazolium ions
  • MIq ' 1,2,4-triazolium ions
  • MIq 1,2,4-triazolium ions
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
  • 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.
  • MIs very particularly preferred pyrrolidinium ions
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 9 are independently of one another hydrogen or methyl.
  • 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.
  • 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 or 2-cyanoethyl.
  • ammonium ions may be mentioned methyl tri (1-butyl) -ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.
  • tertiary amines of which the quaternary ammonium ions of the general formula (IMu) are derived by quaternization with the radicals R mentioned are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl hexylamine, diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2 ethylhexyl) amine, di-isopropylethylamine, di-isopropyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpentylamine, di-iso-propyle
  • Preferred quaternary ammonium ions of the general formula (MIu) are those which are derived from the following tertiary amines by quaternization with the abovementioned radicals R, such as diisopropylethylamine, diethyl-tert-butylamine, diisobutylbutylamine, di-isopropylamine n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.
  • R such as diisopropylethylamine, diethyl-tert-butylamine, diisobutylbutylamine, di-isopropylamine n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.
  • tertiary amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers.
  • Another preferred tertiary amine having three identical residues is triallylamine.
  • MIv guanidinium ions
  • R 1 to R 5 are methyl.
  • MIv guanidinium ion
  • MIw cholinium ions
  • R 1 and R 2 are independently methyl, ethyl, 1-butyl or 1-octyl and R 3 is methyl, ethyl or acetyl;
  • R 1 is methyl, ethyl, 1-butyl or 1-octyl
  • R 2 is a -CH 2 -CH 2 -OR 4 group and R 3 and R 4 are independently methyl, ethyl or acetyl; or
  • R 1 is a -CH 2 -CH 2 -OR 4 group
  • R 2 is a -CH 2 -CH 2 -OR 5 group
  • R 3 to R 5 are independently methyl, ethyl or acetyl.
  • cholinium ions are those in which R 3 is selected from methyl, ethyl, acetyl, 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-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9-trioxa -undecyl, 7-ethoxy-4-oxa
  • phosphonium ions 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.
  • the pyridinium ions, pyrazolinium, pyrazolium ions and imidazolinium and imidazole ions are preferred.
  • ammonium ions are preferred.
  • the anion [Y] n - the ionic liquid is for example selected from
  • R 3 , R b , R c and R d each independently of one another denote hydrogen, C 1 -C 30 -alkyl, if appropriate by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted te imino interrupted C 2 -Ci8 alkyl, C6-Ci 4 -aryl, C5-Ci 2 -cycloalkyl or
  • ⁇ - to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle two of them together having one unsaturated, saturated or aromatic, optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups can form interrupted ring, wherein said radicals each additionally by suitable functional groups, aryl, alkyl, aryloxy, alkyl, oxy, halogen, heteroatoms and / or heterocycles may be 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, heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3, 3 Tetramethylbutyl, benzyl, 1-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butyl),
  • 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-Cis-alkyl are, for example, 5-methoxy-3-oxapentyl, 8-methoxy-3,6- dioxo-octyl, 1 1-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 1 1-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxo-octyl, 1-ethoxy-3,6,9-trioxa-undecyl,
  • 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 especially 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: carboxamide, di- (C 1 -C 4 -alkyl) amino, C 1 -C 4 -alkyloxycarbonyl, cyano or C 1 -C 4 -alkoxy, where CrC 4 -alkyl is methyl , Ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C6-C 4 aryl are for example phenyl, tolyl, xylyl, ⁇ -naphthyl, ß-naphthyl, 4-diphenylyl, chlorophenyl, Dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphth
  • C 5 -C 12 -cycloalkyl optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, halogen, heteroatoms and / or heterocycles are, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butyl - cyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthio cyclohexyl, 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 sulfates, sulfites and sulfonates, the group of phosphates, and the group of carboxylic acids, in particular from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group containing 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 -.
  • Particularly preferred anions are chloride, bromide, iodide, SCN, OCN, CN, acetate, propionate, benzoate, C 1 -C 4 -alkyl sulfates, R a -COO " , R 3 SO 3 " , R a R b PO 4 , Methanesulfonate, tosylate or di- (C 1 -C 4 -alkyl) phosphates.
  • Particularly preferred anions are Ch, CH 3 COO, C 2 H 5 COO, C 3 H 7 COO " , C 6 H 5 COO, CH 3 SO 3 -, (CH 3 O) 2 PO 2 - or (C 2 H 5 O) 2 PO 2 "
  • Particularly preferred anions are Ch, CH 3 SO 3 -, (CH 3 O) 2 PO 2 - or (C 2 H 5 O) 2 PO 2 -
  • CH 3 COO, C 2 H 5 COO, C 3 H 7 COO " or C 6 H 5 COO " are particularly preferred.
  • ionic liquids are used whose anions are selected from the group comprising HSO 4 " , HPO 4 2" , H 2 PO 4 " and HR 3 PO 4 -, in particular HSO 4 -.
  • 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.
  • an ionic liquid of the formula II or a mixture of ionic liquids. th of the formula II, preferably an ionic liquid of the formula II is used.
  • Silylianssmitttel the purposes of this invention are those which are capable of a SiR x R y R z group to a hydroxy group to form an O-SiR x R y R z - to transfer group.
  • silylating agents of formula IV are those which are capable of a SiR x R y R z group to a hydroxy group to form an O-SiR x R y R z - to transfer group.
  • C 1 -C 30 -alkyl radicals for R x , R y and R z are unsubstituted C 1 -C 30 -alkyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted C 1 -C 30 -alkyl radicals, preferably C 1 -C 30 -alkyl radicals, such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2 -Methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl , 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 2-
  • Unsubstituted C 2 -C 3 o-alkenyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen may be mentioned as unsubstituted or substituted C 2 -C 30 -alkenyl radicals for R x , R y and R z , Heteroatoms and / or heterocycles substituted C2-C 3 o alkenyl radicals, preferably C2-C 3 o-alkenyl radicals, such as vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl or trans-2 -Butenyl, particularly preferably vinyl or 2-propenyl; or preferably C 2 -C 30 -alkenyl radicals substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as, for
  • Unsubstituted C 2 -C 3 o-alkynyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen may be mentioned as unsubstituted or substituted C 2 -C 30 -alkynyl radicals for R x , R y and R z , heteroatoms and / or heterocycles substituted C2-C 3 -alkynyl radicals mentioned, preferably C 2 -C 30 -alkynyl radicals, such as, for example, ethynyl, 1-propyn-3-yl, 1-propyn-1-yl or 3-methyl-1-propyn-3-yl, particularly preferably ethynyl or 1-propyn-3 yl.
  • Unsubstituted C 1 -C 8 -cycloalkyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or as unsubstituted or substituted C 3 -C 12 -cycloalkyl radicals for R x , R y and R z are particularly or heterocycles substituted C3-Ci2-cycloalkyl radicals, preferably C3-Ci2-cycloalkyl radicals, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl or butylcyclohexyl and bicyclic system such as norbornyl
  • Unsubstituted Cs-Cs-cycloalkenyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or unsubstituted Cs-Cs-cycloalkenyl radicals may be mentioned as unsubstituted or substituted C 5 -C 12 -cycloalkenyl radicals for R x , R y and R z .
  • C 6 -C 12 aryl radicals or C 6 substituted by suitable functional groups may be mentioned as optionally substituted aryl radicals for R x , R y and R z -Ci2-aryl radicals, preferably C6-Ci2-aryl radicals, such as phenyl, ⁇ -naphthyl or ß-naphthyl, particularly preferably phenyl; or preferably by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl radicals such as ToIyI, XyIyI, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, di
  • Ci-C ⁇ -alkyl radicals as a sub-substituent of X, 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-buty
  • Ci-C ⁇ -haloalkyl radicals as a sub-substituent of X, for example, Ci-C ⁇ -alkyl radical as described above, which are partially or completely substituted by fluorine, chlorine, bromine and / or iodine, called, eg.
  • silylating agents of the formula IV are used, where the radicals have the following meanings:
  • R x , R y , R z is Ci-C 3 O-AIkVl, C 2 -C 3 o-alkenyl, C 2 -C 3 O-Al kinyl, C 3 -C 2 -cycloalkyl, C 5 -C 2 -
  • Cycloalkenyl or aryl these six radicals may be optionally substituted; in particular C 1 -C 30 -alkyl or aryl, where these radicals may optionally be substituted, preferably C 1 -C 6 -alkyl or phenyl; in particular C 1 -C 4 -alkyl or phenyl, preferably C 1 -C 4 -alkyl;
  • X is halogen, imidazol-1-yl, di- (C 1 -C 6 -alkyl) -amine, NH-SiR x RvR z , NH-CO-NH-
  • the silylating agent of the formula IV used is hexamethyldisilazane (HMDS), trimethylsilyldiethylamine or N, O-bis (trimethylsilyl) acetamide.
  • celluloses from a wide variety of sources can be used, e.g. from cotton, flax, ramie, straw, bacteria, etc., or from wood or bagasse, in the cellulose-enriched form.
  • the process of the invention can be used not only for the silylation of cellulose but generally for the silylation of poly-, oligo- and disaccharides, as well as derivatives thereof.
  • polysaccharides in addition to cellulose and hemicellulose, include starch, glycogen, dextran and tunicin.
  • polycondensates of D-fructose such as inulin, as well as chitin, chitosan and alginic acid.
  • Sucrose is an example of a disaccharide.
  • Suitable cellulose derivatives are those whose DS ⁇ 3 is, inter alia, cellulose ethers, such as methylcellulose and carboxymethylcellulose, cellulose esters, such as cellulose acetate, cellulose butyrate and cellulose nitrate, each with a DS ⁇ 3.
  • a polysaccharide such as, for example, cellulose, hemicellulose, starch, glycogen, dextran, tunicin, inulin, chitin, chitosan or alginic acid, preferably cellulose, is silylated by the process according to the invention.
  • a disaccharide e.g. Sucrose, silylated.
  • a cellulose derivative whose DS is ⁇ 3 e.g. a cellulose ether such as methyl cellulose and carboxymethyl cellulose, a cellulose ester such as cellulose acetate, cellulose butyrate, and cellulose nitrate each having a DS ⁇ 3 silylated.
  • a solution of cellulose in ionic liquid is prepared.
  • concentration of cellulose can be varied within wide ranges. Usually, it is in the range of 0.1 to 50 wt .-%, based on the total weight of the solution, preferably 0.2 to 40 wt .-%, particularly preferably 0.3 to 30 wt .-% and particularly preferably at 0.5 to 20% by weight.
  • This dissolution process can be carried out at room temperature or under heating, but above the melting or softening temperature of the ionic liquid, usually at a temperature of 0 to 200 ° C, preferably at 20 to 180 ° C, particularly preferably at 50 to 150 ° C. , But it is also possible to accelerate the dissolution process by intensive stirring or mixing and by entry of microwave or ultrasonic energy or by combining them.
  • the silylating agent of the formula IV can be added in bulk, dissolved in an ionic liquid or in a suitable solvent.
  • suitable solvents include, for example, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, or ketones, such as dimethyl ketone, halogenated hydrocarbons, such as dichloromethane, trichloromethane or dichloroethane, or hydrocarbons, for example aromatic hydrocarbons, such as benzene, Toluene, xylene or mesitylene.
  • the amount of solvent used to dissolve the silylating agent of formula IV should be such that no precipitation of the cellulose occurs upon addition.
  • ionic liquid is preferably the one in which the cellulose itself - as described above - is dissolved.
  • the silylating agent of formula IV is added in bulk.
  • the silylating agent of formula IV is added dissolved in an ionic liquid, with particular preference being given to using the ionic liquid which is also used to dissolve the cellulose.
  • the ionic liquid and the silylating agent of the formula IV are premixed and the cellulose is dissolved in this mixture.
  • Suitable solvents are those solvents which do not adversely affect the solubility of the cellulose, such as aprotic dipolar solvents, for example dimethylsulfoxide, dimethylformamide, dimethylacetamide or sulfolane.
  • aprotic dipolar solvents for example dimethylsulfoxide, dimethylformamide, dimethylacetamide or sulfolane.
  • nitrogen-containing bases such as pyridine, etc., can also be added.
  • the reaction mixture in addition to the ionic liquid and optionally the solvent in which the silylating agent of the formula IV is dissolved less than 5 wt.%, Preferably less than 2 wt.%, In particular less than 0.1 wt. %, based on the total weight of the reaction mixture, of further solvents and / or additional nitrogen-containing bases.
  • a catalyst Mono- or disaccharides, e.g. Glucose or sucrose, or saccharin, preferably saccharin.
  • the catalyst is usually used in amounts of up to 10 mol%, preferably up to 5 mol%, based on the silylating agent of the formula IV.
  • a tertiary amine such as triethylamine, an aromatic nitrogen base such as pyridine, or mixtures thereof; especially when an acid is released during silylation.
  • the teriary amine, the aromatic nitrogen base or the mixtures thereof are usually used in a stoichiometric ratio. On a case-by-case basis, an excess or a deficit can also be beneficial.
  • the reaction is usually carried out at a temperature of the melting point of the ionic liquid up to 200 ° C., preferably from 20 to 180 ° C., in particular from 50 to 150 ° C.
  • the reaction usually takes place at ambient pressure. However, it may also be advantageous on a case-by-case basis to work at overpressure, especially if a volatile silylating agent of the formula IV is used.
  • the reaction is carried out in air or under a protective gas atmosphere, that is, for example, under N 2 , a noble gas, or mixtures thereof.
  • the amount of silylating agent used - in each case in relation to the cellulose used - the reaction time and optionally the reaction temperature is set.
  • silylating agent of the formula IV 3u equivalents of silylating agent of the formula IV are required in the event that the silylating agent transfers a silyl group.
  • the amounts of silylating agent used of formula IV decreases accordingly.
  • the amounts of silylating agent of the formula IV used are usually adjusted (ns ⁇ i y i ⁇ réellesm ⁇ ttei / nAn- hydrogiucoseem felt ⁇ 3, in the event the silylating agent of formula IV transfers a silyl group).
  • the amounts of silylating agent used of the formula IV or the reaction time is reduced accordingly. Furthermore, it is possible to terminate the silylation reaction when the desired degree of silylation is achieved by separating the silylated cellulose from the reaction mixture. This can be achieved, for example, by adding an excess of a suitable solvent in which the silylated cellulose is not soluble but the ionic liquid is readily soluble, such as a lower alcohol such as methanol, ethanol, propanol or butanol, or with a ketone For example, diethyl ketone, etc., or mixtures thereof, take place. The choice of the suitable solvent is also determined by the respective degree of substitution and the substituents of the cellulose. Preferably, an excess of methanol is used.
  • the work-up of the reaction mixture is usually carried out by precipitating the silylated cellulose as described above and filtering off the silylated cellulose. But it is also possible to carry out the separation by centrifugation. From the filtrate or the centrifugate can be recovered by conventional methods, the ionic liquid by the volatile components, such. the precipitant, or excess silylating agent of the formula IV (or reaction products and / or hydrolysis products of the silylating agent of the formula IV) etc. are distilled off. The remaining ionic liquid can be reused in the process according to the invention.
  • reaction mixture in methanol or in another suitable solvent in which the silylated cellulose is not soluble, but the ionic liquid is readily soluble, such as.
  • Another low alcohol such as ethanol, propanol or butanol, or a ketone, such as diethyl ketone, etc., or mixtures thereof initiate and, depending on the embodiment, for example, to obtain fibers, films of silylated cellulose.
  • the choice of the suitable solvent is also determined by the respective degree of substitution and the substituents of the cellulose.
  • the filtrate is worked up as described above.
  • the termination of the silylation reaction can also be carried out so that at a given time still existing silylating agent of the formula IV from the reaction onsgemisch by distillation, stripping or extracting with a solvent which forms two phases with the ionic liquid, is removed.
  • silylated cellulose separates during the reaction of the ionic liquid or the reaction mixture, it may be advantageous to separate the silylated cellulose after completion of the reaction by filtration and optionally to wash with a suitable solvent.
  • a suitable solvent that is immiscible with the reaction mixture but dissolves the silylated cellulose may be added. After phase separation, the silylated cellulose is recovered from the extract by distilling off the added solvent.
  • Suitable solvents are, for example, hydrocarbons, such as aromatic hydrocarbons, for example benzene, toluene, xylene, mesitylene or mixtures thereof, into consideration. From case to case, it may also be advantageous to add this solvent right at the beginning of the reaction, the reaction then taking place in a two-phase (liquid / liquid) system.
  • the cellulose is reacted with a silylating agent of the formula IV in an ionic liquid of the formula I in which [Y] n -R 3 COO "In this case, in addition to the silylation of the cellulose, a Acylation of the cellulose occur, with the remainder R 3 COO is transferred.
  • the cellulose can be reacted with two or more silylating agents of the formula IV which transfer different silyl groups.
  • a mixture of two (or more) silylating agents of the formula IV can be used in analogy to the above procedure.
  • silylated celluloses are obtained which carry two (or more) different silyl radicals (depending on the silylating agent of the formula IV used).
  • 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 , provided, however, that these do not lead to decomposition of the SiIyMe- used agent.
  • the process can be carried out batchwise, semicontinuously or continuously. Furthermore, it may be advantageous to carry out the reaction in the absence of moisture since silylating agents are generally sensitive to moisture.
  • the reagents used, solvents, etc. are dried by conventional laboratory methods, the ionic liquid used and the cellulose can be dried, for example under heating in a vacuum, optionally used solvents and protective gases by methods known in the art, etc.
  • the cellulose used can be dissolved in an ionic liquid of the formula I or II or mixtures thereof, and in step a1) the cellulose is degraded in the presence of an acid, optionally with the addition of water to a desired average degree of polymerization DP, and in a step b) subjecting the resulting degraded cellulose to silylation as described above.
  • Step a1) can be carried out as follows:
  • inorganic acids organic acids or mixtures thereof can be used.
  • 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
  • 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
  • hydrogen halide acids such as HCl or HBr, H2SO4, HN ⁇ 3 ⁇ der H3PO4 used, in particular HCl, H 2 SO 4 or H 3
  • organic acids examples include carboxylic acids, such as
  • C 1 -C 6 -alkanecarboxylic acids for example acetic acid, propionic acid, n-butanecarboxylic acid or pivalic acid,
  • Polycarboxylic acids for example succinic acid, maleic acid or fumaric acid,
  • Hydroxycarboxylic acids for example hydroxyacetic acid, lactic acid, malic acid or citric acid
  • Halogenated carboxylic acids for example C 1 -C 6 -haloalkanecarboxylic acids, for example 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;
  • C 1 -C 6 -alkanesulfonic acids for example methanesulfonic acid or ethanesulfonic acid,
  • Halogenated sulfonic acids for example C 1 -C 6 -haloalkanesulfonic acids, such as trifluoromethanesulfonic acid,
  • Aromatic sulfonic acids for example arylsulfonic acids, such as benzenesulfonic acid or 4-methylphenylsulfonic acid.
  • the organic acids used are preferably C 1 -C 6 -alkanecarboxylic acids, for example acetic acid or propionic acid, halogenated carboxylic acids, for example C 1 -C 6 -haloalkanecarboxylic acids. e.g.
  • 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-Methylphenylsulfonklad.
  • sulfonic acids such as C 1 -C 6 alkanesulfonic acids, for example methanesulfonic acid or ethanesulfonic acid, halogenated sulfonic acids, for example C 1 -
  • acetic acid chlorofluoroacetic acid, trifluoroacetic acid, perfluoropropionic acid, methanesulfonic acid, trifluoromethanesulfonic acid or 4-methyl-phenylsulfonic acid are used.
  • the acid sulfuric acid 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.
  • ionic liquids and acids are used whose anions are identical.
  • these anions are acetate, trifluoroacetate, chloride or bromide.
  • ionic liquids and acids are used whose anions are not identical.
  • the acid and optionally water is added.
  • the addition of water may be necessary if the adhering to the cellulose used water is not sufficient to achieve the desired degree of degradation.
  • 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).
  • substoichiometric amounts of water and acid are added or the reaction is stopped at a given time.
  • the ionic liquid, acid and possibly water are premixed and the cellulose is dissolved in this mixture.
  • Suitable solvents 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.
  • 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.
  • reaction is carried out at ambient pressure.
  • overpressure especially when volatile acids are used.
  • reaction is carried out in air.
  • inert gas for example under N 2, a noble gas, or a mixture thereof.
  • 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.
  • 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.
  • the base used may be a hydroxide which is characterized in that its cation corresponds to that of the ionic liquid used.
  • step b) The solution thus obtained is now used in step b) as described above.
  • the cellulose used can be dissolved in an ionic liquid of the formula I or II or mixtures thereof, and in step a2) the cellulose may optionally be treated with the addition of water at elevated temperature, and in a step b) the so obtained degraded cellulose to be silylated as described above.
  • Step a2) can be carried out as follows:
  • ionic liquids which have no acidic functions
  • degradation is usually carried out at temperatures of from 50 to 200.degree. C., preferably from 80.degree. C. to 180.degree. C., in particular from 80 to 150.degree.
  • Suitable ionic liquids are those whose anions are selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group containing SO 4 2 " , SO 3 2" , R a OS ⁇ 3 " and R a S ⁇ 3 " , and the group containing PO 4 3 " and R a R b PO 4 " .
  • Preferred anions here are chloride, bromide, iodide, SCN, OCN, CN, acetate, CrC 4 alkyl sulfates, R a -COO " , R 3 SO 3 " , R a R b " PO 4 " , methanesulfonate, tosylate or C 1 -C 4 dialkyl phosphates; and especially
  • the 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 -
  • ionic liquids which have acidic functions, then it is possible to carry out the degradation of the cellulose at a temperature of from 0 to 150 ° C., preferably from 20 to 150 ° C., in particular from 50 to 150 ° C. Particular preference is given here to ionic liquids whose anions are selected from the group comprising HSO 4 " , HPO 4 2" , H 2 PO 4 - and HR 3 PO 4 -; especially HSO 4 -.
  • the preparation of the reaction solution and the degradation are carried out at the same temperature.
  • the preparation of the reaction solution and the degradation are carried out at different temperatures.
  • reaction is carried out at ambient pressure. It may also be advantageous from case to case to work at overpressure.
  • the reaction is carried out in air.
  • inert gas that is, for example, under N 2 , a noble gas, or even mixtures thereof.
  • reaction time and the reaction temperature are adjusted.
  • water is added.
  • substoichiometric amounts of water are preferably added or the reaction is stopped.
  • the quantities used are usually tem water adjusted according to the degree of degradation (nAnhydrogiucoseemhe ⁇ ten / nwasser > 1).
  • Suitable solvents 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.
  • 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.
  • step b) The solution thus obtained is now used in step b) as described above.
  • a silylated cellulose having a DS ⁇ 3 may be subjected to acylation.
  • Acylating agents in the context of the present invention are carboxylic acid derivatives and also ketenes and diketenes.
  • Carboxylic acid derivatives in the context of the present invention are carboxylic acid derivatives of the formula V
  • T is halogen, imidazol-1-yl or O-COR 5 ' .
  • Ketenes for the purposes of the present invention are ketene of the formula VIa and diketenes in the sense of the present invention are dicentenes of the formula VIbI or mixed diketenes of the formula VIbb,
  • R 1, R 1 ', R u, R u is hydrogen, Ci-C 30 alkyl, C 2 -C 30 -alkenyl, C 2 -C 30 -alkyl kinyl, C 3 -C 2 -
  • Cycloalkyl C5-Ci2 cycloalkenyl, aryl or heterocyclyl, where the seven ultimately radicals mentioned optionally may be substituted;
  • Ci-C 30 -alkyl radicals for R s , R s' , R 1 , R t? , R u and R u 'in particular, unsubstituted Ci-C rocyclen 30 -alkyl radicals or by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or hetero- substituted Ci-C 30 alkyl Called radicals, preferably C 1 -C 30 -alkyl radicals, such as, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl , 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1
  • C 2 -C 3 o-alkenyl radicals for R s , R s' , R 1 , R t? , R u or R u ' may be mentioned in particular unsubstituted C 2 -C 30 -alkenyl radicals or C 2 -C 30 -alkenyl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, preferably C 2 -C 30 -alkenyl radicals, such as, for example, vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl or trans-2-butenyl, particularly preferably vinyl or 2-propenyl; or C 2 -C 30 -alkenyl radicals which are preferably substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, hal
  • C 2 -C 3 o-alkynyl radicals for R s , R s' , R 1 , R t? R u and R u ' may be mentioned in particular unsubstituted C 2 -C 30 -alkynyl radicals or C 2 -C 3 -alkynyl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, preferably C 2 -C 30 -alkynyl radicals, such as, for example, ethynyl, 1-propyn-3-yl, 1-propyn-1-yl or 3-methyl-1-propyn-3-yl, particularly preferably ethynyl or 1-propyn-3 yl.
  • C 3 -C 2 -cycloalkyl radicals for R s , R s' , R 1 , R 1 ' , R u or R u' are in particular unsubstituted Cs-Cs-cycloalkyl radicals or by functional groups, aryl , Alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles called C3-Ci2-cycloalkyl radicals, preferably C3-Ci2-cycloalkyl radicals, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl , Dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl or butylcyclohexyl, and
  • C 5 -C 12 -cycloalkenyl radicals for R s , R s' , R 1 , R t? R u and R u ' may be mentioned in particular unsubstituted Cs-Cs-cycloalkenyl radicals or Ca-Cs-cycloalkenyl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, preferably Ca-C ⁇ -cycloalkenyl radicals, such as 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl, as well as bicyclic system such as eg norbornyl, more preferably 3-cyclopentenyl, 2-cyclohexenyl or 3-cyclohexenyl; or preferably Ca-Cs-cycloalkenyl radicals substituted by
  • aryl radicals for R s , R s' , R 1 , R t? R u and R u ' may be mentioned in particular unsubstituted C 6 -C 12 -aryl radicals or C 6 -C 12 -aryl radicals which are substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, preferably C 6 -C 12 aryl radicals, such as, for example, phenyl, ⁇ -naphthyl or ⁇ -naphthyl, particularly preferably phenyl; or preferably C6-C12-aryl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as ToIyI, XyIyI, 4-dipheny
  • heterocyclyl radicals which may be mentioned are unsubstituted heteroaryl radicals or heteroaryl radicals which are substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, preferably 5- or 6-membered heteroaryl radicals which have oxygen, nitrogen and / or sulfur atoms, such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl or benzothiazolyl; or preferably 5- or 6-membered heteroaryl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles and having oxygen, nitrogen and / or sulfur atoms, such as methylpyridy, dimethylpyr
  • carboxylic acid derivatives of the formula V are used.
  • carboxylic acid derivatives of the formula V are used, where the radicals have the following meanings:
  • R s , R s' are hydrogen or Ci-C 3 o-alkyl
  • R s is hydrogen or C 1 -C 6 -alkyl, preferably hydrogen or C 1 -C 6 -alkyl; particularly preferably methyl, ethyl or butyl;
  • T halogen preferably chloride.
  • carboxylic acid derivatives of the formula V are used, the radicals having the following meanings:
  • R s is 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
  • T halogen preferably chloride.
  • R s ', R s' are hydrogen or C 1 -C 6 -alkyl, preferably hydrogen or C 1 -C 6 -alkyl; particularly preferably methyl, ethyl or butyl;
  • carboxylic acid derivatives of the formula V are used, the radicals having the following meanings:
  • R s is 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
  • ketenes of the formula VIa are used.
  • ketenes of the formula VIa are used, where the radicals have the following meanings:
  • R 1 is hydrogen or C 1 -C 6 -alkyl, preferably hydrogen or C 1 -C 6 -alkyl; particularly preferably hydrogen, methyl or ethyl; most preferably hydrogen;
  • ketenes of the formula VIa are used, where the radicals have the following meanings:
  • R 1 is 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
  • diketenes of the formula VIbI are used.
  • diketenes of the formula VIbI are used, where the radicals have the following meanings:
  • R 1 is hydrogen or C 1 -C 6 -alkyl, preferably hydrogen or C 1 -C 6 -alkyl, particularly preferably hydrogen, methyl or ethyl, in particular hydrogen;
  • R 1 is 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
  • mixed diketenes of the formula VIbb are used.
  • mixed diketenes of the formula Vlb2 are used, where the radicals have the following meanings:
  • R 1 , R u is hydrogen or C 1 -C 6 -alkyl, preferably hydrogen, methyl or ethyl, in particular hydrogen;
  • R 1 , R u ' is hydrogen.
  • R 1 , R u ' is hydrogen.
  • the acetylation of the silylated cellulose can be carried out in analogy to the methods known to the person skilled in the art. However, it is also possible to carry out the reaction of the silylated cellulose in an ionic liquid.
  • the silylated cellulose is dissolved in a, as described above, ionic liquid.
  • the concentration of silylated cellulose can be varied within a wide range. Usually, it is in the range of 0.1 to 50 wt .-%, based on the total weight of the solution, preferably 0.2 to 40 wt .-%, particularly preferably 0.3 to 30 wt .-% and particularly preferably at 0.5 to 20% by weight.
  • This dissolution process can be carried out at room temperature or under heating, but above the melting or softening temperature of the ionic liquid, usually at a temperature of 0 to 200 ° C, preferably at 20 to 180 ° C, particularly preferably at 50 to 150 ° C. , But it is also possible the dissolution process by intensive stirring or mixing and by entry of To accelerate microwave or ultrasonic energy or by combining them.
  • the carboxylic acid derivative of the formula V or the ketene of the formula VI can be added in bulk, dissolved in an ionic liquid or in a suitable solvent.
  • suitable solvents are, for example, ethers, such as diethyl ether, methyl tert-butyl ether, terahydrofuran or dioxane, or ketones, such as dimethyl ketone, or halogenated hydrocarbons, such as dichloromethane, trichloromethane or dichloroethane.
  • the amount of solvent used to dissolve the carboxylic acid derivative of formula V or the ketene of formula VI should be such that precipitation of the silylated cellulose does not occur upon addition.
  • ionic liquid is preferably the one in which the silylated cellulose itself - as described above - is dissolved.
  • carboxylic acid derivative of the formula V or the ketene of the formula VI is gaseous, this can be gassed into the solution of the silylated cellulose in the ionic liquid.
  • the carboxylic acid derivative of the formula V or the ketene of the formula VI is added in substance.
  • the carboxylic acid derivative of the formula V or the ketene of the formula VI is added dissolved in an ionic liquid, with particular preference being given to using the ionic liquid which is also used to dissolve the cellulose.
  • Suitable solvents are those solvents which do not adversely affect the solubility of the silylated cellulose, such as aprotic dipolar solvents, for example dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane.
  • aprotic dipolar solvents for example dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane.
  • nitrogen-containing bases such as pyridine, etc., can also be added.
  • the reaction mixture in addition to the ionic liquid and optionally the solvent in which the carboxylic acid derivative of the formula V or the ketene of the formula VI is dissolved, contains less than 5% by weight, preferably less than 2% by weight, in particular less than 0.1% by weight, relative to the total weight of the reaction mixture, of other solvents and / or additional nitrogen-containing bases.
  • a tertiary amine, for example triethylamine of an aromatic nitrogen base, for example pyridine. or mixtures thereof.
  • the teriary amine, the aromatic nitrogen base or the mixtures thereof are usually used in a stoichiometric ratio. On a case-by-case basis, an excess or a deficit can also be beneficial.
  • ketenes of the formula VI are used as the acylating agent, it is also possible to carry out the acylation according to the invention in the presence of a catalyst.
  • a catalyst Suitable for this purpose are the alkali metal or alkaline earth metal salts of C 1 -C 4 -alkane carboxylic acids or of benzoic acid. Examples of these are sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium benzoate or potassium benzoate, preferably sodium acetate.
  • the acids themselves ie the C 1 -C 4 -alkanecarboxylic acids or benzoic acid.
  • the catalyst is usually used in amounts of up to 10 mol%, preferably up to 8 mol% based on the ketene of the formula VI.
  • the reaction is usually carried out at a temperature of the melting point of the ionic liquid up to 200 ° C., preferably from 20 to 180 ° C., in particular 50 up to 150 ° C performed.
  • the reaction is usually carried out at ambient pressure. However, it may also be advantageous on a case-by-case basis to work at overpressure, especially when a volatile carboxylic acid derivative of the formula V or ketene of the formula VI is used. As a rule, the reaction is carried out in air. But it is also possible under inert gas, so for example under N2, a noble gas or mixtures thereof, to work.
  • the amount of acylating agent used in each case in relation to the silylated cellulose used, is set to the reaction time and optionally the reaction temperature.
  • acylating agent nAcy istsmit-
  • the amount of acylating agent used is usually adjusted (riAcy mecanicsmit-
  • acylation reaction when the desired 25 degrees of acylation is achieved by separating the acylated cellulose from the reaction mixture.
  • This can be achieved, for example, by adding an excess of water or other suitable solvent in which the acrylated / silylated cellulose is not soluble but the ionic liquid is readily soluble, such as e.g. a lower alcohol, such as methanol, ethanol, propanol or butanol, or with a ketone, for example diethyl ketone, etc., or mixtures thereof.
  • suitable solvent is also determined by the particular degree of substitution and the substituents of the cellulose.
  • an excess of water or methanol is used.
  • the work-up of the reaction mixture is usually carried out by precipitating the acylated / silylated cellulose as described above and filtering off the acylated / silylated cellulose. But it is also possible to carry out the separation by centrifugation. From the filtrate or the centrifugate can be recovered by conventional methods, the ionic liquid by the volatile component
  • nenten such as the precipitant, or excess acylating agent (or reaction products and / or hydrolysis products of the acylating agent) etc. distilled off become.
  • the remaining ionic liquid can be reused in the process according to the invention.
  • reaction mixture in water or in another suitable solvent in which the acylated / silylated cellulose is not soluble, but the ionic liquid is readily soluble, such. a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, for example diethyl ketone etc. or mixtures thereof, and, depending on the embodiment, for example, to obtain fibers, films of acylated / silylated cellulose.
  • suitable Lösusungsmittels is also determined by the respective degree of substitution and the substituents of the cellulose.
  • the filtrate is worked up as described above.
  • the termination of the acylation reaction can also be carried out in such a way that acylating agent still present at a given time is removed from the reaction mixture by distillation, stripping or extraction with a solvent which forms two phases with the ionic liquid.
  • two or more acylating agents are used.
  • a mixture of two (or more) carboxylic acid derivatives of the formula V or ketenes of the formula VI can be used in analogy to the above procedure.
  • acylated / silylated celluloses are obtained which carry two (or more) different acyl groups (depending on the acylating agent used).
  • the ionic liquid is purified in one embodiment, for example, freed of the precipitant, optionally added further solvents, hydrolysis and degradation products of the acylating agent, etc., and used again.
  • the ionic liquid containing up to 15 wt .-%, preferably up to 10 wt .-%, in particular up to 5 wt .-% of precipitant (s), etc. as described above, used again become.
  • the process can be carried out batchwise, semicontinuously or continuously.
  • the cellulose according to the present invention is silylated in an ionic liquid and the resulting silylated cellulose is subjected directly to the acylation without isolation as described above.
  • the ionic liquids were dried overnight at 120 ° C and 0.05 mbar with stirring unless otherwise noted.
  • the average degree of substitution DS of the silylated cellulose was determined by means of IR spectroscopic methods, unless stated otherwise.
  • BMIM benzoate 1-butyl-3-methylimidazolium benzoate
  • BMIM CI 1-butyl-3-methylimidazolium chloride
  • the ionic liquid (about 10 ml) was introduced into a 100 ml two-necked flask with reflux condenser under dry nitrogen, Avicel PH 101 (about 1.0 g) was added and the mixture was heated to 100 ° C. with stirring. After a clear solution was obtained, first 0.02 g of saccharin was added and then the HMDS a) . After 16 hours of stirring at 100 ° C, the reaction mixture was cooled and added with vigorous stirring in 200 ml of methanol at room temperature. The precipitate which formed was filtered off with suction and washed three times with 20 ml of methanol each time. The product thus obtained was dried for 14 hours at 60 ° C in vacuo to constant weight.
  • Example 3 In a 100 ml two-necked flask with reflux condenser was under dry argon 11 ml BMIM Cl, which was previously dried under high vacuum at 100 ° C to constant weight, presented at 100 ° C 1, 17 g Avicel PH 101 was added and stirred until a clear Solution was obtained. After addition of 0.021 g of saccharin and 2.4 g of HMDS was stirred for a further 16 hours at 100 ° C, after about 1 hour, the deposition of a solid product on the IL began. It was then cooled and the reaction mixture was added with vigorous stirring in 200 ml of methanol at room temperature. The precipitate was filtered off and washed three times with 20 ml of methanol. The product thus obtained was dried for 14 hours at 60 ° C in vacuo to constant weight. This gave 2.06 g of a white solid (83% of theory), which has an average degree of substitution of 2.2 (determined by NMR spectroscopy).
  • the ionic liquid (about 10 ml) was placed under dry argon, heated to 100 ° C and added the biopolymer (about 1, 0 g). It is stirred at 100 ° C until a clear solution is formed (about 2 to 4 hours). After a clear solution was obtained, that became
  • the ionic liquid (about 10 ml) was placed under dry argon, heated to 100 ° C and added AVICEL PH 101 (about 1, 0 g). It is stirred at 100 ° C until a clear solution is formed (about 2 to 4 hours). After a clear solution was obtained, the TDMSA and optionally a catalyst was added 9 ) . After 16 hours stirring at 100 ° C.
  • reaction mixture was cooled and added with vigorous stirring in 200 ml of methanol at room temperature.
  • the precipitate which formed was filtered off with suction and washed three times with 50 ml of methanol each time.
  • the product thus obtained was dried for 14 hours at 60 ° C / 0.05 mbar product to constant weight.
  • the reaction mixture was then stirred into 200 ml of methanol, the precipitate was filtered off, washed three times with 20 ml of methanol and The product thus obtained was obtained in a yield of 84% of theory and has a DP of 57 (determined by gel permeation chromatography) and a DS of 2.1 (Bestim - Mung by NMR).
  • reaction mixture was mixed with 20 ml of cyclohexane, the upper phase separated and freeze-dried.
  • the ionic liquid (about 10 ml) was introduced into a 100 ml two-necked flask with reflux condenser under dry nitrogen, and Avicel PH 101 (about 1.0 g) was added and heated with stirring. After a clear solution was obtained, 0.02 g of saccharin was added first followed by the amount of HMDS as shown in Table 6. After stirring for 16 hours at the temperature indicated in Table 6, the reaction mixture was cooled and added either with vigorous stirring in 200 ml of methanol at room temperature, the resulting precipitate was filtered off and washed three times with 20 ml of methanol, or extracted with toluene and concentrated the toluene , The product thus obtained was dried for 14 hours to constant weight.

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Abstract

La présente invention concerne un procédé de silylation de poly-, oligo- ou disaccharides ou de leurs dérivés, selon lequel ces composés sont dissous dans un liquide ionique et mis en réaction avec un agent de silylation.
EP07730232A 2006-06-23 2007-06-19 Procédé de silylation de cellulose Withdrawn EP2035460A1 (fr)

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DE200610029306 DE102006029306A1 (de) 2006-06-23 2006-06-23 Verfahren zur Silylierung von Cellulose
DE200610032569 DE102006032569A1 (de) 2006-07-12 2006-07-12 Verfahren zur Silylierung von Cellulose
DE200610042890 DE102006042890A1 (de) 2006-09-09 2006-09-09 Verfahren zur Silylierung von Cellulose
DE200610054233 DE102006054233A1 (de) 2006-11-15 2006-11-15 Verfahren zur Silylierung von Cellulose
PCT/EP2007/056044 WO2007147813A1 (fr) 2006-06-23 2007-06-19 Procédé de silylation de cellulose

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US20080188636A1 (en) * 2007-02-06 2008-08-07 North Carolina State University Polymer derivatives and composites from the dissolution of lignocellulosics in ionic liquids
US8182557B2 (en) 2007-02-06 2012-05-22 North Carolina State University Use of lignocellulosics solvated in ionic liquids for production of biofuels
WO2008098036A1 (fr) 2007-02-06 2008-08-14 North Carolina State University Préparation et récupération d'un produit issu de la thermolyse de matières lignocellulosiques dans des liquides ioniques
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
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US7919631B2 (en) 2007-02-14 2011-04-05 Eastman Chemical Company Production of ionic liquids
WO2009087184A1 (fr) * 2008-01-09 2009-07-16 Basf Se Procédé de traitement de liquides ioniques
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