EP2041183A1 - Procédé d'obtention d'acétals de cellulose - Google Patents

Procédé d'obtention d'acétals de cellulose

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Publication number
EP2041183A1
EP2041183A1 EP07786907A EP07786907A EP2041183A1 EP 2041183 A1 EP2041183 A1 EP 2041183A1 EP 07786907 A EP07786907 A EP 07786907A EP 07786907 A EP07786907 A EP 07786907A EP 2041183 A1 EP2041183 A1 EP 2041183A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
group
radicals
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.)
Withdrawn
Application number
EP07786907A
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 DE200610031810 external-priority patent/DE102006031810A1/de
Priority claimed from DE200610054213 external-priority patent/DE102006054213A1/de
Application filed by BASF SE, Universitaet Siegen filed Critical BASF SE
Publication of EP2041183A1 publication Critical patent/EP2041183A1/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Withdrawn legal-status Critical Current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
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/08—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with hydroxylated hydrocarbon radicals; Esters, ethers, or acetals thereof
    • 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
    • C08B15/10—Crosslinking of cellulose

Definitions

  • the present invention describes a process for the preparation of cellulose acetals by reacting cellulose with a vinyl ether in an ionic liquid, as well as new cellulose acetals.
  • Cellulose is the most important renewable raw material and represents an important starting material for, for example, the textile, paper and nonwoven industries. It also serves as a raw material for derivatives and modifications of cellulose, to which cellulose ethers, such as, for example, Methylcellulose and carboxymethylcellulose, cellulose esters based on organic acids, e.g. Cellulose acetate, cellulose butyrate, and cellulose esters based on inorganic acids, e.g. Cellulose nitrate, and others count.
  • cellulose ethers such as, for example, 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
  • These derivatives and modifications find a variety of applications, for example in the textile, food, construction and paint industries. Of particular interest here is cellulose acetate. It is still desirable to provide other derivatives of
  • This object has been achieved by dissolving cellulose in an ionic liquid and reacting with a vinyl ether. Furthermore, new cellulose acetals were found.
  • 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.
  • 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 2 nitrogen atoms.
  • nitrogen atom is a suitable carrier of the positive charge in the cation of the ionic liquid from which, in equilibrium, a proton or an alkyl radical can then be transferred to the anion to produce an electrically neutral molecule.
  • 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.
  • Starting, for example, from an ammonia halide halide can be reacted with a Lewis acid, wherein a complex anion is formed 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 can 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.
  • those compounds which contain at least one five- to six-membered heterocycle in particular a five-membered heterocycle, which has at least one nitrogen atom and, if appropriate, an oxygen or sulfur atom.
  • those compounds which contain at least one 5- to 6-membered heterocycle which has one, two or three nitrogen atoms and one sulfur atom or one oxygen atom, very particularly preferably those with two nitrogen atoms.
  • 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.
  • MId MId
  • MIe MIe
  • MIf MIf
  • MIh MIh
  • 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 are hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or suitable functional groups radical having 1 to 20 carbon atoms, wherein the radicals R 1 to R 9 , which in the abovementioned formulas (III) are bonded to a carbon atom (and not to a heteroatom), can additionally also stand for halogen or a functional group; or
  • two adjacent radicals from the series R 1 to R 9 together also represent a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic table, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 30 carbon atoms.
  • the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable.
  • the radicals R 1 to R 9 are, in the cases in which those in the above formulas (IM) to a carbon atom (and not to a heteroatom) bound also be bound directly via the heteroatom.
  • Suitable functional groups are in principle all functional groups which may be bonded to a carbon atom or a heteroatom and which do not react with vinyl ether.
  • 0 in particular as carbonyl group
  • -NR 2 ', NR' and -CN (cyano).
  • Fractional groups and heteroatoms can also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester) 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 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 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.
  • radicals R 1 to R 9 are preferably each independently
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino Ci- Ci ⁇ alkyl;
  • aryl alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, and / or by one or more oxygen and / or sulfur atoms and / or one or more several substituted or unsubstituted imino interrupted C2-Cis alkenyl;
  • aryl optionally substituted by appropriate functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-C12 cycloalkyl;
  • aryl optionally substituted by appropriate functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C5-C12-cycloalkenyl; or
  • 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 one or more 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-methyl-3-p
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles C6-Ci2-aryl is preferably phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ß-naphthyl, 4th -Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, Chloron
  • C5-C12-Cycloalkyl optionally substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl , Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C m F 2 ( m -a) - (ib) H 2a-b with im ⁇ 30, 0 ⁇ a ⁇ m
  • 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.
  • the abovementioned radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups
  • the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the remainder, preferably not more than 4 and very particularly preferably not more than 3.
  • the abovementioned 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
  • Alkyl having a total of 1 to 20 carbon atoms such as 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
  • Glycols, butylene glycols and their oligomers having from 1 to 100 units, all of the above groups having a C 1 to C 6 alkyl radical as end group, 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 ⁇ ) m -CH 2 CH 2 CH 2 CH 2 - with R A and R B preferably methyl or ethyl and n preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3 , 6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-
  • 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 O) m -CH 2 CH 2 - with m equal to 0 to 3.
  • 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 1 and R 2 or R 2 and R 3 is 1, 4-buta-1,3-dienylene and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen;
  • 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) which may be mentioned are 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) -pyridinium, 1 (1-Hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-dodecyl) pyridinium, 1- (1-tetradecyl) pyridinium, 1- (1-hexadecyl) pyridinium, 1, 2-dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2-methylpyridinium, 1- (1-te), 1-
  • 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.
  • 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 1 is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 1-propen-3-yl or 2-cyanoethyl and R 2 to R 4 independently of one another are hydrogen, Methyl or ethyl.
  • MIe Very particularly preferred imidazolium ions
  • MIf very particularly preferred pyrazolium ions
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl.
  • pyrazolium ions are those in which
  • 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
  • R 3 to R 6 are independently hydrogen or methyl.
  • 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.
  • MIm imidazolinium ions
  • R 1 and R 2 are independently hydrogen, methyl or ethyl and R 3 to R 6 are independently hydrogen or methyl.
  • 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.
  • 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 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
  • 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 from which the quaternary ammonium ions of the general formula (IMu) are derived by quaternization with the abovementioned radicals R are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethylhexylamine, Diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2-ethylhexyl ) -amine, di-isopropylethylamine, di-isopropyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpentylamine, di
  • 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.
  • guanidinium ion N, N, N ', N', N ", N" - hexamethylguanidinium.
  • 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.
  • Particularly preferred 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-decyl, 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-hepty
  • Very particularly preferred 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
  • silicates and silicic acid esters of the general formula: SiO 4 4 -, HSiO 4 3 -, H 2 SiO 4 2 -, H 3 SiO 4 -, R 3 SiO 4 3 " , R 3 R b Si0 4 2" , R 3 R b R c Si0 4 -, HR 3 SiO 4 2 " , H 2 R 3 SiO 4 " , HR 3 R b Si0 4 -
  • R a, R b, R c and R d are each independently hydrogen, Ci- C3o-alkyl, optionally substituted by one or more nonadjacent oxygen and / or sulfur atoms and / or one or more substituted or the unsubstituted imino groups te interrupted C2-Ci8-alkyl, C6-Ci4-aryl, C5-Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, wherein two of them together an unsaturated, saturated or aromatic, optionally can form a ring interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups, where the radicals mentioned are each additionally denoted by suitable functional groups, aryl, alkyl, aryloxy, alkoxy, 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), methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl , Pen
  • Optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino interrupted C2-Cis-alkyl for example, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxa- octyl, 1 1-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 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-trioxaundecyl, 7-
  • 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 mean.
  • the number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited, or is automatically limited by the size of the remainder or of the ring building block. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferably not more than 3. Furthermore, at least one, preferably at least two, carbon atoms (e) are generally present between two heteroatoms.
  • Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
  • the term "functional groups” are, for example, to the following: N 1 N-di (Ci-C 4 alkyl) carboxamide, di- (Ci-C 4 alkyl) amino, Ci-C4-alkyloxy- carbonyl Cyano or C 1 -C 4 -alkoxy, where C 1 -C 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, chloronaphthyl,
  • 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, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl , Dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • Preferred anions are selected from the group of halides and halogen-containing compounds, the group of sulfates, sulfites and sulfonates, the group of phosphates, and the group of carboxylic acids, in particular from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group containing 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 ", exceptionally preferably from the group of Halides and halogen-containing compounds.
  • Preferred anions are, in particular, halides, such as chloride, bromide or iodide, or SCN, OCN, CN, acetate, propionate, benzoate, C 1 -C 4 -alkyl sulfates, R 3 -CO 2 ", R 3 " SO 3 -, R 3 R b PO 4 -, methanesulfonate, tosylate or di- (Ci-C 4 -alkyl) phosphates.
  • halides such as chloride, bromide or iodide
  • SCN OCN
  • CN acetate
  • propionate benzoate
  • C 1 -C 4 -alkyl sulfates R 3 -CO 2 ", R 3 " SO 3 -, R 3 R b PO 4 -, methanesulfonate, tosylate or di- (Ci-C 4 -alkyl) phosphates.
  • Particularly preferred anions are Ch, CH 3 COO, C 2 H 5 COO, C 6 H 5 COO, CH 3 SO 3 -, (CH 3 O) 2 PO 2 - or (C 2 H 5 O) 2 PO 2 -
  • Exceptionally preferred anion is chloride.
  • 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.
  • Vinyl ethers for the purposes of the present invention are vinyl ethers of the formula IV,
  • R x, R ⁇ is hydrogen, Ci-C 3 -alkyl, C 2 -C 3 -alkenyl, C 2 -C 3 O-AI kinyl, C 3 -C 2 -cycloalkyl, C5-Ci2 cycloalkenyl , Aryl or heterocyclyl, where the seven last-mentioned radicals may optionally be substituted;
  • R x and R z together form an optionally substituted - (C H2) r -Ys (C H2) t-chain, where
  • Ci-C3o-alkyl radicals for R x, R ⁇ and R z are, in particular unsubstituted Ci-C3o-alkyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and or heterocyclic substituted Ci-C3o-alkyl radicals, preferably Ci-C3o-alkyl radicals, such as methyl, ethyl, 1-propyl, 2-
  • C2-C3o-alkenyl radicals R x, R ⁇ and R z in particular, unsubstituted C2-C3o alkenyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and or heterocycles substituted C2-C3o-alkenyl radicals, preferably C2-C3o-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 example, C m F 2 ( m -a) - (ib)
  • C2-C3o-alkynyl groups for R x, R ⁇ , and R z in particular, unsubstituted C2-C3o alkynyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted C2-C3o-alkynyl radicals, preferably C2-C3o-alkynyl radicals, such as ethynyl, 1-propyn-3-yl, 1-propyn-1-yl or 3-methyl-1-propyne 3-yl, more preferably ethynyl or 1-propyn-3-yl.
  • C3-Ci2-cycloalkyl radicals for R x, R ⁇ and R z in particular, unsubstituted Cs-C ⁇ cycloalkyl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and 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 Butylcyc- lohexyl, as well as bicyclic system such as norbornyl, preferably cyclopen
  • C5-Ci2-cycloalkenyl groups for R x, R ⁇ and R z in particular, unsubstituted Ca-Cs-cycloalkenyl groups or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and or heterocycles substituted Ca-Cs-cycloalkenyl radicals, preferably Ca-Cs-cycloalkenyl radicals, such as 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl, and bicyclic system such as norbornyl, especially preferably 3-cyclopentenyl, 2-cyclohexenyl or 3-cyclohexenyl; or, preferably, by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycle
  • aryl radicals for R x, R ⁇ , and R z in particular, unsubstituted C6-Ci2-aryl radicals or by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, substituted C6-Ci2-aryl radicals, preferably C6-Ci2-aryl radicals, such as phenyl, ⁇ -naphthyl or ß-naphthyl, particularly preferably phenyl; or C 6 -C 12 -aryl radicals which are preferably substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as ToIyI, XyIyI, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichloroph
  • heterocyclyl radicals which may be mentioned are unsubstituted heteroaryl radicals or heteroaryl radicals which are substituted by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, preferably 5- or 6-membered radicals Heteroaryl radicals which contain oxygen, nitrogen and / or sulfur atoms, such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl or benzothiazolyl; or preferably by suitable functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted 5- or 6-membered heteroaryl radicals having oxygen, nitrogen and / or sulfur atoms, such as methylpyri
  • R z and R x together form an optionally substituted - form (C H2) r Ys (C H2) t-chain are preferably a - (CH2) rX s - (CH2) r-chain, especially a - ( CH 2) r (CH 2) r chain, in particular - (CH 2) 2-, - (CHb) 3- or - (CH 2 ) 4 -, very preferably - (CH 2 ) 3 - into account, or a by Ci-C 4- alkyl-substituted - (CH 2) rY s - (CH 2) t-chain, especially a by Ci-C 4 alkyl substituted - (CH 2) r (CH 2) t- chain, in particular one by Ci-C 4 Alkyl- substituted - (CH 2) 2-, - (CH 2) 3- or - (CH 2) 4 - - chain, exceptionally preferably a Ci-C 4 alkyl substituted - (CHb) 3- chain into consideration.
  • vinyl ethers of the formula IV are used, where the radicals have the following meanings:
  • R x is hydrogen or C 1 -C 18 -alkyl, preferably hydrogen or C 1 -C 6 -alkyl; particularly preferably hydrogen, methyl or ethyl; most preferably hydrogen;
  • R ⁇ is hydrogen;
  • R z is Ci-Cis-alkyl, preferably Ci-C ⁇ -alkyl; particularly preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl.
  • vinyl ethers of the formula IV are used, where the radicals have the following meanings:
  • R x is 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
  • R ⁇ is hydrogen;
  • R z is Ci-Cis-alkyl, preferably Ci-C ⁇ -alkyl; particularly preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl.
  • vinyl ethers of the formula IV are used, where the radicals have the following meanings:
  • R x and R z together form a - (CH 2) r (CH 2) t chain, preferably a - (CH 2) 2,
  • celluloses from a wide variety of sources can be used, e.g. of cotton, flax, ramie, straw, bacteria, etc., or of wood or bagasse, in the cellulose-enriched form.
  • the process according to the invention can be used not only for the preparation of cellulose ions but generally for the preparation of poly-, oligo- and disaccharide acetals, as well as derivatives thereof.
  • polysaccharides in addition to cellulose and hemicellulose, starch, glycogen, dextran and tunicin may be mentioned.
  • these include the polycondensates of D-fructose, such as inulin, and u.a. Chitin and alginic acid.
  • Sucrose is an example of a disaccharide.
  • Suitable cellulose derivatives are those whose DS ⁇ 3, i.a.
  • Cellulose ethers such as methylcellulose and carboxymethylcellulose
  • cellulose esters such as cellulose acetate, cellulose butyrate
  • cellulose silyl ethers such as cellulose trimethylsilyl ether
  • cellulose nitrate each with a DS ⁇ 3.
  • a polysaccharide e.g. Cellulose, hemicellulose, starch, glycogen, dextran, tunicin, inulin, chitin or alginic acid, preferably cellulose.
  • a disaccharide e.g. Sucrose
  • a disaccharide e.g. Sucrose
  • a cellulose derivative whose DS is ⁇ 3 for example a cellulose ether, such as methylcellulose and carboxymethylcellulose, a cellulose ester, such as cellulose acetate, cellulose butyrate, a cellulose silyl ether, such as cellulose trimethylsilyl ether, and cellulose nitrate, respectively with a DS ⁇ 3, implemented.
  • a cellulose ether such as methylcellulose and carboxymethylcellulose
  • cellulosic esters such as cellulose acetate, cellulose butyrate and cellulose nitrate.
  • a solution of cellulose in ionic liquid is prepared.
  • concentration of cellulose can be varied within wide ranges. It is usually in the range from 0.1 to 50% by weight, based on the total weight of the solution, preferably from 0.2 to 40% by weight, more preferably from 0.3 to 30% by weight and particularly preferably at 0.5 to 20% by weight.
  • This dissolution process can be carried out at room temperature or with heating, but above the melting or softening temperature of the ionic liquid, usually at a temperature of 0 to 200 ° C., preferably at 20 to 180 ° C., particularly preferably at 50 to 150 ° C.
  • it is also possible to accelerate the dissolution process by intensive stirring or mixing as well as by introduction of microwave or ultrasonic energy or by a combination thereof.
  • the vinyl ether of the formula IV may 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 vinyl ether 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 vinyl ether of the formula IV is gaseous, it can be gassed into the solution of cellulose in the ionic liquid. In a particular embodiment, the vinyl ether of formula IV is added in substance.
  • the vinyl ether of the 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 vinyl ether 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.
  • 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 vinyl ether 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 such as mercury (II) salts, such as mercury (II) acetate, propionate, benzoate, chloride, sulfate and nitrate, or paladium (II) salts, such as palladium (II) acetate, propionate, are suitable for this purpose, for example.
  • the catalyst is usually used in amounts of up to 20 mol%, preferably up to 5 mol%, based on the vinyl ether of the formula IV.
  • the reaction is usually carried out at a temperature of melting point of the ionic liquid to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C, depending on the ionic liquid used and the vinyl ether of the formula IV.
  • the amount of vinyl ether used-in each case in relation to the cellulose used- is adjusted to the reaction time and optionally the reaction temperature.
  • vinyl ethers of the formula IV are required.
  • the amount of vinyl ether used of formula IV is usually adjusted (vinyl acetate / ri anhydroglucose units ⁇ 3).
  • acetalization reaction when the desired degree of acetalization is achieved by separating the acetalated cellulose from the reaction mixture.
  • This can be achieved, for example, by adding an excess of water or other suitable solvent in which the acetalated 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.
  • 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 acetalized cellulose, as described above, and filtering off the acetalated cellulose. From the filtrate, the ionic liquid can be recovered by conventional methods by the volatile components, such as the precipitant, or excess vinyl ether of the formula IV, or its hydrolysis, etc. are distilled off. The remaining ionic liquid can be reused in the process according to the invention. If a catalyst is used in the reaction, it usually remains in the liquid phase and is recycled together with the ionic liquid. In a further embodiment, excess vinyl ethers of the formula IV can also remain in the ionic liquid and be used again in the process according to the invention.
  • reaction mixture in water or in another suitable solvent in which the acetalated cellulose is not soluble, but the ionic liquid is readily soluble, such as. a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, for example diethyl ketone, etc., or mixtures thereof, and, depending on the embodiment, for example, to obtain fibers, films of acetalized cellulose.
  • a lower alcohol such as methanol, ethanol, propanol or butanol
  • a ketone for example diethyl ketone, etc.
  • the choice of suitable Lösusungsmittels is also determined by the respective degree of substitution and the substituents of the cellulose.
  • the filtrate is worked up as described above.
  • the termination of the acetalization reaction can also be carried out in such a way that vinyl ether of the formula IV 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 vinyl ethers of the formula IV are reacted.
  • a mixture of two (or more) vinyl ethers of the formula IV can be used analogously to the preceding procedure.
  • acetalized celluloses wherein the OH groups of the cellulose by two (or more) different O-CH (OR Z) (CHCR X R Y) groups are replaced (depending on the used vinyl ethers of formula IV).
  • the ionic liquid may contain up to 15% by weight, preferably up to 10% by weight, in particular up to 5% by weight of precipitant (s) as described above , contain. Possibly. However, it may then be necessary to use a corresponding excess of vinyl ethers of the formula IV.
  • the process can be carried out batchwise, semicontinuously or continuously.
  • the present invention also acetalized poly, oligo or disaccharides or derivatives thereof, in particular acetalated cellulose, which by the reaction of a poly, oligo or disaccharide or a derivative thereof, in particular cellulose, with a vinyl ether of the formula IV, wherein
  • R x and R z together form an optionally substituted - (C H2) r -Ys (C H2) t-chain, with
  • R ⁇ is hydrogen, Ci-C 30 alkyl, C 2 -C 3 -alkenyl, C 2 -C 30 -alkyl kinyl, C3-Ci2 cycloalkyl, C 5 - C 2 cycloalkenyl, aryl or heterocyclyl, wherein the seven last-mentioned residues may optionally be substituted;
  • acetalized poly- or oligosaccharides obtainable by the process according to the invention by acetalization of poly- or oligosaccharides, in particular cellulose, with a vinyl ether of the formula IV, in particular acetalated cellulose, are suitable, for example, for the production of moldings, fibers and films and coatings. It is particularly advantageous that the products in dissolved form can be converted and subsequently converted into an insoluble, crosslinked form.
  • this crosslinking uses acetalized cellulose which, as described above, is reacted by reacting cellulose with a vinyl ether of the formula IV,
  • R x, R ⁇ is hydrogen, dC ⁇ alkyl, C 2 -C 3 -alkenyl, C 2 -C 30 -alkyl kinyl, C 3 -C 2 -cycloalkyl, C5-Ci2 cycloalkenyl, aryl or heterocyclyl where the last seven radicals may optionally be substituted;
  • R z Ci-C 30 alkyl, C 2 -C 30 -alkenyl, C 2 -C 30 -alkyl kinyl, C3-Ci2 cycloalkyl, C 5 -C 2 cyclo- alkenyl, aryl or heterocyclyl, where these seven radicals mentioned may optionally be substituted;
  • this crosslinking uses acetalated cellulose which is obtained by reacting cellulose with a vinyl ether of the formula IV where the radicals have the following meanings:
  • R x 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;
  • R ⁇ is hydrogen
  • R z is Ci-Cis-alkyl, preferably Ci-C ⁇ -alkyl; particularly preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl;
  • this crosslinking uses acetalized cellulose which is obtained by reacting cellulose with a vinyl ether of the formula IV where the radicals have the following meanings:
  • R z is Ci-Cis-alkyl, preferably Ci-C ⁇ -alkyl; particularly preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl;
  • inorganic acids are hydrogen halides, 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 PO 4 .
  • 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.
  • organic acids preference is given to C 1 -C 6 -alkanecarboxylic acids, for example acetic acid or propionic acid, halogenated carboxylic acids, for example C 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-methylphenylsulfonic acid.
  • 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-methylphenylsulfonic acid are used.
  • the networking can be done in different ways.
  • the cellulose acetal is applied in bulk to an inert surface, eg, as a film, and then vaporized with an appropriate acid, for example by allowing vapors of acetic acid, HCl gas, etc., to flow over this cellulose acetal coated surface.
  • an appropriate acid for example by allowing vapors of acetic acid, HCl gas, etc.
  • the concentration of the acid or the treatment time and the treatment temperature is set.
  • the crosslinked cellulose thus obtained is rinsed with a solvent in which the latter is not soluble.
  • Suitable for this purpose is water or, for example, a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, for example diethyl ketone, etc., or mixtures thereof.
  • a lower alcohol such as methanol, ethanol, propanol or butanol
  • a ketone for example diethyl ketone, etc., or mixtures thereof.
  • the cellulose acetal is dissolved in a solvent in which it is soluble.
  • ionic liquids are generally considered as described above.
  • solvents such as aromatic hydrocarbons, e.g. Benzene, chlorinated hydrocarbons such as methylene chloride, chloroform, 1, 2-dichloroethane, ketones, e.g. Acetone, diethyl ketone or ether, e.g. Tetrahydrofuran or dioxane to use.
  • the acid is then added to this solution in bulk or in solution.
  • the crosslinked cellulose precipitates here. If this is not the case, a solvent is added in which the crosslinked cellulose is not soluble.
  • Particularly suitable for this purpose is water or a lower alcohol, such as methanol, ethanol, propanol or butanol, in particular methanol.
  • reaction mixture obtained in the reaction of cellulose with a vinyl ether of the formula IV is treated with acid as described above.
  • the cellulose acetal is dissolved in a solvent in which it is soluble, as described above.
  • This solution is now dissolved in water or another suitable solvent in which the crosslinked cellulose is not soluble but the solvent is readily soluble, e.g. a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, for example, diethyl ketone, etc., or mixtures thereof, to which acid has been added, and depending on the embodiment, fibers, films, etc. are obtained from crosslinked cellulose.
  • reaction mixture obtained in the reaction of cellulose with a vinyl ether of the formula IV is treated with acid as described above.
  • the amount of acid used is in the range from 0.001 to 10 mol%, based on the number of anhydroglucan units of the cellulose acetal used.
  • catalytic amounts are used, in particular 0.1 to 0.001 mol.
  • this crosslinking is carried out at a temperature of up to 200.degree. C., preferably in the range of 0 to 150.degree. C., in particular in a range of 10 to 100.degree. In a particular embodiment, this crosslinking is carried out at room temperature.
  • the crosslinked cellulose obtained by these processes is novel and also the subject of the present invention.
  • the crosslinking of the acetalated cellulose, as described above, can lead to the formation of intermolecular acetals, which thus connect different "cellulosic chains" with one another (a) and / or to the formation of intramolecular acetals, that is to say between different anhydoglucose units.
  • Cellulose chain "acetals are formed (b). This is shown schematically below, wherein R is H or CH (OR z ) -CHR x R y and wherein the intermolecular or intramolecular bridging is not fixed to the exemplified positions, but can also take place at other positions of the respective Anhdrogluco- unit :
  • the average degree of substitution DS of the as-synthesized cellulose was determined by elemental analysis.

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Abstract

La présente invention concerne un procédé d'obtention d'acétals de poly-, oligo- ou disaccharides, suivant lequel on dissout ceux-ci dans au moins un liquide ionique et on les fait réagir avec un éther vinylique. Les poly- ou oligosaccharides acétalisés ainsi obtenus peuvent être réticulés par un traitement par un acide. La présente invention concerne également des acétals de poly-, oligo- ou disaccharides ainsi que les poly- ou oligosaccharides.
EP07786907A 2006-07-07 2007-06-28 Procédé d'obtention d'acétals de cellulose Withdrawn EP2041183A1 (fr)

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DE200610031810 DE102006031810A1 (de) 2006-07-07 2006-07-07 Verfahren zur Darstellung von Celluloseacetalen
DE200610054213 DE102006054213A1 (de) 2006-11-15 2006-11-15 Verfahren zur Darstellung von Celluloseacetalen
PCT/EP2007/056518 WO2008003643A1 (fr) 2006-07-07 2007-06-28 Procédé d'obtention d'acétals de cellulose

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JP2010516265A (ja) * 2007-01-23 2010-05-20 ビーエーエスエフ ソシエタス・ヨーロピア 多原子アニオンを有するイオン性液体で前処理されたセルロースの酵素的加水分解によりグルコースを製造する方法
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
WO2008098032A2 (fr) 2007-02-06 2008-08-14 North Carolina State University Utilisation de matières lignocellulosiques solvatées dans des liquides ioniques pour la production de biocarburants
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AU2007271219B2 (en) 2012-06-28
US20090187016A1 (en) 2009-07-23
BRPI0714007A2 (pt) 2012-12-18
CA2656225A1 (fr) 2008-01-10
JP2009542875A (ja) 2009-12-03
AU2007271219A1 (en) 2008-01-10
KR20090026358A (ko) 2009-03-12
MY148892A (en) 2013-06-14

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