[go: up one dir, main page]

EP1994060A1 - Procédé pour décomposer de la cellulose - Google Patents

Procédé pour décomposer de la cellulose

Info

Publication number
EP1994060A1
EP1994060A1 EP07726534A EP07726534A EP1994060A1 EP 1994060 A1 EP1994060 A1 EP 1994060A1 EP 07726534 A EP07726534 A EP 07726534A EP 07726534 A EP07726534 A EP 07726534A EP 1994060 A1 EP1994060 A1 EP 1994060A1
Authority
EP
European Patent Office
Prior art keywords
group
cellulose
methyl
general formula
butyl
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Withdrawn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
EP07726534A
Other languages
German (de)
English (en)
Inventor
Klemens Massonne
Giovanni D'andola
Veit Stegmann
Werner Mormann
Markus Wezstein
Wei Leng
Stephan Freyer
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
Original Assignee
BASF SE
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 DE200610011076 external-priority patent/DE102006011076A1/de
Priority claimed from DE200610042891 external-priority patent/DE102006042891A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1994060A1 publication Critical patent/EP1994060A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • 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

Definitions

  • the present invention describes a process for the degradation of cellulose by dissolving the cellulose in an ionic liquid and treating it at elevated temperature, optionally in the presence of water.
  • Cellulose is the most important renewable raw material and represents an important starting material for, for example, the textile, paper and nonwoven industries. It also serves as a raw material for derivatives and modifications of cellulose, to which cellulose ethers, such as, for example, Methylcellulose and carboxymethylcellulose, cellulose esters based on organic acids, e.g. Cellulose acetate, cellulose butyrate, and cellulose esters based on inorganic acids, e.g. Cellulose nitrate, and others count. These derivatives and modifications find a variety of applications, for example in the food, construction and paint industries.
  • cellulose ethers such as, for example, Methylcellulose and carboxymethylcellulose
  • cellulose esters based on organic acids e.g. Cellulose acetate, cellulose butyrate
  • inorganic acids e.g. Cellulose nitrate
  • Cellulose is characterized by insolubility, especially in common solvents of organic chemistry.
  • N-methyl-morpholine-N-oxide, anhydrous hydrazine, binary mixtures such as methylamine / dimethyl sulfoxide, or ternary mixtures such as ethylenediamine / SO 2 / dimethyl sulfoxide are used as solvent today.
  • saline systems e.g. LiCl / dimethylacetamide, LiCl / N-methylpyrrolidone, potassium thiocyanate / dimethyl sulfoxide, etc.
  • cellulose is characterized by the average degree of polymerization (DP).
  • DP average degree of polymerization
  • the DP of cellulose depends on its origin; so the DP of raw cotton can be up to 12,000.
  • cotton linters have a DP of 800 to 1800 and in wood pulp it is in the range of 600 to 1200.
  • the cellulose is suspended in dilute mineral acid and treated at elevated temperature.
  • LOPD level-off DP
  • the LODP appears to be related to the size of the crystalline regions of the cellulose employed. It is dependent on the cellulose used, but also on the reaction medium, if, for example, solvents, such as dimethyl sulfoxide, water, alcohols or methyl ethyl ketone are additionally added.
  • solvents such as dimethyl sulfoxide, water, alcohols or methyl ethyl ketone are additionally added.
  • the yield of degraded cellulose is low, because the amorphous regions or the accessible regions of the cellulose are completely hydrolyzed.
  • cellulose in a homogeneous system to an acidic degradation.
  • cellulose is dissolved, for example, in a mixture of LiCl / dimethylformamide and treated with an acid.
  • the preparation of the solution is very complicated, the work-up complicated and low the yield of degraded cellulose.
  • the oxidative degradation of cellulose is usually carried out with oxygen. As a preliminary step, it usually involves the formation of individual anhydroglucose units, which react further to form unstable intermediates and ultimately lead to a chain break. The control of this reaction is usually difficult.
  • cellulose When degraded by radiation, cellulose can be treated with high-energy radiation, such as X-radiation. Here, the DP of the cellulose is lowered very quickly. However, chemical modification of the cellulose also occurs by forming a high number of carboxylic acid or keto functions. On the other hand, if less energy-rich radiation is used, such as UV / visible light, it is necessary to use photosensitizers. And here, too, there is a modification of the cellulose by formation of keto Functional, or if oxygen is present during the irradiation, to peroxide formation.
  • high-energy radiation such as X-radiation
  • a process has now been found for degrading cellulose by dissolving cellulose in an ionic liquid and treating this solution at elevated temperatures, optionally in the presence of water.
  • [A] + is a quaternary ammonium cation, an oxonium cation, a sulfonium cation or a phosphonium cation, and [Y] ⁇ "is a one-, two- or more -, tri- or tetravalent anion stands;
  • 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.
  • 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 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 radical, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups and having 1 to 20 carbon atoms; and • the radicals R 1 to R 9 independently of one another represent hydrogen, a sulfo
  • radicals R 1 to R 9 which in the abovementioned formulas (III) are bonded to a carbon atom (and not to a heteroatom), may additionally also stand for halogen or a functional group; or
  • two adjacent radicals from the series R 1 to R 9 together also represent a divalent, carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Residue with 1 to 30 carbon atoms.
  • 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 these are attached in the above formulas (III) to a carbon atom (and not to a heteroatom), also be bound directly via the heteroatom.
  • Functional groups and heteroatoms may also be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide ) or -CONR'- (tertiary amide), are included, for example, di (Ci-C4-alkyl) amino, Ci-C4-alkyloxycarbonyl or Ci-C4-alkyloxy.
  • the radicals R ' are the remaining part of the carbon-containing radical.
  • Halogens are fluorine, chlorine, bromine and iodine.
  • the radical R preferably stands for
  • C 1 -C 20 -alkyl which is unsubstituted or branched, unsubstituted or monosubstituted to hydroxyl, halogen, phenyl, cyano, C 1 -C 6 -alkoxycarbonyl and / or SO 3 H and has a total of 1 to 20 carbon atoms, such as, for example, methyl, ethyl, 1 Propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl , 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1 -pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-p
  • Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C 1 -C 5 -alkyl end group, such as R A O- (CHR B -CH 2 -O) m -CHR B -CH 2 - or
  • R A O- (CH 2 CH 2 CH 2 CH 2 ⁇ ) m -CH 2 CH 2 CH 2 CH 2 - with R A and R B is preferably hydrogen, methyl or ethyl and m is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6 Dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;
  • 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 • hydrogen
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups cis-alkyl;
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups cis alkenyl;
  • aryl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C6-Ci2-aryl;
  • aryl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-cycloalkyl;
  • aryl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted C5-Ci2-cycloalkenyl; or
  • Heterocycles substituted and optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups ring.
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles d-cis-alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2- Butyl, 2-methyl-1-propyl (Isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl 2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3methyl-3
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ß-naphthyl, 4-diphenylyl, Chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphth
  • C 5 -C 12 -cycloalkyl optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C m F 2 ( m -a) - (ib) H 2a-b with m ⁇ 30, 0 ⁇ a ⁇ m
  • An optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl, Pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
  • Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more several substituted or unsubstituted imino groups interrupted ring, it is preferably 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3- propylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propenylene, 3-oxa-1, 5-pentylene, 1-aza-1, 3-propenylene, 1-Ci-C4-alkyl 1-aza-1, 3-propenylene, 1,4-butan-1, 3-dienylene, 1-az-1, 4-buta-1,3-dienylene or 2-aza-1,4-buta-1, 3-dienylene.
  • 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.
  • 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
  • Heptyl 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, benzyl, 3-phenylpropyl, 2-cyanoethyl, 2- (methoxycarbonyl) -ethyl, 2- (ethoxycarbonyl) -ethyl, 2- (n-butoxycarbonyl) -ethyl, trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoroisobutyl, undecylfluoropentyl,
  • Glycols, butylene glycols and their oligomers having 1 to 100 units and a hydrogen or a C 1 to C 1 alkyl as end group, such as R A O- (CHR B -CH 2 -O) m -CHR B -CH 2 - or
  • R A O- (CH 2 CH 2 CH 2 CH 2 O) m -CH 2 CH 2 CH 2 CH 2 - with R A and R B is preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9, 12-tetraoxatetradecyl;
  • N, N-di-C 1 -C 6 -alkyl-amino such as N, N-dimethylamino and N, N-diethylamino.
  • the radicals R 1 to R 9 are each independently hydrogen or Ci-Cis-alkyl, such as methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, phenyl for 2-hydroxyethyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N-diethylamino , for chlorine as well as for CH3O-
  • 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 carboxy or carboxamide and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen; or
  • R 1 and R 2 or R 2 and R 3 are 1, 4-buta-1, 3-dienylene and the remaining R 1 , R 2 , R 4 and R 5 are hydrogen;
  • 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)
  • 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; or • R 1 to R 4 are methyl hydrogen.
  • imidazolium ions such as those in which
  • R 1 is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 1-propen-3-yl, 2-hydroxyethyl or 2-cyanoethyl and R 2 to R 4 independently of one another are hydrogen, methyl or ethyl.
  • 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)
  • MIf very particularly preferred pyrazolium ions
  • 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. Very particular preference is given to using as 1-pyrazolinium (Uli) those in which
  • 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 of one another 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.
  • 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
  • IMp oxazolium ions
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are independently hydrogen or methyl.
  • NIq 1,2,4-triazolium ions
  • HIq ' HIq '
  • 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 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.
  • MIu ammonium ions
  • 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, 2-hydroxyethyl 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-iso-propyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpentylamine, di-isoprop
  • Preferred tertiary amines are di-iso-propylethylamine, diethyl-tert-butylamine, di-iso-propylbutylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.
  • 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 hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 ;
  • R 1 is methyl, ethyl, 1-butyl or 1-octyl
  • R 2 is a -CH 2 -CH 2 -OR 4 group and R 3 and R 4 are independently hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 ; or
  • R 1 is a -CH 2 -CH 2 -OR 4 group
  • R 2 is a -CH 2 -CH 2 -OR 5 group
  • R 3 to R 5 are independently hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 are.
  • Particularly preferred cholinium ions are those in which R 3 is selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxa-octyl, 1 1-methoxy 3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9- Methoxy-5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6, 9-trioxa undecyl, 7-ethoxy-4-oxa
  • 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 SiO 4 " HR 3 R b SiO 4 -
  • R a , R b , R c and R d independently of one another are each hydrogen, C 1 -C 30 -alkyl, if appropriate by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted Te imino groups interrupted C2-Ci8-alkyl, C6-Ci4-aryl, C5-Ci2-cycloalkyl or a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle, wherein two of them together an unsaturated, saturated or aromatic , optionally can form a ring interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups, where the radicals mentioned are each additionally denoted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles may be substituted.
  • Ci-cis-alkyl for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3, 3-tetramethylbutyl, benzyl, 1-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-cis-alkyl), for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert
  • C2-Ci8-alkyl for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6- dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 1-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5 oxa-nonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxa-octyl, 1-methoxy-3,6,9-trioxaundecyl, 7- Methoxy-4-oxaheptyl, 11-meth
  • radicals can be taken together, for example, as fused building block 1, 3-propylene, 1,4-butylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa -1, 3-propenylene, 1-aza-1, 3-propenylene, 1-C 1 -C 4 -alkyl-1-aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1-aza -1, 4-buta-1, 3-dienylene or 2-aza-1,4-buta-1,3-dienylene.
  • the number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited, or is automatically limited by the size of the remainder or of the ring building block. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferably not more than 3. Furthermore, at least one, preferably at least two, carbon atoms (e) are generally present between two heteroatoms.
  • Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
  • the term "functional groups" is to be understood as meaning, for example, the following: carboxy, carboxamide, hydroxy, di- (C 1 -C 4 -alkyl) -amino, C 1 -C 4 -alkyloxy-carbonyl, cyano or C 1 -C 4 -alkoxy C 1 -C 4 -alkyl methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
  • C6-C4-aryl substituted by functional groups are, for example, phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ⁇ -naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl nyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylsaphthyl, chlor
  • C5-C12-cycloalkyl which is substituted by functional groups, aryl, alkyl, aryloxy, halogen, heteroatoms and / or heterocycles are, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, Dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.
  • a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle is, for example, furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxy, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl , Difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • Preferred anions are selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates, in particular from the group of halides and halogen-containing compounds, the group of carboxylic acids, the Group containing SO 4 2 " , SO 3 2" , R 3 OSO 3 " and R 3 SO 3 -, and the group containing PO 4 3" and R 3 R b PO 4 -.
  • Preferred anions are chloride, bromide, iodide, SCN, OCN, CN, acetate, CrC 4 alkyl sulfates, R 3 -C00 " , R 3 SO 3 -, R 3 R b PO 4 -, methanesulfonate, tosylate or CrC 4 - Dialkyl phosphates.
  • Particularly preferred anions are Ch, CH 3 COO, C 2 H 5 COO, C 6 H 5 COO, CH 3 SO 3 " , (CH 3 O) 2 PO 2 - or (C 2 H 5 O) 2 PO 2 -
  • ionic liquids are used whose anions are selected from the group comprising HSO 4 " , HPO 4 2" , H 2 PO 4 - and HR 3 PO 4 -; especially HSO 4 -.
  • 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.
  • celluloses from a wide variety of sources can be used, e.g. cotton, flax, ramie, straw, bacteria etc., or wood or bagasse, in the cellulose-enriched form.
  • the process according to the invention can be used not only for the degradation of cellulose but generally for the cleavage or degradation of poly-, oligo- and disaccharides, as well as derivatives thereof.
  • polysaccharides are besides cellulose and hemicellulose, starch, glycogen, dextran and tunicin.
  • polycondensates of D-fructose such as inulin, as well as chitin and alginic acid.
  • Sucrose is an example of a disaccharide.
  • Suitable cellulose derivatives include cellulose ethers, such as methylcellulose and carboxymethylcellulose, cellulose esters, such as cellulose acetate, cellulose butyrate, and cellulose senitrate. The corresponding explanations apply accordingly.
  • 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 150 ° C, preferably at 20 to 150 ° C, particularly preferably at 50 to 150 ° C. , But it is also possible to accelerate the dissolution process by intensive stirring or mixing and by entry of microwave or ultrasonic energy or by combining them.
  • the degradation is carried out depending on the ionic liquid used usually at a temperature of melting point of the ionic liquid from 0 to 200 ° C, preferably from 20 to 180 ° C, in particular from 50 to 150 ° C.
  • ionic liquids which have acidic functions, then it is also possible to lower the reaction temperature.
  • ionic liquids whose anions are selected from the group comprising HSO 4 -, HPO 4 2 " , H 2 PO 4 - and HR 3 PO 4 -, in particular HSO 4 -.
  • Reactions in these ionic liquids are preferably included a temperature of 0 to 150 ° C, preferably from 20 to 150 ° C, in particular from 50 to 150 0 C.
  • ionic liquids which have no acidic functions
  • the reaction is usually carried out from 50 to 200 ° C, preferably from 80 ° C to 180, in particular from 80 to 150 ° C.
  • Suitable ionic liquids are those whose anions are selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group containing SO 4 2 " , SO 3 2" , R 3 OSO 3 " and R 3 SO 3 -, And the group containing PO 4 3 " and R 3 R 0 PO 4 -.
  • Preferred anions here are chloride, bromide, iodide, SCN, OCN, CN, acetate, C 1 -C 4 alkyl sulfates, R a -COC-, R 3 SO 3 " , R a R b PO 4 -, methanesulphonate, tosylate or C 1 -C 4 dialkylphosphates, and especially preferred anions are Cl, CH 3 COO, C 2 H 5 COO, C 6 H 5 COO, CH 3 SO 3 -, (CH 3 O) 2 PO 2 - or (C 2 H 5 O) 2 PO 2 -
  • 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. But it is also possible under inert gas, so for example, under N 2 , a noble gases, CO 2 , or Gemi- see thereof to work.
  • reaction time and the reaction temperature are adjusted.
  • water is added. Through the use of an excess of water based on the anhydroglucose units of the cellulose, complete degradation as far as glucose can be achieved. In case of partial degradation of the cellulose, substoichiometric amounts of water are preferably added or the reaction is stopped.
  • the excess of water must not be so high that the solubility of the cellulose is no longer guaranteed. It can be a surplus be used of at least 3 mol%, but not more than 3000 mol% of water based on x.
  • the amounts of water used are usually adjusted accordingly (n-anhydrogglucose / water > 1 ).
  • nAnhydrogiu ⁇ seikien / nwasser the lower will be under otherwise the same reaction conditions and the same reaction time, the average degradation of celulose and the higher the DP of the degraded cellulose (which will of course be smaller than the DP of the cellulose used) ,
  • 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 degradation reaction when the desired degree of degradation is achieved by separating the cellulose from the reaction mixture.
  • This can be achieved, for example, by adding an excess of water, usually at least 20% by weight, based on the cellulose solution or other suitable solvent in which the degraded cellulose is not soluble, e.g. a lower alcohol, such as methanol, ethanol, propanol or butanol, or with a ketone, for example acetone, etc., or mixtures thereof.
  • a lower alcohol such as methanol, ethanol, propanol or butanol
  • a ketone for example acetone, etc.
  • the workup of the reaction mixture is usually carried out by the cellulose is precipitated as described above and the cellulose is filtered off.
  • the ionic liquid can be recovered from the filtrate by customary methods. by distilling off the readily volatile components, such as the precipitant, the water. The remaining ionic liquid can be reused in the process according to the invention.
  • the ionic liquid to be regenerated contains only a small amount of glucose or its oligomers. Any existing amounts of these compounds can be separated by extraction with a solvent or by adding a precipitant from the ionic liquid.
  • reaction mixture is dissolved in water or in another suitable solvent in which the degraded cellulose is insoluble, such as e.g. a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, for example acetone, etc., or mixtures thereof, initiate and, depending on the embodiment, for example, fibers, films, etc. obtained from degraded cellulose.
  • a suitable solvent in which the degraded cellulose is insoluble such as e.g. a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, for example acetone, etc., or mixtures thereof, initiate and, depending on the embodiment, for example, fibers, films, etc. obtained from degraded cellulose.
  • the filtrate is worked up as described above.
  • the corresponding glucose can be separated from the ionic liquid by conventional methods, such as by precipitation with ethanol.
  • the ionic liquid may contain up to 15% by weight, preferably up to 10% by weight, in particular up to 5% by weight of precipitant (s) as described above , contain.
  • the process can be carried out batchwise, semicontinuously or continuously.
  • Cotton linters hereinafter called Linters
  • Avicel PH 101 microcrystalline cellulose
  • the ionic liquids were dried overnight at 120 ° C and 0.1 to 0.05 mbar with stirring.
  • the average degree of polymerization DP of the used (where necessary) and the degraded cellulose was determined in each case by measuring the viscosity in Cuen solution.
  • Example 7 Degradation of cellulose in BMMIM Cl at 150 ° C 0.5 g dried Avicel PH 101 in 10.0 g BMMIM Cl were stirred at 120 ° C. in a 50 ml protective gas flask with magnetic stirrer bar. After 3 h, a clear solution was obtained. The reaction mixture was then stirred for 2 h at 150 ° C bath temperature; Thereafter, the cellulose was precipitated in twenty times the amount of methanol, filtered, washed with methanol and dried at 80 ° C and 0.1 mbar overnight. The yield of degraded cellulose was 0.475 g (95%). The DP of the cellulose thus obtained was 62. The DP of Avicel PH 101 was 463.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

La présente invention concerne un procédé pour décomposer de la cellulose, ce procédé consistant à dissoudre la cellulose dans un liquide ionique et à la traiter à une température accrue, éventuellement en présence d'eau.
EP07726534A 2006-03-08 2007-02-28 Procédé pour décomposer de la cellulose Withdrawn EP1994060A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE200610011076 DE102006011076A1 (de) 2006-03-08 2006-03-08 Verfahren zum Abbau von Cellulose
DE200610042891 DE102006042891A1 (de) 2006-09-09 2006-09-09 Verfahren zum Abbau von Cellulose
PCT/EP2007/051872 WO2007101812A1 (fr) 2006-03-08 2007-02-28 Procédé pour décomposer de la cellulose

Publications (1)

Publication Number Publication Date
EP1994060A1 true EP1994060A1 (fr) 2008-11-26

Family

ID=37963954

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07726534A Withdrawn EP1994060A1 (fr) 2006-03-08 2007-02-28 Procédé pour décomposer de la cellulose

Country Status (8)

Country Link
US (1) US20090020112A1 (fr)
EP (1) EP1994060A1 (fr)
JP (1) JP2009529075A (fr)
KR (1) KR20080110608A (fr)
AU (1) AU2007222456A1 (fr)
BR (1) BRPI0708584A2 (fr)
CA (1) CA2642866A1 (fr)
WO (1) WO2007101812A1 (fr)

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101589153A (zh) * 2007-01-23 2009-11-25 巴斯夫欧洲公司 通过对可用含多原子阴离子的离子液体预处理的纤维素进行酶促水解制备葡萄糖的方法
US9834516B2 (en) 2007-02-14 2017-12-05 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom
US10174129B2 (en) 2007-02-14 2019-01-08 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom
US8153782B2 (en) * 2007-02-14 2012-04-10 Eastman Chemical Company Reformation of ionic liquids
US7674608B2 (en) 2007-02-23 2010-03-09 The University Of Toledo Saccharifying cellulose
CN100465373C (zh) * 2007-03-08 2009-03-04 上海交通大学 用生物质原料炼制生产纤维素、木质素和木糖的方法
CN101765663B (zh) * 2007-03-14 2014-11-05 托莱多大学 生物质预处理
EP2033973A1 (fr) * 2007-09-06 2009-03-11 The Queen's University of Belfast Procédé de conversion
EP2913409A1 (fr) * 2007-10-09 2015-09-02 BIOeCON International Holding N.V. Processus pour la dissolution sélective de cellulose
CN101250285B (zh) * 2007-10-10 2011-04-20 中国科学院过程工程研究所 一种降解聚对苯二甲酸乙二醇酯的方法
EP2062922A1 (fr) * 2007-11-14 2009-05-27 Basf Se Procédé de fabrication de biopolymères régénérés et résultats régénérés obtenus ensuite
JP2009159904A (ja) * 2008-01-09 2009-07-23 Honda Motor Co Ltd グルコース抽出方法
US20100297532A1 (en) * 2008-01-09 2010-11-25 Basf Se Process for working up ionic liquids
JP2009203454A (ja) * 2008-01-31 2009-09-10 Toyota Central R&D Labs Inc イオン液体を利用したセルロース分解産物の生産方法
US8354525B2 (en) 2008-02-13 2013-01-15 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom
US8158777B2 (en) * 2008-02-13 2012-04-17 Eastman Chemical Company Cellulose esters and their production in halogenated ionic liquids
US8188267B2 (en) 2008-02-13 2012-05-29 Eastman Chemical Company Treatment of cellulose esters
US9777074B2 (en) 2008-02-13 2017-10-03 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom
CA2726126C (fr) * 2008-06-17 2018-07-17 Wisconsin Alumni Research Foundation Transformation chimique de biomasse lignocellulosique en combustibles et produits chimiques
US7999355B2 (en) * 2008-07-11 2011-08-16 Air Products And Chemicals, Inc. Aminosilanes for shallow trench isolation films
US20100044210A1 (en) * 2008-08-20 2010-02-25 The Board Of Regents Of The University Of Texas System METHOD OF DIGESTING CELLULOSE TO GLUCOSE USING SALTS AND MICROWAVE (muWAVE) ENERGY
US20100175691A1 (en) * 2009-01-15 2010-07-15 Celanese Acetate Llc Process for recycling cellulose acetate ester waste
JP5561752B2 (ja) * 2009-02-18 2014-07-30 神奈川県 アルコールの製造方法
US8067488B2 (en) * 2009-04-15 2011-11-29 Eastman Chemical Company Cellulose solutions comprising tetraalkylammonium alkylphosphate and products produced therefrom
US8722878B2 (en) * 2009-07-01 2014-05-13 Wisconsin Alumni Research Foundation Biomass hydrolysis
US8884003B2 (en) * 2010-01-15 2014-11-11 Basf Se Method of chlorinating polysaccharides or oligosaccharides
EP2523977A1 (fr) 2010-01-15 2012-11-21 Basf Se Procédé de chloration de polysaccharides ou d'oligosaccharides
JP2012012568A (ja) * 2010-05-31 2012-01-19 Idemitsu Kosan Co Ltd バイオマスの処理方法
US8980050B2 (en) 2012-08-20 2015-03-17 Celanese International Corporation Methods for removing hemicellulose
DE102011083362A1 (de) 2010-09-28 2012-03-29 Basf Se Isolierung von Cellulose, Hemicellulose und Lignin aus einem Lignocellulosematerial
US9096691B2 (en) 2011-04-13 2015-08-04 Eastman Chemical Company Cellulose ester optical films
US20140048221A1 (en) 2012-08-20 2014-02-20 Celanese International Corporation Methods for extracting hemicellulose from a cellulosic material
EP2981641B1 (fr) 2013-04-04 2024-05-15 Aalto University Foundation sr Procédé pour la production d'articles formés en cellulose
KR101540202B1 (ko) * 2015-04-23 2015-07-28 주식회사 씨티씨 투명성이 향상된 트리아세틸 셀룰로오스 필름 및 이의 제조방법
EP3109793B1 (fr) * 2015-06-22 2020-07-22 Nxp B.V. Système de détection d'empreinte digitale
KR101907868B1 (ko) * 2016-12-02 2018-10-15 건국대학교 산학협력단 이온성 액체를 이용한 자기 조립형 균일계 셀룰로오스 나노입자 및 이의 제조 방법
WO2018138416A1 (fr) 2017-01-30 2018-08-02 Aalto University Foundation Sr Procédé de fabrication d'une fibre ou d'un film de cellulose
US10282651B2 (en) * 2017-03-23 2019-05-07 Idex Asa Sensor array system selectively configurable as a fingerprint sensor or data entry device
US10723859B2 (en) * 2017-07-17 2020-07-28 University Of Kentucky Research Foundation Lignin valorization in ionic liquids and deep eutectic solvent via catalysis and biocatalysis
CN114044917B (zh) * 2021-12-15 2023-02-17 徐州工程学院 一种4-丁基-3-甲基咪唑硫酸氢盐-乙醇二元体系预处理纤维素的方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1943176A (en) * 1930-09-27 1934-01-09 Chem Ind Basel Cellulose solution
US1924238A (en) * 1930-09-27 1933-08-29 Chem Ind Basel Cellulose solution and cellulose derivative and process of making same
AR038161A1 (es) * 2002-01-24 2004-12-29 Basf Ag Procedimiento para separar acidos de mezclas de reaccion quimicas con la ayuda de liquidos ionicos
FI116141B (fi) * 2004-01-05 2005-09-30 Kemira Oyj Depolymerointimenetelmä
DE102004031025B3 (de) * 2004-06-26 2005-12-29 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Verfahren und Vorrichtung zur Herstellung von Formkörpern aus Cellulose
DE102005017733A1 (de) * 2005-04-15 2006-10-19 Basf Ag Löslichkeit von Cellulose in ionischen Flüssigkeiten unter Zugabe von Aminbase

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007101812A1 *

Also Published As

Publication number Publication date
AU2007222456A1 (en) 2007-09-13
US20090020112A1 (en) 2009-01-22
JP2009529075A (ja) 2009-08-13
BRPI0708584A2 (pt) 2011-05-31
WO2007101812A1 (fr) 2007-09-13
CA2642866A1 (fr) 2007-09-13
KR20080110608A (ko) 2008-12-18

Similar Documents

Publication Publication Date Title
EP1994060A1 (fr) Procédé pour décomposer de la cellulose
EP1994059A1 (fr) Procédé pour décomposer de la cellulose en solution
EP1994058A1 (fr) Procédé pour décomposer de la cellulose au moyen de nucléophiles
EP2035458A1 (fr) Procédé d'acylation de cellulose
EP2038307A1 (fr) Procédé d'acylation de la cellulose avec un degré de polymérisation moyen ciblé
EP1893651B1 (fr) Solubilite de la cellulose dans des liquides ioniques, sous apport de base amine
EP1881994B1 (fr) Solutions de cellulose dans des liquides ioniques
EP2035460A1 (fr) Procédé de silylation de cellulose
WO2008003643A1 (fr) Procédé d'obtention d'acétals de cellulose
DE102005062608A1 (de) Lösungssystem auf der Basis geschmolzener ionischer Flüssigkeiten ein Verfahren zu dessen Herstellung sowie zur Herstellung regenerierter Kohlenydrate
WO2007076979A1 (fr) Solution a base de liquides ioniques fondus, sa fabrication et son utilisation pour la fabrication d'hydrates de carbone regeneres
DE102006011076A1 (de) Verfahren zum Abbau von Cellulose
DE102006035830A9 (de) Lösungssystem auf der Basis geschmolzener ionischer Flüssigkeiten, dessen Herstellung sowie Verwendung zur Herstellung regenerierter Kohlenhydrate
DE102006029306A1 (de) Verfahren zur Silylierung von Cellulose
DE102006042891A1 (de) Verfahren zum Abbau von Cellulose
DE102006042892A1 (de) Verfahren zur Acylierung von Cellulose mit gezieltem durchschnittlichen Polymerisationsgrad
DE102006030696A1 (de) Verfahren zur Acylierung von Cellulose mit gezieltem durchschnittlichen Polymerisationsgrad
DE102006031810A1 (de) Verfahren zur Darstellung von Celluloseacetalen
DE102006054213A1 (de) Verfahren zur Darstellung von Celluloseacetalen
DE102006042890A1 (de) Verfahren zur Silylierung von Cellulose
DE102006032569A1 (de) Verfahren zur Silylierung von Cellulose
DE102006054233A1 (de) Verfahren zur Silylierung von Cellulose

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20081008

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20100210

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120901