WO2007144282A1 - Verfahren zur acylierung von cellulose - Google Patents
Verfahren zur acylierung von cellulose Download PDFInfo
- Publication number
- WO2007144282A1 WO2007144282A1 PCT/EP2007/055445 EP2007055445W WO2007144282A1 WO 2007144282 A1 WO2007144282 A1 WO 2007144282A1 EP 2007055445 W EP2007055445 W EP 2007055445W WO 2007144282 A1 WO2007144282 A1 WO 2007144282A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- methyl
- alkyl
- radicals
- formula
- Prior art date
Links
- 0 *C1C(*)C(*)N(*)C(*)C1* Chemical compound *C1C(*)C(*)N(*)C(*)C1* 0.000 description 6
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
Definitions
- the present invention describes a process for the acylation of cellulose by reacting cellulose with a ketene or a diketene in an ionic liquid.
- Cellulose is the most important renewable raw material and represents an important starting material for, for example, the textile, paper and nonwoven industries. It also serves as a raw material for derivatives and modifications of cellulose, to which cellulose ethers, 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 textile, food, construction and paint industries. Of particular interest here is cellulose acetate.
- DS degree of substitution
- the above-mentioned methods thus have various disadvantages.
- the acylated celluloses with a DS less than 3 can not be made directly.
- a reduction of the DP (degree of polymerization) compared to the cellulose used can occur.
- [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.
- the melting point is particularly preferably in the range from -50 ° C. to 150 ° C., particularly preferably in the range from -20 ° C. to 120 ° C. and exceptionally 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.
- the halide can be reacted with a Lewis acid to form a complex anion from halide and Lewis acid.
- replacement of a halide ion with the desired anion is possible. This can be done by adding a metal salt with precipitation of the metal halide formed, via an ion exchanger or by displacement of the halide ion by a strong acid (with liberation of the hydrohalic acid). Suitable methods are, for example, in Angew. Chem. 2000, 12, pp. 3926-3945 and the literature cited therein.
- Suitable alkyl radicals with which the nitrogen atom in the amines or nitrogen heterocycles may be quaternized are C 1 -C 6 -alkyl, preferably C 1 -C 10 -alkyl, particularly preferably C 1 -C 6 -alkyl and very particularly preferably methyl.
- the alkyl group may be unsubstituted or have one or more identical or different substituents.
- aromatic heterocycles are particularly preferred.
- Particularly preferred compounds are those which have a molecular weight below 1000 g / mol, very particularly preferably below 500 g / mol and in particular below 350 g / mol.
- radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups radical having 1 to 20 carbon atoms;
- radicals R 1 to R 9 independently of one another represent hydrogen, a sulfo
- radicals R 1 to R 9 which in the abovementioned formulas (III) to a carbon atom (and not to a heteroatom) may additionally be also halogen or a functional group; or
- the carbon-containing group contains heteroatoms, oxygen, nitrogen, sulfur, phosphorus and silicon are preferable.
- the radicals R 1 to R 9 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.
- Fractional groups and heteroatoms may also be directly adjacent so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (secondary amide ) or -CONR'- (tertiary amide), are included, for example, di (Ci-C4-alkyl) 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
- C 1 -C 20 -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-methyl-2-pentyl, 4-methyl-2-pentyl, 2 Methyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2 Methyl, 2-methyl-2-pentyl,
- 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
- 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.
- Ci-cis-alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2- Butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl 1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl , 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3 -
- aryl, 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 im ⁇ 30, 0 ⁇ a ⁇ m and
- 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
- Ci-Cis-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,
- 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 ⁇ ) m -CH 2 CH 2 CH 2 CH 2 - with R A and R B preferably hydrogen, methyl or ethyl and n preferably 0 to 3, in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6 Dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxa-undecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;
- 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
- 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,
- 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.
- 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.
- MIe imidazolium ions
- 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
- R 2 to R 4 independently of one another are hydrogen, methyl or ethyl.
- Very particularly preferred imidazolium ions are 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) -imidazolium, 1- (1-octyl) -imidazolium, 1- (1-dodecyl) -imidazolium, 1- (1-tetradecyl) imidazolium, 1- (1-hexadecyl) -imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-Butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butyl imidazolium, 1- (1-octyl) -3-methyl
- MIf very particularly preferred pyrazolium ions
- R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl.
- MIh very particularly preferred pyrazolium ions
- R 1 to R 4 are independently hydrogen or methyl.
- R 1 to R 6 are hydrogen or methyl.
- IMj 2-pyrazolinium
- MIj ' 2-pyrazolinium
- 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
- MIp oxazolium ions
- R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are independently hydrogen or methyl.
- MIq 1,2,4-triazolium ions
- MIq ' 1,2,4-triazolium ions
- MIq 1,2,4-triazolium ions
- R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
- Sir 1,3,3-triazolium ions
- IMr ' 1,3,3-triazolium ions
- MIr 1,3,3-triazolium ions
- 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 from which the quaternary ammonium ions of the general formula (MIu) are derived by quaternization with the radicals R mentioned are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl hexylamine, diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2 ethylhexyl) amine, di-isopropylethylamine, di-isopropyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpentylamine, di-iso-propyle
- Preferred quaternary ammonium ions of the general formula (MIu) are those which are derived from the following tertiary amines by quaternization with the abovementioned radicals R, such as diisopropylethylamine, diethyl-tert-butylamine, diisobutylbutylamine, di-isopropylamine n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.
- R such as diisopropylethylamine, diethyl-tert-butylamine, diisobutylbutylamine, di-isopropylamine n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.
- tertiary amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers.
- Another preferred tertiary amine having three identical residues is triallylamine.
- MIv guanidinium ions
- R 1 to R 5 are methyl.
- 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- dioxo-octyl, 1-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, 1-methoxy-4,8-dioxa-undecyl, 15-methoxy-4,8, 12-trioxa-pentadecyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9-trioxa-undecyl, 7-ethoxy-4-oxa
- MIx phosphonium ions
- 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 1 SiO 4 " , HR 3 SiO 4 2” , H 2 R 3 SiO 4 " , HR 3 R b SiO 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 C 2 -C 18 -alkyl, C 6 -C 14 -aryl, C 5 -C 12 -cycloalkyl or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-containing heterocycle, two of them together having an unsaturated, saturated or aromatic, optionally formed by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups interrupted ring, said radicals each additionally by 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.
- 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 is 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 sulfates, sulfites and sulfonates, the group of phosphates, and the group of carboxylic acids, in particular from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group containing SO 4 2 " , SO 3 2" , R 3 OSO 3 " and R 3 SO 3 -, and the group containing PO 4 3" and R 3 R b PO 4 -.
- Particularly preferred anions are chloride, bromide, iodide, SCN, OCN, CN, acetate, propionate, benzoate, C 1 -C 4 -alkyl sulfates, R 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 -
- 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.
- Ketenes for the purposes of the present invention are ketenes of the formula IVa and dicentenes for the purposes of the present invention are diketenes of the formula IVbI or mixed diketenes of the formula IVb2,
- R x, R x ', Rv, Rv' is hydrogen, Ci-C 3 -alkyl, C 2 -C 3 -alkenyl, C 2 -C 3 -alkynyl C 3 -C 2 - cycloalkyl, C5-CI2 Cycloalkenyl, aryl or heterocyclyl, where the seven last-mentioned radicals may be optionally substituted;
- R x and R y or R x ' and R y' together form an optionally substituted
- R z is hydrogen or C 1 -C 6 -alkyl; o is O or i; p is 2, 3, 4, 5, 6, 7 or 8; q, r is 1, 2, 3, 4, 5 or 6;
- C 1 -C 30 -alkyl radicals for R x , R x ' , R y and R y' are unsubstituted C 1 -C 30 -alkyl radicals or by functional groups, aryl, alkyl, aryloxy, alkyloxy , Cycloalkyl, halogen, heteroatoms and / or heterocycles are called substituted Ci-C3o-alkyl radicals, preferably Ci-C3o-alkyl radicals, 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-
- Unsubstituted C 2 -C 30 -alkenyl radicals or by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, are particularly unsubstituted C 2 -C 30 -alkenyl radicals for R x , R x ' , R y and R y' , Halogen, heteroatoms and / or heterocycles are called substituted C 2 -C 30 -alkenyl radicals, preferably C 2 -C 30 -alkenyl radicals, such as, for example, vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl or trans-2 -Butenyl, particularly preferably vinyl or 2-propenyl; or C 2 -C 30 -alkenyl radicals which are preferably substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and /
- C 2 -C 3 o-alkynyl radicals for R x , R x ' , R y . ' or R y' are in particular unsubstituted C 2 -C 30 -alkynyl radicals or by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted C2-C3o-alkynyl radicals mentioned, preferably C2 C 30 -alkynyl radicals, such as, for example, ethynyl, 1-propyn-3-yl, 1-propyn-1-yl or 3-methyl-1-propyn-3-yl, particularly preferably ethynyl or 1-propyn-3-yl , As optionally substituted C 3 -C 12 -cycloalkyl radicals for R x , R x ' , R y .
- R y' are in particular unsubstituted C 1 -C 8 -cycloalkyl radicals or by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted C 3 -C 12 -cycloalkyl radicals mentioned, preferably C3 -C 12 -cycloalkyl radicals, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl or butylcyclohexyl, and bicyclic systems such as norbornyl, preferably cyclopentyl or cyclohexyl ; or preferably substitute
- C 5 -C 2 -cycloalkenyl radicals for R x , R x ' , R y . ' or R y' are in particular unsubstituted Ca-Cs-cycloalkenyl radicals or by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles substituted Ca-Cs-cycloalkenyl radicals called, preferably Ca -Cs-cycloalkenyl radicals, such as, for example, 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl, and bicyclic systems such as, for example, norbornyl, particularly preferably 3-cyclopentenyl, 2-cyclohexenyl or 3-cyclohexenyl; or, preferably, by functional groups, aryl, alkyl, aryloxy
- Unsubstituted C 6 -C 12 -aryl radicals or by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms may be mentioned as unsubstituted or substituted aryl radicals for R x , R x ' , R y or R y' and / or heterocycles substituted C6-Ci2-aryl radicals, preferably C6-Ci2-aryl radicals, such as phenyl, ⁇ -naphthyl or ß-naphthyl, particularly preferably phenyl; or preferably C6-C12-aryl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, such as ToIyI, XyIyI, 4-diphenylyl, chlorophenyl, dichlorophen
- heterocyclyl radicals which may be mentioned are unsubstituted heteroaryl radicals or heteroaryl radicals which are substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles, preferably 5- or 6-membered heteroaryl Radicals which contain oxygen, nitrogen and / or sulfur atoms, such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl or benzothiazolyl; or preferably 5- or 6-membered heteroaryl radicals substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, cycloalkyl, halogen, heteroatoms and / or heterocycles and having oxygen, nitrogen and / or sulfur atoms, such as methylpyridy, di
- ketenes of the formula IVa are used.
- ketenes of the formula IVa are used, the radicals following
- R x is hydrogen or Ci-Ci ⁇ -alkyl, preferably hydrogen or Ci-C ⁇ -alkyl; particularly preferably hydrogen, methyl or ethyl; most preferably hydrogen;
- R ⁇ is hydrogen.
- ketenes of the formula IVa are used, where the radicals have the following meanings:
- R x is 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
- R ⁇ is hydrogen
- diketenes of the formula IVbI are used.
- diketenes of the formula IVbI are used, the radicals having 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, in particular hydrogen;
- R ⁇ is hydrogen
- ketenes of the formula IVbI where the radicals have the following meanings:
- R x is 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl;
- R ⁇ is hydrogen
- mixed diketenes of the formula IVb2 are used.
- mixed diketenes of the formula IVb2 are used, the radicals having the following meanings:
- R x , R x ' are hydrogen or Ci-C ⁇ -alkyl, preferably hydrogen, methyl or
- R ⁇ , R ⁇ ' is hydrogen.
- ketenes of the formula IVb2 are used, where the radicals have the following meanings:
- R x , R x ' is 1-decyl, 1-dodecyl, 1-tetradecyl or 1-hexadecyl R ⁇ , R ⁇ 'is hydrogen.
- 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 of the invention can be used not only for the acylation of cellulose but generally for the acylation of poly-, oligo- and disaccharides, 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 methyl cellulose and carboxymethyl cellulose, cellulose esters, such as cellulose acetate, cellulose butyrate and cellulose nitrate, each with a DS ⁇ 3.
- the corresponding explanations apply accordingly.
- a polysaccharide e.g. Cellulose, hemicellulose, starch, glycogen, dextran, tunicin, inulin, chitin or alginic acid, preferably cellulose, acylated.
- a disaccharide e.g. Sucrose, acylated.
- the process according to the invention acylates a cellulose derivative of which DS ⁇ 3, eg a cellulose ether, such as methylcellulose and carboxymethylcellulose, a cellulose ester, such as cellulose acetate, cellulose butyrate and cellulose nitrate, each with a DS.sup.3 ,
- 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 ketene of formula IV can be added in bulk, dissolved in an ionic liquid or in a suitable solvent.
- suitable solvents are, for example, ethers, such as diethyl ether, methyl tert-butyl ether, terahydrofuran or dioxane, or ketones, such as dimethyl ketone, or halogenated hydrocarbons, such as dichloromethane, trichloromethane or dichloroethane.
- the amount of solvent used is the To dissolve ketene of formula IV should be such that no precipitation of the cellulose occurs during the addition.
- the ionic liquid is preferably that in which the cellulase itself is dissolved as described above.
- the ketene of formula IV may be passed into the solution of cellulose in the ionic liquid.
- the ketene of formula IV is added in substance.
- the ketene of the formula IV is added dissolved in an ionic liquid, wherein it is particularly preferable to use the ionic liquid which is also used to dissolve the cellulose.
- the ionic liquid and the ketene of formula IV are premixed and the cellulose 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 dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane.
- aprotic dipolar solvents for example dimethyl sulfoxide, dimethylformamide, dimethylacetamide or sulfolane.
- nitrogen-containing bases such as pyridine, etc., can also be added.
- the reaction mixture in addition to the ionic liquid and optionally the solvent in which the ketene of the formula IV is dissolved, the reaction mixture contains less than 5% by weight, preferably less than 2% by weight, in particular less than 0.1 % By weight, based on the total weight of the reaction mixture, of further solvents and / or additional nitrogen-containing bases. It is also possible to carry out the process according to the invention in the presence of a catalyst.
- the alkali metal or alkaline earth metal salts of C1-C4-alkanecarboxylic acids or benzoic acid are suitable. Examples of these are sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium benzoate or potassium benzoate, preferably sodium acetate.
- the catalyst is usually used in amounts of up to 10 mol%, preferably up to 8 mol%, based on the ketene 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 ketene of formula IV.
- ketenes of formula IV which are liquid or solid at the reaction temperature
- the reaction is usually carried out at ambient pressure.
- the reaction is carried out in air. But it is also possible under inert gas, so for example under N2, a noble gas, CO2 or mixtures thereof to work.
- ketenes of formula IV which are gaseous at the reaction temperature, it may be advantageous to carry out the reaction under the autogenous pressure of the reaction mixture at the desired reaction temperature or at a pressure which is higher than the autogenous pressure of the reaction system.
- the amount of acylating agent used - in each case in relation to the cellulose used - the reaction time and optionally the reaction temperature is set.
- acylated cellulose it is possible to terminate the acylation reaction when the desired degree of acylation is achieved by separating the acylated cellulose from the reaction mixture.
- This can be achieved, for example, by the addition of an excess of water or other suitable solvent in which the acylated cellulose is not soluble but the ionic liquid is readily soluble, e.g. a lower alcohol, such as methanol, ethanol, propanol or butanol, or with a ketone, for example diethyl ketone, etc., or mixtures thereof.
- suitable solvent is also determined by the particular degree of substitution and the substituents of the cellulose.
- an excess of water or methanol is used.
- the work-up of the reaction mixture is usually carried out by precipitating the acylated cellulose as described above and filtering off the acylated cellulose. From the filtrate, the ionic liquid can be recovered by conventional methods by dissolving the volatile components, e.g. the precipitant, or excess ketene of formula IV, etc. are distilled off. The remaining ionic liquid can be used again in the process according to the invention. In a further embodiment, excess ketene may also remain in the ionic liquid and be reused in the process according to the invention.
- reaction mixture in water or in another suitable solvent in which the acylated cellulose is not soluble, but the ionic liquid is readily soluble, such. a lower alcohol, such as methanol, ethanol, propanol or butanol, or a ketone, for example diethyl ketone, etc., or mixtures thereof, initiate and, depending on the embodiment, for example, fibers to obtain films of acylated cellulose.
- a suitable solvent is also determined by the respective degree of substitution and the substituents of the cellulose.
- the filtrate is worked up as described above.
- acylation reaction when the desired degree of acylation is achieved by cooling and working up the reaction mixture.
- the work-up can be carried out according to the methods described above.
- the termination of the acylation reaction can also be carried out so that at a given time still existing ketene of formula IVa or diketene of formula IVb from the reaction mixture by distillation, stripping or extraction with a solvent which forms two phases with the ionic liquid, is removed.
- two or more ketenes of the formula IV are reacted.
- a mixture of two (or more) ketenes of formula IV can be used in analogy to the above procedure.
- acylated celluloses are obtained which carry two (or more) different acyl groups (depending on the ketenes of formula IV used).
- the ionic liquid may contain up to 15% by weight, preferably up to 10% by weight, in particular up to 5% by weight of precipitant (s) such as described above.
- the process can be carried out batchwise, semicontinuously or continuously.
- the present invention also provides acylated celluloses which are obtainable by the reaction of cellulose with a diketene of the formula IVbI or of the formula IVb2 in an ionic liquid of the formulas I or II.
- acylated celluloses obtainable by the process according to the invention by acylating cellulose with a diketene of the formula IVbI or IVb are suitable for the production of films and fibers or of materials.
- the ionic liquid was dried overnight at 120 ° C and 0.05 mbar with stirring.
- the average degree of substitution DS of the acylated cellulose was determined by NMR spectroscopic methods.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/305,017 US20090326216A1 (en) | 2006-06-16 | 2007-06-04 | Process for acylating cellulose |
AU2007260114A AU2007260114B2 (en) | 2006-06-16 | 2007-06-04 | Process for acylating cellulose |
JP2009514748A JP2009540075A (ja) | 2006-06-16 | 2007-06-04 | セルロースのアシル化法 |
EP07729833A EP2035458A1 (de) | 2006-06-16 | 2007-06-04 | Verfahren zur acylierung von cellulose |
BRPI0713461-4A BRPI0713461A2 (pt) | 2006-06-16 | 2007-06-04 | processo para acilar polissacarìdeos, oligossacarìdeos ou dissacarìdeos ou seus derivados, celulose acilada, e, uso da glicose acilada |
CN2007800269389A CN101490089B (zh) | 2006-06-16 | 2007-06-04 | 纤维素的酰化方法 |
CA002654107A CA2654107A1 (en) | 2006-06-16 | 2007-06-04 | Process for acylating cellulose |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006028165A DE102006028165A1 (de) | 2006-06-16 | 2006-06-16 | Verfahren zur Acylierung von Cellulose |
DE102006028165.9 | 2006-06-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007144282A1 true WO2007144282A1 (de) | 2007-12-21 |
Family
ID=38332423
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/055445 WO2007144282A1 (de) | 2006-06-16 | 2007-06-04 | Verfahren zur acylierung von cellulose |
Country Status (12)
Country | Link |
---|---|
US (1) | US20090326216A1 (de) |
EP (1) | EP2035458A1 (de) |
JP (1) | JP2009540075A (de) |
KR (1) | KR20090023694A (de) |
CN (1) | CN101490089B (de) |
AU (1) | AU2007260114B2 (de) |
BR (1) | BRPI0713461A2 (de) |
CA (1) | CA2654107A1 (de) |
DE (1) | DE102006028165A1 (de) |
MY (1) | MY149031A (de) |
WO (1) | WO2007144282A1 (de) |
ZA (1) | ZA200900300B (de) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008098037A2 (en) * | 2007-02-06 | 2008-08-14 | North Carolina State University | Polymer derivatives and composites from the dissolution of lignocellulosics in ionic liquids |
WO2008100566A1 (en) * | 2007-02-14 | 2008-08-21 | Eastman Chemical Company | Cellulose esters and their production in carboxylated ionic liquids |
US20090203900A1 (en) * | 2008-02-13 | 2009-08-13 | Eastman Chemical Comapany | Production of cellulose esters in the presence of a cosolvent |
US20090203898A1 (en) * | 2008-02-13 | 2009-08-13 | Eastman Chemical Company | Cellulose esters and their production in halogenated ionic liquids |
WO2009103681A1 (de) * | 2008-02-22 | 2009-08-27 | Basf Se | Verfahren zur herstellung fester materialien auf der basis von synthetischen polymeren und/oder biopolymeren und ihre verwendung |
WO2010019244A1 (en) * | 2008-08-13 | 2010-02-18 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom |
WO2010019245A1 (en) * | 2008-08-13 | 2010-02-18 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
US7959765B2 (en) | 2007-02-06 | 2011-06-14 | North Carolina State Universtiy | Product preparation and recovery from thermolysis of lignocellulosics in ionic liquids |
US8067488B2 (en) | 2009-04-15 | 2011-11-29 | Eastman Chemical Company | Cellulose solutions comprising tetraalkylammonium alkylphosphate and products produced therefrom |
US8182557B2 (en) | 2007-02-06 | 2012-05-22 | North Carolina State University | Use of lignocellulosics solvated in ionic liquids for production of biofuels |
US8188267B2 (en) | 2008-02-13 | 2012-05-29 | Eastman Chemical Company | Treatment of cellulose esters |
JP2012519740A (ja) * | 2009-03-06 | 2012-08-30 | フラウンホーファー − ゲゼルシャフト ツル フェーデルング デル アンゲヴァントテン フォルシュング エー.ファォ. | 多糖誘導体の調製方法 |
US8729253B2 (en) | 2011-04-13 | 2014-05-20 | Eastman Chemical Company | Cellulose ester optical films |
WO2015177242A1 (en) * | 2014-05-21 | 2015-11-26 | Titan Wood Limited | Process for acetylation of wood in the presence of an acetylation catalyst |
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 |
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 |
US10442870B2 (en) | 2014-03-19 | 2019-10-15 | Daicel Corporation | Cellulose acylate-oxoalkanoate |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
WO2009087184A1 (de) * | 2008-01-09 | 2009-07-16 | Basf Se | Verfahren zur aufarbeitung ionischer flüssigkeiten |
CN102712698A (zh) * | 2010-01-15 | 2012-10-03 | 巴斯夫欧洲公司 | 将多糖或寡糖氯化的方法 |
US8980050B2 (en) | 2012-08-20 | 2015-03-17 | Celanese International Corporation | Methods for removing hemicellulose |
JP2014511946A (ja) * | 2011-03-29 | 2014-05-19 | ビーエーエスエフ ソシエタス・ヨーロピア | グルカンを用いることによるセルロース材のコーティング方法 |
US20140048221A1 (en) | 2012-08-20 | 2014-02-20 | Celanese International Corporation | Methods for extracting hemicellulose from a cellulosic material |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993003063A1 (en) * | 1991-08-09 | 1993-02-18 | Eastman Chemical Company | Cellulose acetoacetates |
WO2005023873A1 (en) * | 2003-09-11 | 2005-03-17 | Kemira Oyj | Starch esterification method |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3342806A (en) * | 1965-07-23 | 1967-09-19 | Nat Starch Chem Corp | Novel acetoacetylated starch derivatives |
US5750677A (en) * | 1994-12-30 | 1998-05-12 | Eastman Chemical Company | Direct process for the production of cellulose esters |
US6528643B1 (en) * | 2000-05-05 | 2003-03-04 | Hercules Incorporated | Esterified polysaccharide products and B-lactone ring opened ketene dimer products containing the compositions, and process of making the same |
GB0123595D0 (en) * | 2001-10-02 | 2001-11-21 | Univ Belfast | Zeolite reactions |
US6824599B2 (en) * | 2001-10-03 | 2004-11-30 | The University Of Alabama | Dissolution and processing of cellulose using ionic liquids |
JP5007985B2 (ja) * | 2004-06-25 | 2012-08-22 | 国立大学法人 東京大学 | ポリマーブラシ化合物及びその調製方法 |
US8148518B2 (en) * | 2007-02-14 | 2012-04-03 | Eastman Chemical Company | Cellulose esters and their production in carboxylated ionic liquids |
-
2006
- 2006-06-16 DE DE102006028165A patent/DE102006028165A1/de not_active Withdrawn
-
2007
- 2007-06-04 WO PCT/EP2007/055445 patent/WO2007144282A1/de active Application Filing
- 2007-06-04 KR KR1020097000810A patent/KR20090023694A/ko not_active Application Discontinuation
- 2007-06-04 CA CA002654107A patent/CA2654107A1/en not_active Abandoned
- 2007-06-04 EP EP07729833A patent/EP2035458A1/de not_active Withdrawn
- 2007-06-04 MY MYPI20085076A patent/MY149031A/en unknown
- 2007-06-04 US US12/305,017 patent/US20090326216A1/en not_active Abandoned
- 2007-06-04 BR BRPI0713461-4A patent/BRPI0713461A2/pt not_active IP Right Cessation
- 2007-06-04 CN CN2007800269389A patent/CN101490089B/zh not_active Expired - Fee Related
- 2007-06-04 AU AU2007260114A patent/AU2007260114B2/en not_active Ceased
- 2007-06-04 JP JP2009514748A patent/JP2009540075A/ja active Pending
-
2009
- 2009-01-14 ZA ZA200900300A patent/ZA200900300B/xx unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993003063A1 (en) * | 1991-08-09 | 1993-02-18 | Eastman Chemical Company | Cellulose acetoacetates |
WO2005023873A1 (en) * | 2003-09-11 | 2005-03-17 | Kemira Oyj | Starch esterification method |
Cited By (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8182557B2 (en) | 2007-02-06 | 2012-05-22 | North Carolina State University | Use of lignocellulosics solvated in ionic liquids for production of biofuels |
US7959765B2 (en) | 2007-02-06 | 2011-06-14 | North Carolina State Universtiy | Product preparation and recovery from thermolysis of lignocellulosics in ionic liquids |
WO2008098037A2 (en) * | 2007-02-06 | 2008-08-14 | North Carolina State University | Polymer derivatives and composites from the dissolution of lignocellulosics in ionic liquids |
WO2008098037A3 (en) * | 2007-02-06 | 2008-12-11 | Univ North Carolina State | Polymer derivatives and composites from the dissolution of lignocellulosics in ionic liquids |
US7919631B2 (en) | 2007-02-14 | 2011-04-05 | Eastman Chemical Company | Production of ionic liquids |
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 |
WO2008100566A1 (en) * | 2007-02-14 | 2008-08-21 | Eastman Chemical Company | Cellulose esters and their production in carboxylated ionic liquids |
KR101551500B1 (ko) | 2007-02-14 | 2015-09-08 | 이스트만 케미칼 캄파니 | 셀룰로스 에스터 및 카복실화된 이온성 액체에서의 이의 제조 |
JP2010518244A (ja) * | 2007-02-14 | 2010-05-27 | イーストマン ケミカル カンパニー | セルロースエステルおよびカルボキシル化イオン液体中でのその製造 |
US8148518B2 (en) | 2007-02-14 | 2012-04-03 | Eastman Chemical Company | Cellulose esters and their production in carboxylated ionic liquids |
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 |
US9156918B2 (en) | 2008-02-13 | 2015-10-13 | Eastman Chemical Company | Treatment of cellulose esters |
US8158777B2 (en) * | 2008-02-13 | 2012-04-17 | Eastman Chemical Company | Cellulose esters and their production in halogenated ionic liquids |
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 |
US8188267B2 (en) | 2008-02-13 | 2012-05-29 | Eastman Chemical Company | Treatment of cellulose esters |
US9175096B2 (en) | 2008-02-13 | 2015-11-03 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
US8273872B2 (en) | 2008-02-13 | 2012-09-25 | Eastman Chemical Company | Cellulose esters and their production in halogenated ionic liquids |
US20090203898A1 (en) * | 2008-02-13 | 2009-08-13 | Eastman Chemical Company | Cellulose esters and their production in halogenated ionic liquids |
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 |
US20090203900A1 (en) * | 2008-02-13 | 2009-08-13 | Eastman Chemical Comapany | Production of cellulose esters in the presence of a cosolvent |
WO2009103681A1 (de) * | 2008-02-22 | 2009-08-27 | Basf Se | Verfahren zur herstellung fester materialien auf der basis von synthetischen polymeren und/oder biopolymeren und ihre verwendung |
US8198219B2 (en) | 2008-02-22 | 2012-06-12 | Basf Se | Method for producing solid materials on the basis of synthetic polymers and/or biopolymers and use thereof |
WO2010019244A1 (en) * | 2008-08-13 | 2010-02-18 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom |
EP3239179A1 (de) * | 2008-08-13 | 2017-11-01 | Eastman Chemical Company | Anhand eines verfahrens unter verwendung von carboxylierten ionischen flüssigkeiten erzeugte regioselektiv substituierte celluloseester und daraus hergestellte produkte |
WO2010019245A1 (en) * | 2008-08-13 | 2010-02-18 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
JP2012519740A (ja) * | 2009-03-06 | 2012-08-30 | フラウンホーファー − ゲゼルシャフト ツル フェーデルング デル アンゲヴァントテン フォルシュング エー.ファォ. | 多糖誘導体の調製方法 |
JP2012524144A (ja) * | 2009-04-15 | 2012-10-11 | イーストマン ケミカル カンパニー | テトラアルキルアンモニウムアルキルホスフェートイオン液体法で製造される、位置選択的に置換されたセルロースエステル、およびそれから製造される製品 |
US8524887B2 (en) | 2009-04-15 | 2013-09-03 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a tetraalkylammonium alkylphosphate ionic liquid process and products produced therefrom |
US8067488B2 (en) | 2009-04-15 | 2011-11-29 | Eastman Chemical Company | Cellulose solutions comprising tetraalkylammonium alkylphosphate and products produced therefrom |
EP3216806A1 (de) * | 2009-04-15 | 2017-09-13 | Eastman Chemical Company | In einem verfahren unter verwendung von tetraalkylammoniumalkylphosphat als ionischer flüssigkeit erzeugte, regioselektiv substituierte celluloseester und daraus hergestellte produkte |
US8871924B2 (en) | 2009-04-15 | 2014-10-28 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a tetraalkylammonium alkylphosphate ionic liquid process and products produced therefrom |
US9926384B2 (en) | 2009-04-15 | 2018-03-27 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a tetraalkylammonium alkylphosphate ionic liquid process and products produced therefrom |
US8729253B2 (en) | 2011-04-13 | 2014-05-20 | Eastman Chemical Company | Cellulose ester optical films |
US9096691B2 (en) | 2011-04-13 | 2015-08-04 | Eastman Chemical Company | Cellulose ester optical films |
US9796791B2 (en) | 2011-04-13 | 2017-10-24 | Eastman Chemical Company | Cellulose ester optical films |
US9975967B2 (en) | 2011-04-13 | 2018-05-22 | Eastman Chemical Company | Cellulose ester optical films |
US10494447B2 (en) | 2011-04-13 | 2019-12-03 | Eastman Chemical Company | Cellulose ester optical films |
US10836835B2 (en) | 2011-04-13 | 2020-11-17 | Eastman Chemical Company | Cellulose ester optical films |
US10442870B2 (en) | 2014-03-19 | 2019-10-15 | Daicel Corporation | Cellulose acylate-oxoalkanoate |
WO2015177242A1 (en) * | 2014-05-21 | 2015-11-26 | Titan Wood Limited | Process for acetylation of wood in the presence of an acetylation catalyst |
US10982011B2 (en) | 2014-05-21 | 2021-04-20 | Titan Wood Limited | Process for acetylation of wood in the presence of an acetylation catalyst |
Also Published As
Publication number | Publication date |
---|---|
BRPI0713461A2 (pt) | 2012-01-24 |
AU2007260114B2 (en) | 2012-01-19 |
US20090326216A1 (en) | 2009-12-31 |
EP2035458A1 (de) | 2009-03-18 |
MY149031A (en) | 2013-06-28 |
AU2007260114A1 (en) | 2007-12-21 |
DE102006028165A1 (de) | 2007-12-20 |
CN101490089B (zh) | 2013-01-09 |
JP2009540075A (ja) | 2009-11-19 |
KR20090023694A (ko) | 2009-03-05 |
ZA200900300B (en) | 2010-03-31 |
CA2654107A1 (en) | 2007-12-21 |
CN101490089A (zh) | 2009-07-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2007144282A1 (de) | Verfahren zur acylierung von cellulose | |
WO2008000666A1 (de) | Verfahren zur acylierung von cellulose mit gezieltem durchschnittlichen polymerisationsgrad | |
WO2007101812A1 (de) | Verfahren zum abbau von cellulose | |
WO2007101811A1 (de) | Verfahren zum abbau von cellulose in lösung | |
EP2035460A1 (de) | Verfahren zur silylierung von cellulose | |
WO2007101813A1 (de) | Verfahren zum abbau von cellulose mit nucleophilen | |
EP2041183A1 (de) | Verfahren zur darstellung von celluloseacetalen | |
EP1893651B1 (de) | Löslichkeit von cellulose in ionischen flüssigkeiten unter zugabe von aminbase | |
EP1881994B1 (de) | Lösungen von cellulose in ionischen flüssigkeiten | |
EP1966284B1 (de) | Lösungssystem auf der basis geschmolzener ionischer flüssigkeiten, dessen herstellung sowie verwendung zur herstellung regenerierter kohlenhydrate | |
DE102005062608A1 (de) | Lösungssystem auf der Basis geschmolzener ionischer Flüssigkeiten ein Verfahren zu dessen Herstellung sowie zur Herstellung regenerierter Kohlenydrate | |
DE102006035830A1 (de) | Lösungssystem auf der Basis geschmolzener ionischer Flüssigkeiten, dessen Herstellung sowie Verwendung zur Herstellung regenerierter Kohlenhydrate | |
DE102006011076A1 (de) | Verfahren zum Abbau von Cellulose | |
DE102006029306A1 (de) | Verfahren zur Silylierung von Cellulose | |
DE102006031810A1 (de) | Verfahren zur Darstellung von Celluloseacetalen | |
DE102006042892A1 (de) | Verfahren zur Acylierung von Cellulose mit gezieltem durchschnittlichen Polymerisationsgrad | |
DE102006030696A1 (de) | Verfahren zur Acylierung von Cellulose mit gezieltem durchschnittlichen Polymerisationsgrad | |
DE102006054213A1 (de) | Verfahren zur Darstellung von Celluloseacetalen | |
DE102006042891A1 (de) | Verfahren zum Abbau von Cellulose | |
DE102006054233A1 (de) | Verfahren zur Silylierung von Cellulose | |
DE102006032569A1 (de) | Verfahren zur Silylierung von Cellulose | |
DE102006042890A1 (de) | Verfahren zur Silylierung von Cellulose |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200780026938.9 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07729833 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2654107 Country of ref document: CA |
|
REEP | Request for entry into the european phase |
Ref document number: 2007729833 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007729833 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007260114 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12305017 Country of ref document: US Ref document number: 2009514748 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2007260114 Country of ref document: AU Date of ref document: 20070604 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020097000810 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 277/CHENP/2009 Country of ref document: IN |
|
ENP | Entry into the national phase |
Ref document number: PI0713461 Country of ref document: BR Kind code of ref document: A2 Effective date: 20081216 |