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
• • 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
• • 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
  • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof

Definitions

• the present invention describes a process for chlorinating polysaccharides or oligosaccharides, which comprises
• Cellulose is the most important renewable raw material and represents an important starting material for, for example, the textile and paper and nonwovens industries. It also serves as raw material for cellulose derivatives and modification methods and processes, including cellulose ethers and cellulose esters. These derivatives and modi- fications have several uses, for example in the textile, food, building and surface coating industries. Therefore there is a particular interest in processes by which cellulose may by modified and also in modified cellulose for various technical applications.
• cellulose or modified cellulose of low molecular weight which corresponds to a low degree of polymerization (DP) is required in many technical applications.
• acylation and degradation of cellulose in ionic liquids is described.
• the process is a two step process. In a first step the DP of the cellulose is lowered according to the teachings of WO 2007/10181 1 or WO 2007/101812 and in a second step the obtained low molecular weight cellulose is acylated.
• step A) of the process a polysaccharide or oligosaccharide is dissolved in a solvent system which comprises at least one ionic liquid.
• polysaccharides or oligosaccharides examples include cellulose, and hemicellulose and also starch, glycogen, dextran and tunicin. Further examples are the polyconden- sates of D-fructose, e.g. inulin, and also, inter alia, chitin, and alginic acid.
• the polysaccharides or oligosaccharides, in particular cellulose, may to some extent be chemically modified, for example by etherification or esterification of hydroxyl groups.
• the polysaccharide or oligosaccharide is cellulose, hemicellulose or chemically modified cellulose.
• cellulose is used as polysaccharide. Most preferably the cellulose used is unmodified.
• Preferred poly-or oligosaccharides, in particular cellulose, used for the process have a degree of polymerization (DP) of at least 50, more preferably of at least 150 or most preferred of at least 300.
• the maximum DP may, for example, be 1000, more prefera- bly 800 or at maximum 600.
• the degree of polymerization is the number of repeat units in an average polymer chain.
• the molecular weight is the weight average molecular weight.
• DP can be measured by Gel Permeable Chromatography (GPC) or Size Exclusion Chromatography (SEC).
• the solvent system may be one solvent or a mixture of solvents.
• the solvent system might be an ionic liquid, only, or a mixture of different ionic liquids or a mixture of ionic liquids and other organic, non-ionic solvents.
• non-ionic solvents polar solvents which can be mixed homogeneously with ionic liquids and do not lead to precipitation of the polysaccharide may be used, for example ethers or ketons, for example dioxane, dimethyl sulfoxide, dimethylformamide, dimethy- lacetamide or sulfolane. Preffered is dioxane.
• the content of ionic liquids in the solvent system is preferably at least 20 % by weight, more preferably at least 50 % by weight and most preferably at least 80 % or 90 % by weight.
• the solvent system is a mixture comprising one or more ionic liquids and at least one non ionic solvent, in particular dioxane.
• the content of ionic liquids is preferably from 20 to 90 % by weight, the reminder being the non-ionic solvent or solvents.
• the solvent system preferably has no content or only a low content of water of below 5 % by weight.
• the content of water is below 2 % by weight.
• the term ionic liquid refers to salts (compounds composed of cations and anions) which at atmospheric pressure (1 bar) have a melting point of less than 200°C, preferably less than 150°C, particularly preferably less than 100°C and very particularly preferably less than 80°C.
• the ionic liquids are liquid under normal conditions (1 bar, 21 °C), i.e. at room temperature.
• Preferred ionic liquids comprise an organic compound as cation (organic cation).
• the ionic liquid can comprise further cations, in- eluding metal cations, in addition to the organic cation.
• the cations of particularly preferred ionic liquids are exclusively an organic cation or, in the case of polyvalent anions, a mixture of different organic cations.
• Suitable organic cations are, in particular, organic compounds having heteroatoms such as nitrogen, sulfur, oxygen or phosphorus; in particular, the organic cations are compounds having an ammonium group (ammonium cations), an oxonium group (oxonium cations), a sulfonium group (sulfonium cations) or a phosphonium group (phosphonium cations).
• the organic cations of the ionic liquid are ammonium cations, which for the present purposes are non aromatic compounds having a localized positive charge on the nitrogen atom, e.g. compounds comprising tetravalent nitrogen (quaternary ammonium compounds) or compounds comprising trivalent nitro- gen, with one bond being a double bond, or aromatic compounds having a delocalized positive charge and at least one nitrogen atom, preferably one or two nitrogen atoms, in the aromatic ring system.
• Preferred organic cations are quaternary ammonium cations which preferably have three or four aliphatic substituents, particularly preferably C1 -C12-alkyl groups, which may optionally be substituted by hydroxyl groups, on the nitrogen atoms. Particular preference is given to organic cations which comprise a heterocyclic ring system having one or two nitrogen atoms as constituent of the ring system.
• bicyclic systems Monocyclic, bicyclic, aromatic or nonaromatic ring systems are possible. Mention may be made of, for example, bicyclic systems as are described in WO 2008/043837.
• the bicyclic systems of WO 2008/043837 are diazabicyclo derivatives, preferably made up of a 7-membered ring and a 6-membered ring, which comprise an amidinium group; particular mention may be made of the 1 ,8-diazabicyclo[5.4.0]undec-7-enium cation.
• Very particularly preferred organic cations comprise a five- or six-membered heterocyc- lie ring system having one or two nitrogen atoms as constituent of the ring system.
• Possible organic cations of this type are, for example, pyridinium cations, pyridazinium cations, pyrimidinium cations, pyrazinium cations, imidazolium cations, pyrazolium cations, pyrazolinium cations, imidazolinium cations, thiazolium cations, triazolium cations, pyrrolidinium cations and imidazolidinium cations. These cations are, for example, mentioned in WO 2005/1 13702.
• the nitrogen atoms of the cations are substituted by hydrogen or an organic group which generally has not more than 20 carbon atoms, preferably a hydrocarbon group, in particular a C1 -C16-alkyl group, in particular a C1 -C10-alkyl group, particularly preferably a C1 -C4-alkyl group, if such substitution is necessary to have a positive charge.
• the carbon atoms of the ring system can also be substituted by organic groups which generally have not more than 20 carbon atoms, preferably a hydrocarbon group, in particular a C1 -C16-alkyl group, in particular a C1 -C10-alkyl group, particularly pref- erably a C1 -C4-alkyl group.
• organic groups which generally have not more than 20 carbon atoms, preferably a hydrocarbon group, in particular a C1 -C16-alkyl group, in particular a C1 -C10-alkyl group, particularly pref- erably a C1 -C4-alkyl group.
• ammonium cations are quaternary ammonium cations, imidazolium cations, pyrimidinium cations and pyrazolium cations.
• R is an organic group with 1 to 20 carbon atoms
• R1 to R5 are, independently from each other, a hydrogen atom or an organic group with 1 to 20 carbon atoms, in case of imidazolium (formula I) and pyrazolium cations (formula lii), R1 is preferably an organic group with 1 to 20 carbon atoms. Most preferred are imidazolium cations of formula I; in particular imidazolium cations where R and R1 are each an organic radical having from 1 to 20 carbon atoms and R2, R3, and R4 are each an H atom or an organic radical having from 1 to 20 carbon atoms.
• R and R1 each being, independently of one another, an organic radical having from 1 to 10 carbon atoms.
• R and R1 are each an aliphatic radical, in particular an aliphatic radical without further heteroatoms, e.g. an alkyl group.
• R and R1 each being, independently of one another, a C1 -C10- or C1 -C4-alkyl group.
• R2, R3 and R4 each being, independently of one another, an H atom or an organic radical having from 1 to 10 carbon atoms; in particular R2, R3 and R4 are each an H atom or an aliphatic radical.
• R2, R3 and R4 each being, independently of one an- other, an H atom or an alkyl group; in particular R2, R3 and R4 are each, independently of one another, an H atom or a C1 -C4-alkyl group.
• the ionic liquids can comprise inorganic or organic anions. Such anions are mentioned, for example, in the abovementioned WO 03/029329, WO 2007/076979,
• Possible anions are in particular anions from the following groups:
• M is a metal and Hal is fluorine, chlorine, bromine or iodine, r and t are positive integers and indicate the stoichiometry of the complex and s is a positive integer and indicates the charge on the complex; the group of sulfides, hydrogensulfides, polysulfides, hydrogenpolysulfides and thiolates of the general formulae:
• R a , R b , R c and R d are each independently of one another, hydrogen; Ci-C3o-alkyl and aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, -0-, -CO-, -CO-O- or -CO-N ⁇ substituted derivatives thereof, for example methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, 2-methyl-1 -propyl (isobutyl), 2-methyl-
• C3-Ci2-cycloalkyl and aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, car- boxy-, formyl-, -0-, -CO- or -CO-O-substituted derivatives thereof, for example cyclopentyl, 2-methyl-1 -cyclopentyl, 3-methyl-1 -cyclopentyl, cyclohexyl, 2-methyl-1 - cyclohexyl, 3-methyl-1 -cyclohexyl, 4-methyl-1 -cyclohexyl or C q F2( q -a)-(i-b)H2a-b where q ⁇ 30, 0 ⁇ a ⁇ q and b 0 or 1 ;
• Aryl or heteroaryl having from 2 to 30 carbon atoms and alkyl-, aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, -0-, -CO- or -CO-O- substituted derivatives thereof, for example phenyl, 2-methylphenyl (2-tolyl),
• Anions which may be mentioned are, for example, chloride; bromide; iodide; thiocy- anate; hexafluorophosphate; trifluoromethanesulfonate; methanesulfonate; the car- boxylates, in particular formate; acetate; mandelate; nitrate; nitrite; trifluoroacetate; sulfate; hydrogensulfate; methylsulfate; ethylsulfate; 1 -propylsulfate; 1 -butylsulfate; 1 -hexylsulfate; 1 -octylsulfate; phosphate; dihydrogenphosphate; hydrogenphosphate; C1 -C4-dialkylphosphates; propionate; tetrachloroaluminate; AI2CI7 " ; chlorozincate; chloroferrate; bis(trifluoromethylsulfonyl)imi
• R a is a C1 -C12-alkyl group, preferably a C1-C6-alkyl group, alkylsulfonates
• R a is a C1 -C12 alkyl group, preferably a C1-C6-alkyl group, halides, in particular chloride and bromide, and pseudohalides, such as thiocyanate, dicyanamide, carboxylates R a COO;
• R a is a C1 -C20-alkyl group, preferably a C1-C8-alkyl group, in particular acetate, phosphates,
• dialkylphosphates of the formula R a R b P04 " where R a and R b are each, independently of one another, C1 -C6-alkyl groups; in particular, R a and R b are the same alkyl group, for example dimethylphosphate and diethylphosphate, and phosphonates, in particular monoalkylphosphonic esters of the formula R a R b P03 " , where R a and R b are each, independently of one another, a C1 -C6-alkyl group.
• Very particularly preferred anions are: chloride, bromide, hydrogensulfate, tetrachloroaluminate, thiocyanate, dicyanamide, methylsulfate, ethylsulfate, methanesulfonate, formate, acetate, dimethylphosphate, diethylphosphate, p-toluenesulfonate, tetrafluoroborate and hexafluorophosphate, me- thylmethylphosphonate (methylester of methylphosphonate).
• Particularly preferred ionic liquids consist exclusively of an organic cation together with one of the anions mentioned.
• imdazolium salts with an imidazolium cation according to formula I and one of the above anions specifically one of the particularly preferred anions, specifically acetate, chloride, dimethylphosphate or diethylphosphate or methylmethyl- phosphonate. Most preffered is acetate or chloride.
• the molecular weight of the ionic liquid is preferably less than 2000 g/mol, particularly preferably less than 1500 g/mol, particularly preferably less than 1000 g/mol and very particularly preferably less than 750 g/mol; in a particular embodiment, the molecular weight is in the range from 100 to 750 g/mol or in the range from 100 to 500 g/mol.
• a solution of the poly- or oligosaccharide, preferably cellulose, in the solvent system is prepared.
• concentration of the poly- or oligosaccharide can be varied within a wide range. 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, particularly preferably from 0.3 to 30% by weight and very particularly preferably from 0.5 to 20% by weight.
• This dissolution procedure can be carried out at room temperature or with heating, but above the melting point or softening temperature of the ionic liquid, usually at a tem- perature of from 0 to 200°C, preferably from 20 to 180°C, particularly preferably from 50 to 150°C.
• it is also possible to accelerate dissolution by intensive stirring or mixing or by introduction of microwave or ultrasonic energy or by a combination of these.
• a solvent system comprising ionic liquids and non-ionic solvents is used, the poly- or oligosaccharide may be dissolved in the ionic liquid first and the non-ionic sol- vent be added thereafter.
• step B) the poly- or oligosaccharides, preferably cellulose, are reacted with a chlorinating agent.
• the chlorinating agent may, for example, be added as such or in form of a solution in an appropriate solvent to the solution obtained after step A).
• Usual chlorinating agents may be used, for example thionyl chloride, methanesulfonyl chloride, chlorodimethyliminium chloride, phosphoryl chloride or para-toluenesulfonic chloride.
• a preferred chlorinating agent is thionyl chloride.
• the chlorinating agent should be added at least in amounts to achieve the desired degree of substitution.
• the degree of substitution (DS) of poly- or oligosaccharides is the average number of hydroxyl groups per six-ring unit of the polysaccharides or oligosaccharides substituted by a chloride.
• the degree of substitution (DS) of a given chlorinate cellulose is defined as the average number of substituted hydroxyl groups per anhydroglucose unit (AGU). DS is determined from the chlorine content detected in elemental analysis.
• the chlorinated polysaccharides or oligosaccharides obtained by the process of the invention preferably have a degree of substitution (DS) of at least 0.5.
• DS degree of substitution
• the first hydroxyl group in cellulose to be substituted by a chlorine atom will usually be the hydroxyl of the hydroxyl-methylene- group.
• a preferred DS of the chlorinated cellulose obtained by the process of the invention is 0.5 to 3, more preferred is a DS of 0.8 to 3.
• Suitable chlorinated cellulose obtained by the process of the instant invention may have, for example a DS of 0.5 to 1 .5 or from 0.8 to 1 .5.
• a DS in chlorinated cellulose of at least 1.0 can be easily achieved.
• the chlorinating agent may be added in excess, which means that more chlorinating agent may be added than required for the maximum DS.
• Non -reacted chlorinating agents may be removed by usual means, thionyl chloride may, for example, be removed by evaporation.
• the chlorinating agent in particular thionyl chloride, does not only effect the substitution of the hydroxyl group by a chlorine atom but leads also to a degradation of the poly- or oligosaccharides, in particular cellulose. This degradation is caused by the fact that the chlorinating agent hydrolyzes the oxygen bridging between the repeating units of the main chain of the oligo- or polysaccharide ( ⁇ -1 ,4- glycosidic bonds.
• the process of the instant invention is in fact also a process for chlorinating and hydrolyzing poly- or oligosaccharides.
• the obtained chlorinated poly- or oligosaccharides for example chlorinated cellulose, preferably have a degree of polymerization (DP) which is lower less than the DP of the non-chlorinated polysaccharides or oligosaccharides, in particular the DP of the obtained chlorinated poly- or oligosaccharides may be less than 90 %, preferably less than 80 %, more preferably less than 50 %, and most preferably less than 20 or even less than 10 % of the DP of the non chlorinated starting material.
• DP degree of polymerization
• degraded chlorinated cellulose may be obtained with a DP of less than 100, for example with a DP of 5 to 100, or of 10 to 100, or of 10 to 50.
• a chlorinated cellulose which may have, for example, a DS of 0.5 to 3, specifically of 0.5 to 1 .5 and a DP of 10 to100, specifically of 10 to 50. Most preferred is chlorinated cellulose with a DS of 0.5 to 1 .5 and a DP of 5 to 100 or chlorinated cellulose of a DS of 0.8 to 1.5 and a DP of 10 to 50.
• the reaction mixture is preferably kept at an elevated temperature; the temperature may be for example from 30 to 150°C, more preferably from 80 to 130°C at ambient pressure (1 bar).
• the reaction is carried out in air.
• inert gas i.e., for example, under N2, a noble gas or a mixture thereof.
• Temperature and reaction time may be selected to achieve the desired degree of DS and DP.
• no further additives like acids or nucleophiles (see WO 2007/10181 1 , degradation by the use of acids or WO 2007/101813, degradation by nucleophils) are required.
• the use of a base is not required.
• the chlorination is performed in absence of an additional base.
• solutions are obtained which comprise ionic liquid and chlorinated polysaccharides or oligosaccharides.
• the chlorinated polysaccharides or oligosaccharides may be isolated from such solutions, if desired, by usual means.
• the chlorinated polysaccharides or oligosaccharides may for example be obtained from the solution by adding a coagulating solvent (non-solvent for chlorinated polysaccharides or oligosaccharides) or other coagulating agent, in particular a base or basic salt, for example ammonia or a solution comprising NH4OH and separating the coagulated chlorinated polysaccharides or oligosaccharides from the solvent system.
• a coagulating solvent non-solvent for chlorinated polysaccharides or oligosaccharides
• other coagulating agent in particular a base or basic salt, for example ammonia or a solution comprising NH4OH
• different chlorinated species can be obtained.
• predominantly mono chlorinated species are obtained by pouring the coagulation solvent into the reaction mixture.
• the isolated chlorinated polysaccharides or oligosaccharides in particular chlorinated cellulose, may be obtained in specific shapes. If desired it can be obtained in form of fibers, films or pearls, depending on the specific conditions under which the chlorinated polysaccharides or oligosaccharides are precipitated.
• Chlorinated cellulose of low DP could be used as intermediates to produce cati- onicamphiphilic, nonionic, and anionic cellulose oligomers which also have a variety of possible technical applications.
• One embodiment of this invention is a process of modifying the chlorinated species by at least partially substituting chlorine by bisphenol A.
• the new substituent is given by the following formula:
• Di- oxan was added as a co-solvent.
• the reaction was cooled to 60°C and thionyl chloride (5eq.) was added.
• the mixture was stirred at 60°C for 2 hours after which the excess of thionyl chloride was removed in vacuo. After which, the mixture was cooled down to 5°C and NH4OH was added. Precipitation was filtered off and washed with warm water and dried in vacuum oven at 65°C.
• BMIMCI 1 -butyl-3-methyl imida
• Chlorinated cellulose oligomers suffer from the poor solubility and hence, could not be analyzed by solution state NMR. IR showed the typical CH2-CI vibration at 1428 cm- 1 and C-CI band at 751 cm- 1 . CP-MAS NMR Spectroscopy
• FIG. 1 Structure of anhydroglucose unit (AGU) of chlorocellulose showing numbering of carbon atoms.
• AGU anhydroglucose unit
• C-6 chlorination can be clearly seen in CP-MAS NMR (solid state NMR) spectrum as a shift in a chemical shift for C-6 carbon.
• C6-CI signal is observed at 40 ppm whereas unsubstituted C-6 (C6-OH) has a chemical shift at around 60 ppm.
• Dichlorination (C-6 and C-1 ) was seen as a shifted chemical signal of C-1 from 104 ppm to 97 ppm (C-1 chlorination) and C-6 chlorination at 40 ppm.
• Crystallinity of cellulose can be estimated by interpreting the C-4 signal. Two signals for C-4 are observed in the spectrum of native cellulose. This means that there are both amorphous and crystalline cellulose present in the structure. After homogeneous chemical modification in which cellulose is fully dissolved in a given solvent, the crystallinity of cellulose vanishes leaving mostly the less ordered (amorphous) cellulose de- rivative as a product.
• the signal at 81 .7 ppm has been stated to originate from less ordered carbohydrates such as cellulose oligomers. This can be seen in a case of chlorocellulose oligomer for which only a less ordered (amorphous) C-4 signal is detected.

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