Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B11/00—Preparation of cellulose ethers
  • C08B11/02—Alkyl or cycloalkyl ethers
  • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
  • C08B11/14—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups
  • C08B11/145—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups with basic nitrogen, e.g. aminoalkyl ethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B31/00—Preparation of derivatives of starch
  • C08B31/08—Ethers
  • C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
  • C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
  • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids

Definitions

• the present invention relates to a method for cationization of polysaccharides, and to new eutectic mixtures, to their manufacture, as well as to their use in the cationization of polysaccharides.
• Cationization of polysaccharides is generally carried out with a cationizing reagent.
• cationization reagents are quaternary ammonium compounds, combinations of formaldehyde and dimethylamine agents, and epoxy reagents, such as glycidyl trimethyl ammonium chloride (GTAC), typically used under basic conditions.
• GTAC glycidyl trimethyl ammonium chloride
• solubilization dissolving
• Proper solubilization is also need for achieving uniform substitution throughout the cationized material.
• polysaccharides are difficult to dissolve.
• An example of such polysaccharide is cellulose, which is used for example as starting material in the manufacture of regenerated cellulose. Particularly homogeneous processing of cellulose is challenging due to low or negligible solubility of cellulose in water or most organic solvents.
• Various methods have been developed for dissolving cellulose and the main industrial processes for the manufacture of regenerated cellulose via cellulose dissolution are the traditional derivatization viscose process based cellulose xanthate derivative, and the non-derivatization (Lyocell) process based on interaction with NMMO (N-methyl-morpholine-N-oxide). Both methods are associated with environmental, technical and/or economical disadvantages.
• Cationic starch is an example of cationic polysaccharides.
• Starch can be cationized with a cationizing reagent containing a suitable cationic, such as amino, immonium, ammonium, sulfonium or phosphonium, or alternatively cationic starches may be obtained by etherifying with compounds containing tertiary amino groups or quaternary ammonium groups.
• Modified choline chloride has also been suggested as a cationizing reagent for cationization of starch.
• the current cationization methods involve modification of choline chloride with petroleum based and/or toxic reagents, such as epichlorhydrin, for providing sufficiently high degree of substitution of the product.
• JP 2010180320 A describes a process for the cationization of polysaccharides, particularly starch, where sodium hydroxide is added to dry starch, followed by the addition of GTAC.
• ionic liquid is a salt in the liquid state.
• ionic liquids refer to salts having melting point below 100°C.
• Ordinary liquids, such as water and gasoline are predominantly composed of neutral molecules, but ionic liquids are made of ions and short lived ion-pairs.
• Eutectic mixtures are a sub-class of ionic liquids with special properties.
• a eutectic mixture forms a eutectic with a melting point much lower than any of the individual components.
• the first generation eutectic solvents were based on mixtures of quaternary ammonium salts with hydrogen donors, such as amines and carboxylic acids. The phenomenon was first described in 2003 for a mixture of choline chloride and urea in a 1 : 2 mole ratio, respectively.
• Choline chloride has a melting point of 302°C and that of urea is 133°C.
• the eutectic mixture melts at 12°C.
• a eutectic mixture formed of choline chloride and urea has been studied in cellulose modifications and dissolution, however only modest concentrations of cellulose of less than 4 wt% were dissolved in said mixture.
• An object of the invention is to provide a method for cationization of polysaccharides.
• a further object of the invention is to provide new eutectic mixtures.
• Another object of the invention is to provide a method for the manufacture of the eutectic mixtures.
• Another object of the invention is to provide uses of said new deep eutectic mixtures in the cationization of polysaccharides.
• the present invention relates to a method for cationization of polysaccharides, where a polysaccharide is mixed with a eutectic mixture formed of glycidyl trimethyl ammonium chloride and a hydrogen donor, in the presence of a base, and the mixing is continued until a product is formed. Typically the product is viscous.
• the hydrogen donor may also act as the base, whereby no additional base is needed.
• the present invention also relates to new eutectic mixtures comprising glycidyl trimethyl ammonium chloride, and a hydrogen donor.
• the present invention also relates to the method for the manufacture of eutectic mixtures.
• the present invention also relates to the use of the new eutectic mixtures in the cationization of polysaccharides.
• glycol trimethyl ammonium chloride or GTAC refers here to (2,3- epoxypropyl) trimethyl ammonium chloride having chemical formula I below.
• boric acid refers here to H3BO3, an inorganic Lewis acid having melting point of 170.9°C. It is also called as hydrogen borate, boracic acid, ortho-boric acid and acidum bo cum.
• polysaccharides can be cationized in a very efficient manner to provide cationized polysaccharides having uniform substitution throughout the cationized material and high DS (degree of substitution), by using a eutectic mixture comprising GTAC and a hydrogen donor.
• a direct method is provided for cationization of polysaccharides.
• GTAC forms a eutectic mixture with a hydrogen donor, and said eutectic mixture can be used as an inner solvent and simultaneously cationization reagent in the cationization of polysaccharides.
• the eutectic mixture comprises GTAC, and a hydrogen donor.
• Said hydrogen donor is a compound that is not capable of reacting with an epoxy ring, yet capable of activating polysaccharides via complexation and/or of disruption of hydrogen bonding.
• the hydrogen donor is selected from boric acid, metaboric acid, urea, mono-, di- and tri-alkyl ureas, oxamide, mono- and dialkyl oxamides, guanidine, mono-, di-, tri- and tetra-alkylguanidines, imides, such as phthalimide and succinimide, and hydrated borate salts, and any combinations thereof.
• GTAC typically comprises at least 70 % by weight of glycidyl trimethyl ammonium chloride, less than 5% of alcohols (ethanol) and water. If desired, the alcohol may be removed by washing with water, whereby also water soluble/miscible impurities are removed . Water may be removed for example by centrifugation or other suitable methods, and the purified GTAC may be dried for example using heat to obtain dry GTAC powder. Typically some amounts of water remain in GTAC.
• the eutectic mixture comprises a ratio from 5 : 1 to 1 : 1, preferably from 3 : 1 to 1 : 1 by mol of glycidyl trimethyl ammonium chloride and a hydrogen donor, respectively.
• the eutectic mixture may comprise 0-50 wt%, preferably 0.01-50 wt%, particularly preferably 0.01- 30 wt%, even more preferably 2-15 wt% of water, calculated from the total weight of the mixture.
• the amount of water may be decreased for example by distillation, evaporation etc., or it may be increased during the manufacture of the mixture.
• the eutectic mixture may comprise a base.
• the base is selected from organic and inorganic bases, preferably as such as 1,8-diazabicyclo undec-7-ene, potassium t-butoxide, pyridine, triethyl amine, alkali metal hydroxides and borates and earth alkaline metal hydroxides and borates, ammonium hydroxide, ammonium borate and ammonia gas.
• NaOH is used.
• the hydrogen donor is a basic compound, such as guanidine or alkyl guanidine, no additional base is necessary.
• the pH of the eutectic mixture is suitably at least 7.
• the base is used for the pH adjustment.
• the method for the manufacture of the eutectic mixture comprises the steps, where glycidyl trimethyl ammonium chloride is mixed with a hydrogen donor.
• the hydrogen donor is preferably selected from boric acid, metaboric acid, urea, mono-, di- and tri- alkyl ureas, oxamide, mono- and dialkyl oxamides, guanidine, mono-, di-, tri- and tetra-alkylguanidines, imides, such as phthalimide and succinimide, and hydrated borate salts, and any combinations thereof.
• the amounts of the components are selected to provide ratio from 5 : 1 to 1 : 1, preferably from 3 : 1 to 1 : 1 of glycidyl trimethyl ammonium chloride and the hydrogen donor, respectively.
• water may be added at any stage of the method, before or after mixing the glycidyl trimethyl ammonium chloride with the hydrogen donor.
• 0-50 wt% preferably 0.01-50 wt%, particularly preferably 0.01- 30 wt%, more preferably 2-15 wt% of water, calculated from the total weight of the mixture is added.
• the water may be tap water, ion exchanged water or purified water.
• Water may optionally be added in stepwise manner, preferably 50 wt% of water is added in the first step followed by mixing and adding the remaining 50 wt% in at least one step followed by mixing. The last added amount of water may be 2 wt%.
• a base is added to the mixture to adjust the pH of the mixture to at least 7 or more.
• the base is selected from inorganic and organic bases, preferably such as 1,8- diazabicyclo undec-7-ene, potassium t-butoxide, pyridine, triethyl amine, alkali metal hydroxides and borates and earth alkaline metal hydroxides and borates, ammonium hydroxide, ammonium borate and ammonia gas.
• bases preferably such as 1,8- diazabicyclo undec-7-ene, potassium t-butoxide, pyridine, triethyl amine, alkali metal hydroxides and borates and earth alkaline metal hydroxides and borates, ammonium hydroxide, ammonium borate and ammonia gas.
• NaOH is used.
• the hydrogen donor is a basic compound, such as guanidine or alkyl guanidine, no additional base is necessary.
• the mixing may be carried out at a temperature of 20-60°C, preferably 30-55°C, particularly preferably 35-45°C.
• the mixing may be carried out under a pressure from 100 mbar to 10 bar, suitably normal atmospheric pressure is used.
• the mixing is carried out until an essentially clear mixture is formed.
• the method for the cationization of polysaccharides comprises the steps where a polysaccharide is mixed with a eutectic mixture formed of glycidyl trimethyl ammonium chloride and a hydrogen donor, in the presence of a base, and the mixing is continued until a cationized product is formed.
• the product is typically viscous.
• a eutectic mixture formed of GTAC with a hydrogen donor is used as an inner solvent and simultaneously as a cationization reagent in the cationization of polysaccharides.
• the method comprises the steps, where 10-55 wt%, preferably 15-50wt% of a polysaccharide is mixed with 90-45, preferably 85-50 wt% of a eutectic mixture formed of glycidyl trimethyl ammonium chloride and a hydrogen donor.
• the mixing is carried out at a temperature of 10-150°C, suitably at constant temperature.
• a base is added to the mixture to adjust the pH of the mixture to at least 7.
• the mixing is continued until a product is formed, suitably from 1 to 50 hours.
• the cationized product is typically viscous.
• the product may be precipitated, suitably from a lower alcohol (C1-C5), such as ethanol, filtered, washed with alcohol (ethanol) and dialyzed against water using a membrane whereby a final product is obtained.
• a lower alcohol C1-C5
• alcohol ethanol
• the base is selected from organic and inorganic bases, such as 1,8-diazabicyclo undec-7-ene, potassium t-butoxide, pyridine, triethyl amine, alkali metal hydroxides and borates and earth alkaline metal hydroxides and borates, ammonium hydroxide, ammonium borate and ammonia gas.
• organic and inorganic bases such as 1,8-diazabicyclo undec-7-ene, potassium t-butoxide, pyridine, triethyl amine, alkali metal hydroxides and borates and earth alkaline metal hydroxides and borates, ammonium hydroxide, ammonium borate and ammonia gas.
• NaOH is used.
• the base acts as a catalyst in the reaction.
• the hydrogen donor is a basic compound, such as guanidine or alkyl guanidine, no additional base is necessary.
• the method is a non-aqueous "dry" cationization method, where no additional water is used.
• the eutectic mixture may comprise 0.01-30 wt%, preferably 2-15 wt% of water.
• the mixing temperature is 30-90°C.
• the mixing is carried out for 15 min - 24 hours, as total mixing time.
• the polysaccharide is suitably ground or milled prior to the cationization step to obtain smaller particles, whereby the solubilization time is shorter.
• the polysaccharide is suitably selected from cellulose, cellulose derivatives, starch, starch derivatives, xylanes, hemicelluloses, lignins, pectins, tannines, maltodextrines, dextranes alginates, chitosans, algal polysaccharides, microbial polysaccharides, bacterial polysaccharides and lignocellulosic materials and combinations thereof.
• the polysaccharide swells vigorously.
• the obtained cationized polysaccharides are homogenous products having high DS.
• OH groups are directed to desired 1-, 2-, and 3-positions.
• the eutectic mixture of the invention cationizes polysaccharides by incorporating nitrogen in the polysaccharide, whereby the nitrogen content in the cationized polysaccharide may be even 5.6 wt%. Accordingly quaternization of polysaccharides is achieved with the method.
• the final product contains not more than 10 wt% of water.
• the DS (degree of substitution) of the final product is not more than 3, preferably in the range of 1.4 - 2.
• the cationized polysaccharides may be used for the manufacture of films, flocculants, particularly for water purification, retention aids in paper manufacture, cosmetics, sizing compounds, fixatives, cleaning aids, detergents etc.
• the present invention provides several advantages.
• the method for the cationization of polysaccharides is very simple, rapid and products with surprisingly high DS values are obtained.
• the components are recyclable, no harmful emissions are released.
• the method provides a new concept for providing cationized polysaccharides. Proper solubilization assures uniform substitution throughout the cationized material.
• the new eutectic mixture is an effective, low cost and environmentally acceptable solvent and cationization agent.
• the cationized polysaccharides may also be obtained as highly viscous materials, which are particularly suitable for extrusion processes and the like where highly viscous materials are processed.

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• Polysaccharides And Polysaccharide Derivatives (AREA)

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Citations (4)

• 2014
  • 2014-03-28 FI FI20145289A patent/FI20145289A/fi not_active Application Discontinuation
• 2015
  • 2015-03-26 WO PCT/FI2015/050206 patent/WO2015144991A1/en active Application Filing

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