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WO2013085053A1 - Procédé pour la production de solution aqueuse de cellulose et procédé pour la production de dérivé de cellulose - Google Patents

Procédé pour la production de solution aqueuse de cellulose et procédé pour la production de dérivé de cellulose Download PDF

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Publication number
WO2013085053A1
WO2013085053A1 PCT/JP2012/081857 JP2012081857W WO2013085053A1 WO 2013085053 A1 WO2013085053 A1 WO 2013085053A1 JP 2012081857 W JP2012081857 W JP 2012081857W WO 2013085053 A1 WO2013085053 A1 WO 2013085053A1
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Prior art keywords
cellulose
aqueous
quaternary ammonium
solution
producing
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English (en)
Japanese (ja)
Inventor
貴志 酒井
正 依馬
小原　則行
拓三 小見山
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Daicel Corp
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Daicel Corp
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Priority to CN201280049066.9A priority Critical patent/CN103842384B/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/08—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with hydroxylated hydrocarbon radicals; Esters, ethers, or acetals thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • 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
    • C08B11/155—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups with cyano groups, e.g. cyanoalkyl ethers
    • 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
    • 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
    • C08B3/22—Post-esterification treatments, including purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/02—Cellulose; Modified cellulose
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/14—Secondary fibres

Definitions

  • the present invention relates to a method for producing a cellulose aqueous solution and a method for producing a cellulose derivative using the cellulose aqueous solution obtained by the production method.
  • Cellulose derivatives represented by acetylcellulose, nitrocellulose, cyanoethylcellulose, etc. are widely used in a wide range of industrial sectors such as packaging, textiles, plastics, photography, surface coating, military demand, airplanes, recording, chemicals, pharmaceuticals, tobacco, and electricity. It is an extremely important material for industrial use.
  • Cellulose derivatives are generally produced by introducing (derivatizing) various functional groups into hydroxy groups of cellulose.
  • cellulose has three hydroxy groups per unit of glucopyranose, and since these hydrogen groups have extremely strong hydrogen bonding forces between molecules or between molecules, cellulose is insoluble in water and most organic solvents. It is hardly soluble. Therefore, prior to the production of the cellulose derivative, in order to enable cellulose to be dissolved in various solvents, treatments for hydrogen bond cleavage and prevention of re-formation are performed by the following dissolution methods.
  • a method of forming a cellulose complex is commonly used.
  • copper is ⁇ coordinated to the hydroxyl groups at the C (2) and C (3) positions of cellulose (see (a) below).
  • Ca (SCN) 2 it is considered that the calcium ion is coordinated to the C (5) position and the C (6) position to form a five-membered ring structure (see (b) below).
  • SO 2 / diethylamine method a SO 2 -amine complex is formed at a ratio of 1: 1 to all the hydroxy groups of cellulose (see (c) below).
  • a cellulose derivative having a substitution degree of 0.1 to 0.5 is soluble in an alkaline aqueous solution, and a cellulose derivative having a substitution degree of around 1 is soluble in water.
  • a method of solvating cellulose is known.
  • a concentrated inorganic acid / water system sulfuric acid, phosphoric acid, polyphosphoric acid aqueous solution, etc.
  • a concentrated inorganic salt / water system such as ZnCl 2 aqueous solution
  • a sodium hydroxide aqueous solution system etc.
  • water is first hydrated to the solvent component to form a hydrated structure.
  • the hydrated structure interacts (solvates) with the cellulose to dissolve the cellulose. Therefore, in order to maintain the hydration structure or promote solvation, there are many low temperature dissolution type dissolution systems in which dissolution proceeds at lower temperatures.
  • DMAC N, N-dimethylacetamide
  • LiCl LiCl
  • DMSO dimethylsulfoside DMSO dimethylsulfoside
  • TBAF tetrabutylammonium fluoride Trihydrate
  • a method using an ionic liquid is not suitable for industrial use because the ionic liquid is expensive and it is difficult to separate products.
  • Non-Patent Document 1 Non-Patent Document 2 and Non-Patent Document 3
  • cellulose forms an addition compound (amine cellulose) with various amines, thereby swelling or dissolving cellulose, and tetramethyl as the amine.
  • Ammonium hydroxide, tetraethylammonium hydroxide, and the like are mentioned, and the larger the alkyl group of the amine, the lower the minimum concentration at which cellulose is dispersed and dissolved.
  • Non-Patent Document 4 includes tetrabutylphosphonium. It describes that cellulose is made into a solution using hydroxide (TBPH) or tetrabutylammoniumhydroxide (TBAH). However, it can be said that TBPH has major problems with respect to problems such as raw material costs and wastewater treatment. Also, the table in this document 2 shows an experiment in which the concentration of water in TBAH and the amount of cellulose were changed. Looking at the result of 60% (equivalent to 40% TBAH), it can be seen that cellulose does not dissolve even at 0.5 wt%.
  • TBPH hydroxide
  • TBAH tetrabutylammoniumhydroxide
  • Non-Patent Document 5 describes a method of reacting cellulose with sodium hydroxide and an unsaturated nitrile.
  • sodium hydroxide is used in this method, there is a problem that hydrolysis of cyano groups introduced into cellulose occurs as a side reaction.
  • the present invention provides a means capable of dissolving cellulose under a mild condition using a relatively safe substance (in other words, producing a cellulose solution). Objective.
  • cellulose can be easily dissolved by bringing cellulose into contact with an aqueous quaternary ammonium hydroxide solution such as tetrabutylammonium hydroxide (TBAH).
  • TBAH tetrabutylammonium hydroxide
  • the present inventors have investigated the cause, and by selecting a product in which the concentration of metal ions (for example, alkali metal inorganic salt such as KBr) mixed in the aqueous quaternary ammonium hydroxide solution is a predetermined value or less, It has been found that a practical dissolution system capable of reliably dissolving cellulose can be used.
  • metal ions for example, alkali metal inorganic salt such as KBr
  • cellulose was dissolved when a cyclic polyether (sometimes called “crown ether”) was added to an aqueous quaternary ammonium hydroxide solution even in the presence of the metal ions.
  • the cyclic polyether functions not only as a metal ion scavenger but also as an accelerator for improving the water solubility of cellulose in cooperation with quaternary ammonium hydroxide, and remarkably accelerates the dissolution rate. Increase the transparency of the resulting solution.
  • DMSO or PEG which is a chain polyether, and is unique to cyclic polyethers.
  • the cellulose aqueous solution (dissolving system) obtained as described above is extremely useful for the production of cellulose derivatives, the recovery of cellulose, and the like. That is, acrylonitrile, epoxide, acetic anhydride, acrylic acid ester is added to the cellulose aqueous solution. , By adding alkyl halides and mixing at room temperature, the corresponding derivatives of cyanoethyl cellulose, hydroxyalkyl cellulose, acetyl cellulose, etc. can be produced quantitatively, or cellulose such as methanol can be added to the cellulose aqueous solution. The inventors have found that cellulose can be easily precipitated and collected by adding a poor solvent, and the present invention has been completed.
  • a method for producing an aqueous cellulose solution comprising a step of contacting a purified cellulose or a substance containing cellulose (hereinafter collectively referred to as “cellulose raw material”) with an aqueous quaternary ammonium hydroxide solution.
  • a method for producing an aqueous cellulose solution comprising a step of contacting a purified cellulose or a substance containing cellulose (hereinafter collectively referred to as “cellulose raw material”) with an aqueous quaternary ammonium hydroxide solution,
  • cellulose raw material a purified cellulose or a substance containing cellulose
  • the total concentration of the alkali metal halide and / or alkaline earth metal halide dissolved in the aqueous quaternary ammonium hydroxide solution in the state of contact with the cellulose raw material is 1% by weight or less.
  • a method for producing an aqueous cellulose solution comprising a step of contacting a cellulose raw material with an aqueous quaternary ammonium hydroxide solution, wherein the contact between the cellulose raw material and the aqueous quaternary ammonium hydroxide solution is carried out in the presence of a cyclic polyether.
  • the manufacturing method of the cellulose aqueous solution characterized by performing. *
  • the cyclic polyether is at least selected from the group consisting of 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6 and diaza-18-crown-6
  • a cellulose comprising a step of mixing an aqueous cellulose solution obtained by the production method according to any one of [1] to [7] and a hydroxy group-reactive compound used as a raw material for a cellulose derivative.
  • a method for producing a derivative is
  • the hydroxy group-reactive compound is selected from the group consisting of ⁇ , ⁇ -unsaturated nitriles, epoxides, organic carboxylic acid anhydrides, ⁇ , ⁇ -unsaturated carboxylic acid esters, and alkyl halides.
  • a method for producing a cellulose film comprising a step of removing a solvent by drying from an aqueous cellulose solution obtained by the production method according to any one of [1] to [7].
  • [14] A cellulose film obtained by the production method according to [13].
  • [15] A method for producing a cellulose fiber, comprising spinning an aqueous cellulose solution obtained by the production method according to any one of [1] to [7].
  • a pretreatment for dissolving cellulose is unnecessary, and an aqueous cellulose solution can be easily produced simply by bringing a cellulose raw material and an aqueous quaternary ammonium hydroxide solution into contact with each other at room temperature.
  • a cellulose raw material not only a purified product of cellulose, but also a cellulose product such as filter paper and a plant waste material such as sawdust can be used.
  • the cellulose aqueous solution obtained by the present invention is a versatile raw material that can be used for producing various derivatives and recovering cellulose. That is, if various compounds for derivatization are added to this aqueous cellulose solution, each derivative can be quantitatively produced simply by mixing under mild conditions, and a poor solvent such as methanol is added to the aqueous cellulose solution. If added, the cellulose derivative can be isolated by reprecipitation.
  • the present invention can be carried out under mild conditions without requiring special equipment or technology, it is possible to safely produce purified cellulose, cellulose derivatives, processed products thereof, etc. on an industrial large scale, safely. It is expected that it will be possible to manufacture at a cost.
  • Example 8 Visually and optically observed images of the coating liquid prepared from cellulose and 40 wt% TBAH aqueous solution in (2).
  • Example 8 Visually and optically observed images of the coating liquid prepared from cellulose and a 55 wt% TBAH aqueous solution in (3). The photograph which shows precipitation of the quaternary ammonium salt of the cellulose from a supernatant liquid and a residue in [Example 9].
  • Comparative Example of Mixed Solution in [Example 11-1] (KBr addition effect). Comparative photograph of the mixed solution in [Example 11-2] (addition effect of 18C6). Comparative photograph of the mixed solution in [Example 11-3] (difference in dissolution with and without metal ions and crown ether). Comparative photograph of the mixed solution in (1) of [Example 11-4] (when 40% TBAH aqueous solution or ion-exchanged water is used instead). Comparative photograph of the mixed solution in (2) of [Example 11-4] (when KOH or NaOH is used instead of 40% TBAH aqueous solution). The comparative photograph of the mixed solution in (3a) of [Example 11-4] (when DMSO is mixed instead of 18C6). The comparative photograph of the mixed solution in (3b) of [Example 11-4] (when PEG is mixed instead of 18C6).
  • the method for producing an aqueous cellulose solution according to the present invention includes a step of contacting a cellulose raw material (purified cellulose or a substance containing cellulose) with an aqueous quaternary ammonium hydroxide solution.
  • the substance dissolved in the aqueous solution obtained by the above process is presumed to be a cellulose / quaternary ammonium complex produced by the reaction of quaternary ammonium hydroxide with any hydroxy group of cellulose.
  • an aqueous solution in which such a complex is estimated to be dissolved will be referred to as a “cellulose aqueous solution”.
  • the “cellulose raw material” in the present invention may be a purified cellulose, that is, a general product such as cellulose powder or cellulose having the same degree of purity, or other substances containing cellulose, It may be a processed product such as a paper product obtained from a plant raw material (pulp), or may be a crop, plant waste, or other plant substance.
  • the wood usually contains a relatively large amount of hemicellulose, lignin and the like in addition to cellulose, but the present invention can be applied.
  • the cellulose raw material may be refined and pulverized to an appropriate size as necessary. For example, it can be used in the form of sawdust, wood chips or the like produced as a by-product during lumbering.
  • the concentration of the aqueous quaternary ammonium hydroxide used in the method for producing an aqueous cellulose solution of the present invention must be not less than a predetermined value at which the cellulose dissolution reaction proceeds, preferably not less than 35% by weight. It is desirable to do.
  • the “predetermined value” relating to the concentration of the quaternary ammonium hydroxide aqueous solution is estimated to be between 32 and 35% by weight under the conditions of Examples described later. If the concentration in the aqueous quaternary ammonium hydroxide solution is lower than a predetermined value, the cellulose does not dissolve and the aqueous cellulose solution may not be obtained.
  • the upper limit of the concentration of the aqueous quaternary ammonium hydroxide solution can be set while taking other conditions into consideration, if necessary. If the concentration of the aqueous quaternary ammonium solution satisfies the above-mentioned concentration conditions (for example, a product having a concentration of 40% by weight is readily available), there is no need to increase it.
  • the amount of quaternary ammonium hydroxide in the aqueous quaternary ammonium hydroxide solution relative to the amount of glucopyranose units constituting the cellulose in the cellulose raw material when the cellulose raw material is brought into contact with the aqueous quaternary ammonium hydroxide solution
  • the ratio needs to be a predetermined value or more so that the cellulose is sufficiently dissolved in water. If the amount of quaternary ammonium hydroxide is insufficient, the cellulose may not be sufficiently dissolved.
  • the lower limit of the above ratio may vary depending on the concentration of the aqueous quaternary ammonium hydroxide used. For example, when the concentration of the quaternary ammonium hydroxide aqueous solution is 55% by weight, the lower limit value can be 1.5 as described above. However, when the concentration of the quaternary ammonium hydroxide aqueous solution is 40% by weight, when the ratio is 1.5, the solubility of cellulose is poor, and it is appropriate to raise the lower limit to about 2.
  • the quaternary ammonium hydroxide used in the present invention preferably has a substituted or unsubstituted alkyl group and / or a substituted or unsubstituted aryl group as four substituents. That is, the four substituents of the quaternary ammonium hydroxide can be each independently a substituted alkyl group, an unsubstituted alkyl group, a substituted aryl group, or an unsubstituted aryl group.
  • the four substituents of the quaternary ammonium hydroxide can be selected from the substituents of known quaternary ammonium hydroxides.
  • the total number of carbon atoms is 4 to 60, preferably Is preferably a combination of substituents such as 4-24.
  • TBAH tetrabutylammonium hydroxide
  • TMAH tetramethylammonium hydroxide
  • BTMAH benzyltrimethylammonium
  • the method for producing an aqueous cellulose solution of the present invention comprises an alkali metal halide and / or an alkaline earth metal halide dissolved in an aqueous quaternary ammonium hydroxide solution in contact with a cellulose raw material (
  • the total concentration of “may be referred to as“ inorganic salt impurities. ”) Must be a predetermined value or less that does not inhibit the dissolution reaction of cellulose, and the concentration is preferably 1% by weight or less. .
  • the “predetermined value” is estimated to exist between 1 and 2% by weight under the conditions of the examples described later.
  • the concentration of the inorganic salt impurities dissolved in the quaternary ammonium hydroxide aqueous solution is higher than a predetermined value, the cellulose dissolution reaction may be inhibited, and the cellulose aqueous solution may not be obtained. It is ideal that the inorganic salt impurity is not substantially contained at all, that is, it is considered that the concentration should be as low as possible. Therefore, the lower limit value of the concentration of the inorganic salt impurity may not be provided (may be 0). However, if necessary, it may be set in consideration of other conditions.
  • the concentration of the inorganic salt impurity dissolved in the aqueous quaternary ammonium hydroxide solution is not limited to the above range, and may exceed the above range. It is possible to dissolve cellulose.
  • the concentration may be adjusted according to the change.
  • inorganic salt impurities include, but are not limited to, KBr, LiBr, and NaBr. When a plurality of types of inorganic salt impurities coexist, the above concentration conditions are considered based on the total concentration of each inorganic salt impurity.
  • Quaternary ammonium hydroxide that satisfies the above conditions for inorganic salt impurities can be obtained as a specific product.
  • an inorganic salt impurity (KBr, etc.) is not substantially mixed in an aqueous solution of quaternary ammonium hydroxide (TBAH, etc.) manufactured by Aldrich, and is suitable as a product that satisfies the above requirements.
  • TBAH quaternary ammonium hydroxide
  • a predetermined purification step membrane purification, recrystallization, extraction, etc.
  • the inorganic salt impurities dissolved in the aqueous quaternary ammonium hydroxide solution are assumed to be mainly contained in the aqueous quaternary ammonium hydroxide solution (for example, those mixed in the manufacturing process of the product). It can also be assumed that it is contained (for example, what was originally contained in the cellulose raw material, or that was mixed in the pretreatment performed if necessary).
  • the manufacturing method of the cellulose aqueous solution by this invention is obtained while improving the dissolution rate of a cellulose, when a cellulose raw material and quaternary ammonium hydroxide are made to contact in presence of cyclic polyether (crown ether). Since transparency of a solution can be improved, it is more preferable. Even if the cyclic polyether is brought into contact with the cellulose raw material alone without using quaternary ammonium hydroxide, the cellulose can hardly be dissolved.
  • the cyclic polyether examples include 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, and diaza-18-crown-6.
  • the cyclic polyether is considered to function not only as a metal ion scavenger but also as an accelerator for improving water solubility (dissolution rate and transparency) of cellulose in cooperation with quaternary ammonium hydroxide. ing. While considering the effect, an appropriate cyclic polyether may be used according to conditions such as the kind of alkali metal ions and / or alkaline earth metal ions present in the aqueous quaternary ammonium hydroxide solution. When potassium ions are present in the aqueous quaternary ammonium hydroxide, 15-crown-5 and 18-crown-6 are preferred.
  • the use of the cyclic polyether in the present invention is not limited to the case where the total concentration of the inorganic salt impurities is 1% by weight or less, but rather the total concentration of the inorganic salt impurities is more than 1% by weight. In some cases, it is suitable as a means for enabling dissolution of cellulose.
  • the amount of the cyclic polyether used is not particularly limited.
  • the concentration of quaternary ammonium hydroxide, the amount of cellulose, the total concentration of alkali metal halide and / or alkaline earth metal halide, cyclic polyether is usually 0.01 to 5M, although it can be adjusted as appropriate in consideration of the type of compound and the degree of desired effect (dissolution rate, transparency). Preferably it is 0.5-2M.
  • the step of bringing the cellulose raw material into contact with the aqueous quaternary ammonium hydroxide can be performed by mixing them in a reaction vessel while stirring.
  • a quaternary ammonium hydroxide for example, a quaternary ammonium hydroxide aqueous solution and a cyclic polyether may be mixed in advance, and this solution and cellulose may be mixed.
  • the reaction time may be sufficient for cellulose to dissolve depending on the cellulose raw material to be used and the form of the aqueous quaternary ammonium hydroxide, but it is generally about 1 to 6 hours. If a cyclic polyether is used, this time can be reduced to 10 minutes.
  • the reaction temperature can usually be room temperature, but if necessary, it may be heated or cooled so that the reaction proceeds at an appropriate rate.
  • a method for producing a cellulose / quaternary ammonium complex according to the present invention comprises mixing a cellulose aqueous solution obtained by the production method as described above and a poor solvent for cellulose. Including a step of precipitating a quaternary ammonium complex.
  • the quaternary ammonium hydroxide used for dissolving cellulose can be reused after removing a poor solvent such as methanol from which cellulose has been reprecipitated.
  • the method for producing a cellulose / quaternary ammonium complex of the present invention can be used as a method for obtaining a cellulose / quaternary ammonium complex as an intermediate product in the course of the production method for obtaining a desired final product. it can.
  • the use of the cellulose / quaternary ammonium complex recovered by the method of the present invention is not particularly limited.
  • the efficiency of enzymatic saccharification of cellulosic biomass used for bioethanol production can be improved.
  • cellulose has a crystal structure
  • crystalline cellulose has a complex structure surrounded by hemicellulose and lignin, and solid-liquid reaction is used until the final stage of saccharification.
  • the manufacturing method of the cellulose film by this invention includes the process of removing a solvent by drying from the cellulose aqueous solution obtained by the above manufacturing methods.
  • the solvent used in the cellulose aqueous solution of the present invention is water, it can be easily removed by natural drying or general drying means. Therefore, for example, by removing the solvent after spreading the aqueous cellulose solution on a flat surface, a film that is dissolved in the aqueous cellulose solution, that is, formed from a cellulose / quaternary ammonium complex, is re-dissolvable in water ( In the present invention, this is referred to as “cellulose film”).
  • cellulose aqueous solution various cellulose products can be manufactured, such as manufacturing a cellulose fiber using a solution (wet) spinning method, for example.
  • the cellulose fiber production method using the cellulose aqueous solution of the present invention can be applied to a conventional cellulose fiber production method.
  • the cellulose aqueous solution can be applied from a spinning nozzle to an appropriate coagulating liquid (for example, methanol or the like).
  • Cellulose fibers composed of a cellulose / quaternary ammonium complex can be produced by extrusion into a solvent), recovery, washing and the like.
  • the manufacturing method of the cellulose derivative by this invention includes the process of mixing the cellulose aqueous solution obtained by the above manufacturing methods, and the hydroxy group reactive compound used as the raw material of a cellulose derivative.
  • hydroxy group-reactive compound a compound having a functional group capable of reacting with the hydroxy group of the cellulose in a cellulose solution, desirably under mild conditions (for example, only by stirring at room temperature) is used. be able to.
  • a compound is selected according to the target cellulose derivative, and a compound used in a conventional method for producing a cellulose derivative can also be used in the present invention.
  • hydroxyl group-reactive compound examples include ⁇ , ⁇ -unsaturated nitriles, epoxides, organic carboxylic acid anhydrides such as acetic anhydride, ⁇ , ⁇ -unsaturated carboxylic acid esters, and alkyl halides. Any compound can be added to an aqueous cellulose solution and stirred at room temperature for a sufficient time to react with the cellulose / quaternary ammonium complex to produce a predetermined derivative.
  • ⁇ , ⁇ -unsaturated nitrile, epoxide, and organic carboxylic acid anhydride are, in order, cyanoethyl cellulose, hydroxyalkyl (ethyl, propyl, hexyl, etc.) cellulose, acyl (acetyl, etc.), respectively. ) It can be used as a raw material for producing cellulose.
  • alkyl cellulose ester compounds such as methyl cellulose
  • alkyl halide such as methyl chloride
  • the mode of the reaction between the cellulose / quaternary ammonium complex and the hydroxy group-reactive compound in the cellulose aqueous solution is not particularly limited.
  • epoxy hexane see [Example 6] described later
  • quaternary ammonium hydroxide is added to some hydroxy groups in the cellulose.
  • cyanoethyl cellulose is recovered after a treatment in which the quaternary ammonium hydroxide is further removed by addition of an acid to return it to a hydroxy group.
  • the step of mixing the aqueous cellulose solution and the hydroxy group-reactive compound in this method for producing a cellulose derivative can be performed as a continuous step from the aforementioned method for producing an aqueous cellulose solution. That is, when a cellulose aqueous solution in which a cellulose / quaternary ammonium complex is produced according to the present invention is produced, a hydroxy group-reactive compound can be added to the cellulose aqueous solution to perform the step.
  • the process of the method for producing a cellulose derivative may be performed again.
  • the cellulose derivatization reaction is preferably allowed to proceed under mild conditions as described above (for example, only by stirring at room temperature). However, if necessary, heating, cooling, and other purposes of the present invention are lost. You may make it advance by adding operation of the grade which is not made to reject.
  • the produced cellulose derivative can be recovered by using a known method, for example, filtering after adding a poor solvent and precipitating.
  • the cellulose derivative obtained by the production method of the present invention can be used in the same application as the cellulose derivative obtained by a conventional method.
  • packaging eg packaging film: acetylcellulose
  • woven fabric eg fiber: acetylcellulose
  • plastic eg molded product: acetylcellulose, ethylcellulose
  • photograph eg film: acetylcellulose
  • surface coat eg lacquer: nitro
  • a processed product formed from the cellulose derivative using an aqueous solution of the cellulose derivative obtained by the production method as described above.
  • the solvent of the cellulose derivative aqueous solution can be easily removed by natural drying or general drying means, a film made of the cellulose derivative is produced by removing the solvent after the cellulose derivative aqueous solution is developed. can do.
  • carboxyethyl cellulose can be produced by reacting cyanoethyl cellulose with sodium hydroxide.
  • Example 1-2 The cellulose-ammonium complex was isolated according to the procedure shown in FIG. Although cellulose itself is insoluble in DMSO, the solid after the reaction of cellulose and TBAH was dissolved in DMSO after washing with ethyl acetate, ethanol and acetone. It was presumed to be an ammonium salt of cellulose (not an attached substance).
  • the IR spectrum of the collected solid is shown in FIG. It shows that the collected solid is a substance different from cellulose.
  • the 1 H-NMR spectrum is shown in FIG. 3 (bottom). This indicates that the recovered solid has a tetrabutylammonium moiety, and it is considered that any hydroxy group of cellulose is ammoniumated.
  • Example 2 Cellulose and filter paper were each dissolved in tetrabutylammonium hydroxide (Aldrich, 40% in water), and the resulting solution was transferred to a petri dish and allowed to dry naturally. A film was formed from each.
  • tetrabutylammonium hydroxide Aldrich, 40% in water
  • the TBAH product 2 contains about 2.1% by weight of K + and about 2.4% by weight of Br ⁇
  • the TBAH product 3 contains about 2.0% by weight of K + and about 1% of Br ⁇ . 9% by weight (refer to columns K-KA and BR-KA, respectively), but TBAH product 1 (Aldrich) contains virtually no K + and Br ⁇ it is conceivable that. It has been confirmed that cellulose can always be dissolved when TBAH product 1 is used, whereas cellulose cannot be dissolved when TBAH products 2 and 3 are used (depending on the lot).
  • Example 3-2 The TBAH product 1 (manufactured by Aldrich) with KBr added at the following levels was added to a 20 ml test tube containing 500 mg of a small cut filter paper (qualitative filter paper No. 2). The solubility of cellulose after standing at 10 ° C. for 12 hours was visually confirmed, and the state where the filter paper was dissolved was evaluated as “ ⁇ ”, and the state where the filter paper was not dissolved was evaluated as “X” (see FIG. 5). The results are shown in the table below. Entry where KBr concentration in TBAH exceeds 5% by weight In No. 4, cellulose could not be dissolved.
  • Example 3-3 Salt was added to 10 ml of an aqueous quaternary ammonium hydroxide solution at each level, and 500 mg of small cut filter paper (qualitative filter paper No. 2) was added to a 20 ml test tube and allowed to stand at 10 ° C. for 12 hours. The results are shown in the table below. The evaluation criteria for solubility are the same as in Example 3-2. Tetrabutylammonium hydroxide (TBAH), tetramethylammonium hydroxide (TMAH), and benzyltrimethylammonium hydroxide (BTMAH) are all manufactured by Aldrich, and all of the products are initial (when no KBr is added). The KBr concentration is approximately 0% by weight.
  • TBAH Tetrabutylammonium hydroxide
  • TMAH tetramethylammonium hydroxide
  • BTMAH benzyltrimethylammonium hydroxide
  • the inorganic salt When the inorganic salt was 1% by weight or less, cellulose was dissolved in any aqueous solution of quaternary ammonium salt (concentration 40% by weight). On the other hand, when the inorganic salt was 2% by weight or more, it did not dissolve in any aqueous solution of quaternary ammonium salt, and did not dissolve even when the concentration of quaternary ammonium salt was increased.
  • Example 4 A small cut filter paper (qualitative filter paper No. 2) was placed in a 20 ml test tube, 10 ml of each of the following levels of diluted tetrabutylammonium hydroxide (TBAH) was added, and the mixture was allowed to stand at 10 ° C. for 24 hours. The results are shown in the table below. The evaluation criteria for solubility are the same as in Example 3-2. In the case of TBAH, it was confirmed that cellulose was dissolved at a concentration of 35% by weight or more. However, at 32% by weight, cellulose could not be dissolved regardless of the amount of cellulose.
  • TBAH diluted tetrabutylammonium hydroxide
  • the manufacturing method of the conventional cyanoethyl cellulose uses NaOH, and as a side reaction, there is a problem that hydrolysis occurs in the cyano group introduced into cellulose.
  • the above-described method according to the present invention is advantageous in that hydrolysis is unlikely to occur because an aqueous solution of a quaternary ammonium hydroxide (TBAH or the like) that is a weak base is used.
  • TBAH quaternary ammonium hydroxide
  • FIG. 7 shows the 1 H-NMR spectrum of the collected solid. Proton peaks of CH 2 CN, glucopyranose, and tetrabutylammonium were confirmed. From these results, it was estimated that the recovered solid was an ammonium salt of cyanoethyl cellulose.
  • Example 5-1 A stirring bar and the solid recovered in Example 5-1 were placed in a 10 ml two-necked reactor, and N 2 was substituted. Water was added and stirring was started to completely dissolve the cellulose. 10% hydrochloric acid was added and stirred at room temperature for 1 hour. Reprecipitation was performed with methanol, and suction filtration was performed to collect a solid. The recovered amount was 2.32 g. The recovered solid was soluble in both DMSO and water.
  • Example 5-3 160 mg of the solid (cyanoethyl cellulose) recovered in Example 5-1 was dissolved in 3 ml of water, transferred to a petri dish and naturally dried for 36 hours to form a film. This film was translucent.
  • the IR spectrum of the collected solid is shown in FIG. Absorption of a cyano group was confirmed at 2252.7 cm ⁇ 1 .
  • the 1 HNMR spectrum is shown in FIG. Although the protons of CH 2 CN and glucopyranose were confirmed, the proton peak of the tetrabutylammonium moiety disappeared. From these results, it was estimated that the recovered solid was cyanoethyl cellulose.
  • FIG. 11 shows the IR spectrum of the obtained white solid.
  • the NMR spectrum is shown in FIG. 1 H-NMR (300 MHz, DMSO) ⁇ 0.80-1.00 (m), 1.20-1.48 (m) 3.00-5.80 (m); IR (KBr) 3174, 2869, 2364, 2129, 2044, 1643, 1431, 1049, 675cm -1 ; From these spectral data, it was judged that cellulose was modified.
  • the appearance and IR spectrum of the obtained white solid are shown in FIG. 1735.8 Absorption of a carbonyl group was confirmed at cm- 1 .
  • the 1 H-NMR spectrum is shown in FIG. 1 H-NMR (300 MHz, DMSO) ⁇ 1.80-2.10 (m), 4.10 (q) 3.00-5.80 (m); IR (KBr) 3228,2896,1735,1654, 1375, 1244, 1033, 896, 613cm -1 ; Signals of glucopyranose and acetyl group were confirmed. From these results, it was judged that acetylcellulose was produced.
  • the said IR spectrum corresponded with the IR spectrum with a commercial item (Kishida Chemical Co., Ltd. acetylcellulose, acetic acid degree 55%).
  • Acetylcellulose (299 mg), N, N-dimethylaminopyridine (DMAP) (150 mg, mmol), propionic anhydride (4.5 ml, mmol) were added to replace N 2 , DMSO (4 ml), pyridine (4.5 ml) ) And stirred at 100 ° C. for 1 h.
  • the product was precipitated by adding 15 ml of methanol, filtered and dried with a vacuum pump to obtain 321 mg of the desired product as a white solid.
  • Example 8 A coating solution was prepared by mixing 560 mg of cellulose (Merck, Inc., 102330) and 3 g of an aqueous acrylic resin (Washin Paint aqueous polish varnish, solid content 30%). This coating solution was applied onto a flat plate, and the state of cellulose before dissolution was observed visually and with an optical microscope. The coated sample was white, and when observed with an optical microscope, cellulose fine particles were observed as they were (see FIG. 17).
  • Example 9 Extraction of cellulose from sawdust Wood was cut with an electric saw to prepare sawdust. A 10 ml two-necked reactor was charged with 200 mg of a stir bar and its sawdust and replaced with N 2 . 5 ml of tetrabutylammonium hydroxide aqueous solution (Aldrich, 40% in water, MW 259.47, d0.99, 7.71 mmol) was added, and the mixture was stirred at room temperature for 3 days. When the supernatant (2.89 g) was transferred to a vial and 9 ml of methanol was added, cellulose / quaternary ammonium salt was precipitated. Further, when 9 ml of methanol was added to the residue, cellulose / quaternary ammonium salt was precipitated from here.
  • tetrabutylammonium hydroxide aqueous solution Aldrich, 40% in water, MW 259.47, d0.99, 7.71 mmol
  • Example 10-1 515 mg (3.2 mmol) of cellulose was added to 5 ml of tetrabutylammonium hydroxide (TBAH) (manufactured by Aldrich, 40 wt% aqueous solution, 2.39 equivalents with respect to cellulose) while stirring little by little.
  • Sample A after standing for 1 week and Sample B after standing for 1 day were observed with a 40 ⁇ bright field and a polarizing microscope (POM).
  • Neither sample A nor B was considered to be an isotropic solution because no fibrous substance was observed and birefringence based on the anisotropy (crystallinity) of the sample was not observed in the POM image.
  • Example 10-2 Cellulose (515mg, 3.2 mmol) and 5 ml of TBAH (Aldrich, 40% aqueous solution, 2.39 equivalents) were added, and after 5 h, 15 ml of methanol was added for reprecipitation. The white solid was collected by filtration and dried with a vacuum pump for 5 h to obtain 601 mg of a crisp solid.
  • FIG. 22 shows a wide-angle X-ray analysis profile (measurement conditions: sample shape, pulverized in a mortar for 2 minutes; room temperature; sampling every 0.01 °; scan speed, 2 ° / min) of this solid (reprecipitation sample).
  • Cellulose type I is a crystal system unique to natural cellulose.
  • the amorphous halo is bimodal, and the peak position corresponds to the cellulose II crystal.
  • Cellulose II is a crystal system peculiar to a sample precipitated (regenerated) through a molecularly dispersed dissolved state, and cellophane, rayon, and the like are applicable. Together with the results of observation with a polarizing microscope, it is considered that cellulose is dissolved in this solvent as it appears.

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Abstract

La présente invention vise à fournir un moyen capable de dissoudre une cellulose dans des conditions douces au moyen d'une substance relativement sans danger. À cet effet, l'invention concerne un procédé pour la production d'une solution aqueuse de cellulose, comprenant une étape lors de laquelle une cellulose purifiée ou une substance contenant une cellulose est amenée en contact avec une solution aqueuse d'hydroxyde d'ammonium quaternaire, caractérisé en ce que la concentration totale d'halogénures de métal alcalin et/ou d'halogénures de métal alcalino-terreux dissous dans la solution aqueuse d'hydroxyde d'ammonium quaternaire est égale ou inférieure à 1% dans un état où la solution aqueuse d'hydroxyde d'ammonium quaternaire est en contact avec le matériau cellulose de départ. En variante, l'invention concerne un procédé pour la production d'une solution aqueuse de cellulose, comprenant une étape lors de laquelle un matériau cellulose de départ est amené en contact avec une solution aqueuse d'hydroxyde d'ammonium quaternaire, et caractérisé en ce que le matériau cellulose de départ est amené en contact avec la solution aqueuse d'hydroxyde d'ammonium quaternaire en présence d'un polyéther cyclique.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140212670A1 (en) * 2013-01-25 2014-07-31 Daicel Corporation Process for producing solid cellulose and process for producing cellulose ester
CN107177040A (zh) * 2017-06-05 2017-09-19 武汉大学 一种纤维素溶液及其溶解方法和应用
CN113564731A (zh) * 2021-06-17 2021-10-29 武汉纺织大学 一种回收利用牛仔激光废灰的方法及回收物

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106591975B (zh) * 2016-12-08 2020-02-28 新乡化纤股份有限公司 一种再生纤维素长丝纤维的离心式纺丝工艺
CN113861446B (zh) * 2021-10-13 2023-07-14 东华理工大学 一种纤维素溶剂、纤维素溶解方法及纤维素溶液
CN116732620A (zh) * 2023-06-02 2023-09-12 新乡化纤股份有限公司 一种基于新型溶剂体系纺丝的浆粕除杂方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58151217A (ja) * 1982-03-05 1983-09-08 Asahi Chem Ind Co Ltd セルロ−スド−プから得られる繊維及びフイルム
JP2008266625A (ja) * 2007-03-28 2008-11-06 Sanyo Chem Ind Ltd セルロースエーテルの製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE176785T1 (de) * 1995-02-21 1999-03-15 Cellcat Gmbh Zellulosepartikel, verfahren zu deren herstellung und deren verwendung
DE102005017715A1 (de) * 2005-04-15 2006-10-19 Basf Ag Lösungen von Cellulose in ionischen Flüssigkeiten
CN1851063A (zh) * 2006-05-19 2006-10-25 东华大学 以离子液体为溶剂制备纤维素纤维的方法
WO2011111612A1 (fr) * 2010-03-09 2011-09-15 凸版印刷株式会社 Dispersion liquide de fines fibres de cellulose et procédé de production de celle-ci, film de cellulose et corps laminé

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58151217A (ja) * 1982-03-05 1983-09-08 Asahi Chem Ind Co Ltd セルロ−スド−プから得られる繊維及びフイルム
JP2008266625A (ja) * 2007-03-28 2008-11-06 Sanyo Chem Ind Ltd セルロースエーテルの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CELLULOSE CHEMISTRY AND TECHNOLOGY, vol. 18, 1984, pages 379 - 387 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140212670A1 (en) * 2013-01-25 2014-07-31 Daicel Corporation Process for producing solid cellulose and process for producing cellulose ester
US9217043B2 (en) * 2013-01-25 2015-12-22 Daicel Corporation Process for producing solid cellulose and process for producing cellulose ester
CN107177040A (zh) * 2017-06-05 2017-09-19 武汉大学 一种纤维素溶液及其溶解方法和应用
CN113564731A (zh) * 2021-06-17 2021-10-29 武汉纺织大学 一种回收利用牛仔激光废灰的方法及回收物
CN113564731B (zh) * 2021-06-17 2023-05-02 武汉纺织大学 一种回收利用牛仔激光废灰的方法及回收物

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