US20180273698A1 - Ionic liquid and method for dissolving cellulose using the same - Google Patents

Ionic liquid and method for dissolving cellulose using the same Download PDF

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US20180273698A1
US20180273698A1 US15/912,576 US201815912576A US2018273698A1 US 20180273698 A1 US20180273698 A1 US 20180273698A1 US 201815912576 A US201815912576 A US 201815912576A US 2018273698 A1 US2018273698 A1 US 2018273698A1
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ionic liquid
cellulose
liquid composition
inventive example
dissolved
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Takahiro Aoki
Tomoko Kawashima
Haruka Kusukame
Yuko Taniike
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Assigned to PANASONIC INTELLECTUAL PROPERTY MANAGEMENT CO., LTD. reassignment PANASONIC INTELLECTUAL PROPERTY MANAGEMENT CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUSUKAME, HARUKA, AOKI, TAKAHIRO, KAWASHIMA, TOMOKO, TANIIKE, YUKO
Publication of US20180273698A1 publication Critical patent/US20180273698A1/en
Priority to US16/796,170 priority Critical patent/US10875973B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/096—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to an ionic liquid and a method for dissolving cellulose using the same.
  • Patent Literature 1 discloses using an ionic liquid as an enzyme saccharification pretreatment agent of cellulosic biomass. Patent Literature 1 discloses choline acetate as an ionic liquid in the paragraph [0037] thereof. Furthermore, in the paragraph [0022] thereof, Patent Literature 1 discloses that an example of the anion of the ionic liquid is an amino acid anion such as glutaminic acid anion.
  • Patent Literature 2 discloses an ionic liquid, a purification method of the ionic liquid, and a treatment method of cellulose-based biomass.
  • Patent Literature 2 discloses in the paragraphs [0024]-[0026] thereof that an example of the anion of the ionic liquid is an anion of an amino acid such as alanine, lysine, threonine, isoleucine, asparagine, valine, phenylalanine, tyrosine, methionine, leucine, or ornithine.
  • Non Patent Literature 1 and Non Patent Literature 2 disclose degradation of cellulose using a cellulose-degrading enzyme (namely, an enzyme capable of hydrolyzing cellulose) together with the degradation accelerator of an ionic liquid consisting of [(CH 3 ) 3 NCH 2 CH 2 OH] + [NH 2 (CH 2 ) 4 CH(NH 2 )COO] ⁇ (hereinafter, referred to as “[Ch][Lys]”).
  • a cellulose-degrading enzyme namely, an enzyme capable of hydrolyzing cellulose
  • an ionic liquid consisting of [(CH 3 ) 3 NCH 2 CH 2 OH] + [NH 2 (CH 2 ) 4 CH(NH 2 )COO] ⁇
  • the present invention provides an ionic liquid represented by the following chemical formula (I):
  • L is —(CH 2 ) 2 — or —(CH 2 ) 3 —.
  • the present invention provides an ionic liquid capable of dissolving cellulose without an cellulose-degrading enzyme (namely, an enzyme capable of hydrolyzing cellulose).
  • FIG. 1 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 1A.
  • FIG. 2 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 1B.
  • FIG. 3 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 1C.
  • FIG. 4 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the comparative example 1A.
  • FIG. 5 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the comparative example 1B.
  • FIG. 6 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 2A.
  • FIG. 7 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 2B.
  • FIG. 8 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 2C.
  • FIG. 9 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the comparative example 2A.
  • FIG. 10 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the comparative example 2B.
  • the ionic liquid according to the present embodiment is represented by the following chemical formula (I).
  • L is —(CH 2 ) 2 — or —(CH 2 ) 3 —.
  • the ionic liquid composition according to the present embodiment contains the ionic liquid represented by the chemical formula (I) and water. Unlike the disclosure of Non Patent Literature 1 and Non Patent Literature 2, the ionic liquid composition according to the present embodiment does not contain a cellulose-degrading enzyme (namely, an enzyme capable of hydrolyzing cellulose).
  • a cellulose-degrading enzyme namely, an enzyme capable of hydrolyzing cellulose
  • a molar ratio of [(CH 3 ) 3 N(CH 2 ) 2 OH] + to [NH 2 -L-COO] ⁇ is not less than 0.86 and not more than 1.12.
  • a weight ratio of the water to the ionic liquid composition is not more than 4.7%.
  • cellulose is added to the ionic liquid composition according to the present embodiment.
  • the cellulose is dissolved in the ionic liquid composition to provide a cellulose solution.
  • the cellulose has weight average molecular weight of not less than 30,000. More desirably, the cellulose has weight average molecular weight of not more than 500,000.
  • an ionic liquid is composed of a cation and an anion.
  • the cation is a choline cation represented by the chemical formula [(CH 3 ) 3 N(CH 2 ) 2 OH] + (hereinafter, referred to as “[Ch]”).
  • Choline is an aqueous nutrient essential for a human.
  • the anion is represented by the chemical formula [NH 2 -L-COO] ⁇ .
  • the anion is a ⁇ -alanine anion represented by the chemical formula [NH 2 —CH 2 —CH 2 —COO] ⁇ or a ⁇ -aminobutyric acid anion represented by the chemical formula [NH 2 —CH 2 —CH 2 —CH 2 —COO] ⁇ .
  • ⁇ -alanine and ⁇ -aminobutyric acid are each one kind of amino acids.
  • choline cation, ⁇ -alanine anion, and ⁇ -aminobutyric acid anion may be represented by [Ch], [ ⁇ -Ala], and [GABA] respectively in the present specification.
  • [Ch], [ ⁇ -Ala], and [GABA] exist in a human body, and are materials having high safety for a living body for the reason of holding of matabolic pathway in a body and other reasons.
  • the ionic liquid according to the present disclosure is capable of weaking hydrogen bonds between the cellulose chains and the effect of improving solubility of cellulose is expected.
  • the ionic liquid represented by the chemical formula [Ch][ ⁇ -Ala] may be synthesized on the basis of the following chemical reaction formula (II).
  • choline is mixed with ⁇ -alanine.
  • the molar quantity of choline is as much as that of ⁇ -alanine.
  • the mixture solution containing choline and ⁇ -alanine is heated under vacuum, and then dried to provide the ionic liquid represented by the chemical formula [Ch][ ⁇ -Ala] through dehydration reaction between the hydroxyl ion of choline and the hydrogen ion of the carboxyl group of the ⁇ -alanine.
  • the ionic liquid represented by the chemical formula [Ch][GABA] may also synthesized similarly.
  • the molar ratio of [(CH 3 ) 3 N(CH 2 ) 2 OH] + to [NH 2 -L-COO] ⁇ is not less than 0.86 and not more than 1.12.
  • the molar ratio is less than 0.86, cellulose fails to be dissolved in the ionic liquid composition within forty-eight hours.
  • the molar ratio is more than 1.12, cellulose fails to be dissolved in the ionic liquid composition within forty-eight hours.
  • a weight ratio of the water to the ionic liquid composition is not more than 4.7%.
  • cellulose fails to be dissolved in the ionic liquid composition within forty-eight hours. Time necessary for dissolving cellulose is also decreased with a decrease in the weight ratio. Therefore, it is desirable that the weight ratio is small.
  • the lower limit of the weight ratio is 1.6%. However, cellulose may be dissolved even when the weight ratio is less than 1.6%.
  • chemical reaction formula (II) note that water is generated as by-product upon the synthesis of the ionic liquid.
  • the ionic liquid composition according to the present embodiment dissolves cellulose within forty-eight hours, desirably, within twenty-four hours, after the cellulose is added to the ionic liquid composition according to the present embodiment.
  • a cellulose-degrading enzyme is not used.
  • a cellulose film is formed from the ionic liquid composition to which the cellulose has been added, namely, from the cellulose solution.
  • the ionic liquid composition to which the cellulose has been added is heated in order to promote the dissolution.
  • the ionic liquid composition to which the cellulose has been added is heated at a temperature of not less than 70 degrees Celsius and not more than 100 degrees Celsius at a pressure of not less than 0.01 MPa and not more than 0.1 MPa for forty-eight hours.
  • the ionic liquid composition to which the cellulose has been added may be left at rest until the cellulose is dissolved in the ionic liquid composition.
  • the ionic liquid composition to which the cellulose has been added may be stirred.
  • a kind of the cellulose dissoluble in the ionic liquid of the present disclosure is not limited particularly.
  • native cellulose derived from plant species, native cellulose of biological origin, regenerated cellulose such as cellophane, or artificial cellulose such as cellulose nanofiber may be applied.
  • it does not depend on the crystalline state of original cellulose.
  • cellulose has an I-type-IV-type crystalline structure or a non-crystalline structure. Cellulose having any structure may be dissolved.
  • the ionic liquid composition according to the present embodiment may contain the ionic liquid and other components.
  • An example of the other components is an aprotic polar solvent.
  • the ionic liquid composition according to the present embodiment is in a liquid state.
  • the ionic liquid composition according to the present embodiment may contain an aprotic polar solvent in order to control a viscosity thereof.
  • An example of the aprotic polar solvent is dimethyl sulfoxide.
  • the weight ratio of the aprotic polar solvent to the ionic liquid may be not less than 309%.
  • the dimethyl sulfoxide may be added before, during, or after the dissolution of the cellulose.
  • the ionic liquid composition according to the present embodiment does not contain cellulose-degrading enzyme.
  • the experiment 1 is composed of inventive examples 1A-1H and comparative examples 1A-1D.
  • the cation was derived from choline and the anion was derived from ⁇ -alanine.
  • ⁇ -alanine available from Tokyo Chemical Industry Co., Ltd., 8.9 grams, 100 millimoles
  • a choline aqueous solution available from Tokyo Chemical Industry Co., Ltd., 24.7 grams, 100 millimoles
  • the mixture solution was dried at a temperature of 100 degrees Celsius under reduced pressure for three hours. In this way, an ionic liquid composition containing an ionic liquid represented by the chemical formula [Ch][ ⁇ -Ala] was provided.
  • the thus-provided [Ch][ ⁇ -Ala] ionic liquid composition was confirmed by using nuclear magnetic resonance spectrum measurement.
  • the structure of the ionic liquid composition fabricated in the present example were determined with nuclear magnetic resonance spectrum (measured with Inova-400 made by Varian company, 400 MHz: 1 H-NMR).
  • the measurement was conducted using deuterated DMSO and indicated with ⁇ value (ppm) when tetramethyl silane (i.e., TMS) was an internal standard.
  • FIG. 1 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement.
  • a water amount contained in the [Ch][ ⁇ -Ala] ionic liquid composition was measured by Karl Fischer's method. In this method, the weight of the [Ch][ ⁇ -Ala] ionic liquid composition was measured three times to calculate the average weight thereof, and then this ionic liquid composition was injected to a moisture measurement device CA-100 (available from Mitsubishi Chemical Analytech Co., Ltd). The weight of the residual moisture was measured and a water ratio was calculated by dividing by the weight of the ionic liquid composition. As a result, the water amount of the [Ch][ ⁇ -Ala] ionic liquid composition was 1.7% (8.5 milligrams).
  • the [Ch][ ⁇ -Ala] ionic liquid composition having a weight of 0.97 grams was supplied to a glass bottle.
  • Cellulose (0.03 grams, available from Sigma-Aldrich, trade name: Avicel PH-101, average molecular weight measured by a gel-permeation chromatography—multi angle light scattering method: approximately 30,000) was added to the glass bottle.
  • the solution was left at rest at a temperature of 90 degrees Celsius at a pressure of 0.02 MPa.
  • the present inventors observed visually whether or not the added cellulose was dissolved in the [Ch][ ⁇ -Ala] ionic liquid composition.
  • the ratio of the [Ch] cation to the [ ⁇ -Ala] anion in the provided [Ch][ ⁇ -Ala] ionic liquid composition was measured as below.
  • three peaks each having a shift value of not less than 3.0 are derived from choline.
  • the values of area ratio of the three peaks are 0.18, 0.19, and 0.81.
  • a choline molecular has fourteen hydrogen atoms. However, one hydroxyl group included in the choline molecular does not appear in the 1 H-NMR spectrum. Therefore, in FIG. 1 , the thirteen hydrogen atoms included in the choline molecular appear.
  • ⁇ -alanine two peaks each having a shift value of less than 3.0 are derived from ⁇ -alanine.
  • the values of area ratio of these two peaks are 0.16 and 0.20.
  • One ⁇ -alanine anion has six hydrogen atoms.
  • two hydrogen atoms included in the amino acid group included in the ⁇ -alanine molecule do not appear in the 1 H-NMR spectrum. Therefore, in FIG. 1 , four hydrogen atoms included in the ⁇ -alanine molecular appears.
  • the area of 1 H-NMR is proportional to the number of the hydrogen atoms. Therefore, the ratio of the [Ch] cation to the [ ⁇ -Ala] anion included in the [Ch][ ⁇ -Ala] ionic liquid composition is calculated on the basis of the following mathematical formula (X). Hereinafter, the ratio is referred to as “RCA”.
  • RCA ((the sum total of the area ratio of the peaks derived from the cation)/(the number of the hydrogen atom(s)which is/are included in the cation and appear(s) in the 1 H-NMR spectrum))/((the sum total of the area ratio of the peaks derived from the anion)/(the number of the hydrogen atom(s)which is/are included in the anion and appear(s) in the 1 H-NMR spectrum)) (X)
  • FIG. 2 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 1B.
  • the value of RCA calculated on the basis of FIG. 2 was 0.86.
  • the cellulose was dissolved after fifteen hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • FIG. 3 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 1C.
  • the value of RCA calculated on the basis of FIG. 3 was 1.12.
  • the cellulose was dissolved after fifteen hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • inventive example 1D an experiment similar to the inventive example 1A was conducted, except of using bleached pulp made from wood (average molecular weight: approximately 300,000-500,000) in place of the cellulose (trade name: Avicel).
  • the cellulose was dissolved after forty-eight hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • the inventive example 1E an experiment similar to the inventive example 1A was conducted, except that the ionic liquid composition (0.97 grams) according to the inventive example 1A further contained water (0.029 grams, 4.7 weight percent) and except of using bleached pulp made from wood (average molecular weight: approximately 300,000-500,000) in place of the cellulose (trade name: Avicel).
  • the cellulose was dissolved after forty-eight hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • FIG. 4 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the comparative example 1A.
  • the value of RCA calculated on the basis of FIG. 4 was 0.79.
  • the cellulose was not dissolved.
  • FIG. 5 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the comparative example 1B.
  • the value of RCA calculated on the basis of FIG. 5 was 1.19.
  • the cellulose was not dissolved, even after two hundred and forty hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • the ionic liquid composition (0.97 grams) according to the inventive example 1A further contained water (0.049 grams, 6.7 weight percent) and except of using bleached pulp made from wood (average molecular weight: approximately 300,000-500,000) in place of the cellulose (trade name: Avicel).
  • the cellulose was not dissolved, even after two hundred and forty hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • the cellulose was dissolved in the ionic liquid composition within 48 hours after the mixture of the ionic liquid composition and the cellulose. On the other hand, if the water amount is not less than 6.7%, the cellulose was not dissolved in the ionic liquid composition even after 240 hours.
  • DMSO dimethyl sulfoxide
  • the weight ratio thereof to the ionic liquid [Ch][ ⁇ -Ala]: 103%) was added to the cellulose solution (1.00 gram) provided in the inventive example 1D. Then, this solution was left at rest at a temperature of 90 degrees Celsius at normal pressures for 48 hours. The present inventors observed visually whether or not the cellulose and the DMSO were dissolved in each other.
  • Example 1D TABLE 2 Weight ratio of DMSO to [Ch][ ⁇ -Ala] Result Inventive 103 Dissolved in each other Example 1F Inventive 206 Dissolved in each other.
  • Example 1G Inventive 309 Dissolved in each other Example 1H Comparative 412 Cellulose was precipitated.
  • Example 1D TABLE 2 Weight ratio of DMSO to [Ch][ ⁇ -Ala] Result Inventive 103 Dissolved in each other Example 1F Inventive 206 Dissolved in each other.
  • Example 1G Inventive 309 Dissolved in each other Example 1H Comparative 412 Cellulose was precipitated.
  • Example 1D Example 1D
  • the experiment 2 is composed of inventive examples 2A-2H and comparative examples 2A-2D.
  • the cation was derived from choline and the anion was derived from ⁇ -aminobutyric acid.
  • ⁇ -aminobutyric acid available from Wako Pure Chemical Industries, Ltd., 10.3 grams, 100 millimoles
  • a choline aqueous solution available from Tokyo Chemical Industry Co., Ltd., 24.7 grams, 100 millimoles
  • the mixture solution was dried at a temperature of 100 degrees Celsius under reduced pressure for three hours.
  • an ionic liquid composition containing [Ch][GABA] ionic liquid was provided.
  • the provided [Ch][GABA] ionic liquid composition was confirmed by using nuclear magnetic resonance spectrum measurement.
  • the water amount of the [Ch][GABA] ionic liquid composition was 1.6% (8.0 milligrams).
  • FIG. 6 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 2A.
  • the value of RCA calculated on the basis of FIG. 6 was 1.00.
  • the cellulose was dissolved. Furthermore, as a basis that the peak derived from the crystalline property of the cellulose disappeared in the X-ray diffraction analysis result, the present inventors also confirmed the dissolution of the cellulose.
  • FIG. 7 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 2B.
  • the value of RCA calculated on the basis of FIG. 7 was 0.89.
  • the cellulose was dissolved after thirteen hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • FIG. 8 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the inventive example 2C.
  • the value of RCA calculated on the basis of FIG. 8 was 1.10.
  • the cellulose was dissolved after thirteen hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • inventive example 2D an experiment similar to the inventive example 2A was conducted, except of using bleached pulp made from wood (average molecular weight: approximately 300,000-500,000) in place of the cellulose (trade name: Avicel).
  • the cellulose was dissolved after forty-four hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • the ionic liquid composition (0.97 grams) according to the inventive example 2A further contained water (0.029 grams, 4.6 weight percent) and except of using bleached pulp made from wood (average molecular weight: approximately 300,000-500,000) in place of the cellulose (trade name: Avicel).
  • the cellulose was dissolved after forty-four hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • FIG. 9 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the comparative example 2A.
  • the value of RCA calculated on the basis of FIG. 9 was 0.79.
  • the cellulose was not dissolved.
  • FIG. 10 shows a result of the nuclear magnetic resonance spectrum 1 H-NMR measurement in the comparative example 2B.
  • the value of RCA calculated on the basis of FIG. 10 was 1.19.
  • the cellulose was not dissolved, even after two hundred and forty hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • the ionic liquid composition (0.97 grams) according to the inventive example 2A further contained water (0.049 grams, 6.6 weight percent) and except of using bleached pulp made from wood (average molecular weight: approximately 300,000-500,000) in place of the cellulose (trade name: Avicel).
  • the cellulose was not dissolved, even after two hundred and forty hours elapsed from the mixture of the ionic liquid composition and the cellulose.
  • the cellulose was dissolved in the ionic liquid composition within 48 hours after the mixture of the ionic liquid composition and the cellulose. On the other hand, if the water amount is not less than 6.6%, the cellulose was not dissolved in the ionic liquid composition even after 240 hours.
  • DMSO dimethyl sulfoxide
  • the weight ratio thereof to the ionic liquid [Ch][GABA]: 103%) was added to the cellulose solution (1.00 gram) provided in the inventive example 2D. Then, this solution was left at rest at a temperature of 90 degrees Celsius at normal pressures for 48 hours. The present inventors observed visually whether or not the cellulose and the DMSO were dissolved in each other.
  • Example 2D TABLE 4 Weight ratio of DMSO to [Ch][GABA] Result Inventive 103 Dissolved in each other Example 2F Inventive 206 Dissolved in each other. Example 2G Inventive 309 Dissolved in each other Example 2H Comparative 412 Cellulose was precipitated. Example 2D
  • the present invention provides an ionic liquid composition capable of dissolving cellulose without an cellulose-degrading enzyme, namely, an enzyme capable of hydrolyzing cellulose.

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