WO2012077798A1 - Procédé pour la dissolution de cellulose et procédé pour la mesure de la distribution de la masse moléculaire de la cellulose - Google Patents

Procédé pour la dissolution de cellulose et procédé pour la mesure de la distribution de la masse moléculaire de la cellulose Download PDF

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Publication number
WO2012077798A1
WO2012077798A1 PCT/JP2011/078601 JP2011078601W WO2012077798A1 WO 2012077798 A1 WO2012077798 A1 WO 2012077798A1 JP 2011078601 W JP2011078601 W JP 2011078601W WO 2012077798 A1 WO2012077798 A1 WO 2012077798A1
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WIPO (PCT)
Prior art keywords
cellulose
solution
lithium
ionic liquid
molecular weight
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PCT/JP2011/078601
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English (en)
Japanese (ja)
Inventor
芳孝 伊藤
真也 武野
暁 奥村
エーエス カルモカ
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株式会社ブリヂストン
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Publication of WO2012077798A1 publication Critical patent/WO2012077798A1/fr

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    • 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
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
    • G01N2030/885—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds involving polymers

Definitions

  • the present invention relates to a method for dissolving cellulose and a method for measuring molecular weight distribution of cellulose, and more specifically, a cellulose dissolving method and cellulose having a shorter working time, versatility, and cost-effectiveness than conventional methods.
  • the present invention relates to a method for measuring the molecular weight distribution.
  • cellulose Since cellulose has a strong hydrogen bond in its structure, it is not melted or dissolved by a general method, and therefore various dissolution methods and dilute solution preparation methods have been proposed.
  • Examples of the method for dissolving cellulose include a method in which cellulose is derivatized with carbon disulfide and dissolved.
  • a method of complexing and dissolving cellulose using a copper ethylenediamine aqueous solution or a dimethylacetamide solution of lithium halide is also known.
  • Patent Documents 1 and 2 methods for hydrating and dissolving cellulose using an ionic liquid such as an imidazolium salt have been reported (for example, Patent Documents 1 and 2).
  • the cellulose dissolution method using an ionic liquid is easy to dissolve cellulose, has a short preparation time of the cellulose solution, and is excellent in process.
  • the method for dissolving cellulose using an ionic liquid has a drawback that the viscosity of the ionic liquid is very high and the versatility is poor.
  • the ionic liquid is expensive, there has been a problem in using it for a wide range of uses, including application to analysis such as measurement of molecular weight distribution of cellulose.
  • an object of the present invention is to provide a cellulose dissolution method and a cellulose molecular weight distribution measurement method that have a shorter working time than conventional ones, are versatile, and are superior in cost.
  • the cellulose dissolution method of the present invention is a cellulose dissolution method including a step of dissolving cellulose in an ionic liquid.
  • the anion of the ionic liquid is a halogen ion, and the obtained cellulose solution is diluted with a lithium complex salt solution.
  • the halogen ion is preferably a chloride ion.
  • the lithium complex salt is preferably lithium halide.
  • the solvent of the lithium complex salt solution is preferably a solvent having an acetamide group.
  • the lithium halide is preferably lithium chloride.
  • the solvent having an acetamide group is preferably dimethylacetamide.
  • the cation of the ionic liquid preferably has an imidazolium skeleton, and the imidazolium skeleton is preferably 1-n-butyl-3-methylimidazolium. Furthermore, in the present invention, it is preferable to add dimethylacetamide to the ionic liquid.
  • the method for measuring the molecular weight distribution of cellulose of the present invention is characterized by subjecting the cellulose solution prepared by the cellulose dissolution method of the present invention to a size exclusion chromatograph using a dimethylacetamide solution of lithium halide as a mobile phase. It is what.
  • a cellulose dissolution method and a cellulose molecular weight distribution measurement method that have a shorter working time than conventional ones, are versatile, and are superior in cost.
  • the cellulose dissolution method of the present invention is a cellulose dissolution method including a step of dissolving cellulose in an ionic solution.
  • the anion of the ionic liquid is a halogen ion, and it is important to dilute the obtained cellulose solution with a lithium complex salt solution.
  • the ionic liquid can dissolve most cellulose species, and a cellulose solution can be prepared regardless of the cellulose species. In order to dissolve cellulose in the ionic liquid, it may be contacted at 80 to 110 ° C. for about 2 to 8 hours. More preferably, it is 80 to 90 ° C. for about 3 to 5 hours.
  • the obtained cellulose solution is diluted with a lithium complex salt solution.
  • the cellulose hydrated by the ionic liquid forms a complex with lithium and becomes soluble in the solvent.
  • the work is simplified and shortened.
  • the amount of ionic liquid used can be reduced to 1/100 or less of the conventional one, which is excellent in terms of cost.
  • the cellulose dissolution method of the present invention can be applied to many cellulose species, and a dilute solution can be prepared in a short time and easily under the same conditions. Furthermore, by using an ionic liquid whose anion is halogen as an ionic liquid and a lithium complex salt dilute solution, it can be diluted to any magnification, so it is suitable for sample preparation for measuring the molecular weight distribution of cellulose. Can be used.
  • the viscosity of a diluted solution obtained by diluting a cellulose solution with a lithium complex salt solution is approximately the same as that of a lithium complex salt solution used in the mobile phase of the method for measuring the molecular weight distribution of cellulose of the present invention described later. Therefore, the measurement of the molecular weight distribution of cellulose also has an advantage that it can be analyzed under the same conditions as those of the conventional molecular weight distribution measurement using a lithium complex salt solution.
  • the cation of the ionic liquid used in the present invention preferably has an imidazolium skeleton.
  • Specific examples of the cation having an imidazolium skeleton include 1-ethyl-3-methylimidazolium ion, 1-n-propyl-3-methylimidazolium ion, 1-n-butyl-3-methylimidazolium ion, 1 -N-pentyl-3-methylimidazolium ion, 1-n-hexyl-3-methylimidazolium ion, 1-n-octyl-3-methylimidazolium ion, 1-ethyl-2,3-dimethylimidazolium ion
  • An ionic liquid cation having a methylimidazolium skeleton such as 1-n-butyl-2,3-dimethylimidazolium ion, 1-allyl-3-methylimidazolium, or the like is preferable.
  • the anion of the ionic liquid is a halogen ion such as fluoride ion, chloride ion, bromide ion or iodide ion, and preferably chloride ion.
  • a halogen ion such as fluoride ion, chloride ion, bromide ion or iodide ion, and preferably chloride ion.
  • anions other than these for example, inorganic anions such as HSO 4 ⁇ , CH 3 SO 3 — and carboxylic acid anions, for example, carboxylic acid anions such as formate anion, acetate anion, propionate anion will be described later. This is not preferable because precipitation occurs when diluted with a lithium complex salt.
  • 1-n-butyl-3-methylimidazolium chloride which is a suitable combination of anion and cation
  • the ionic liquid the ionic liquid may be used alone, but it is also preferable to use dimethylacetamide in combination. Thereby, the viscosity of an ionic liquid can be reduced and solubility can be improved.
  • dimethylacetamide is suitable as a mixed solvent because it is used in the mobile phase of the method for measuring the molecular weight distribution of cellulose described later. In consideration of the solubility of cellulose in the ionic liquid, the amount of dimethylacetamide in the mixed solution is preferably about 25 to 50% by mass.
  • lithium halides such as lithium fluoride, lithium chloride, lithium bromide, and lithium iodide can be suitably used as the lithium complex salt in the lithium complex salt solution used for diluting the cellulose solution. .
  • the ionic liquid in which the cellulose is dissolved is replaced by the lithium complex salt and dissolved by the lithium ion-cellulose hydroxyl group interaction.
  • Particularly preferred is lithium chloride.
  • the lithium complex salt concentration of the lithium complex salt solution can be about 0.5 to 10% by mass.
  • the method for measuring the molecular weight distribution of cellulose of the present invention is to measure the molecular weight distribution of cellulose by size exclusion chromatography using a solution prepared by the method of dissolving cellulose of the present invention.
  • the molecular weight distribution of cellulose is usually analyzed by size exclusion chromatography using dimethylacetamide added with lithium chloride or lithium bromide as a mobile phase. Since the viscosity of the solution obtained by the cellulose dissolution method of the present invention is almost the same as that of the above mobile phase, molecular weight distribution using a conventional lithium complex salt solution is also used for measuring the molecular weight distribution of cellulose. Analysis can be performed under the same conditions as in the measurement method.
  • the concentration of lithium halide in dimethylacetamide as the mobile phase can be about 0.5 to 10% by mass, but is preferably the same as the solvent composition of the cellulose solution.
  • a separation column used in the size exclusion chromatograph a column using a packing material based on a methacrylate polymer can be used, and as a detector, for example, a differential bending rate detector (RI) is used. Can do.
  • Example 1-1 A 1-n-butyl-3-methylimidazolium chloride / dimethylacetamide 75/25 (mass ratio) solvent was added to a pulp for papermaking having a polymerization degree of 1000 to 1500 dehydrated by drying at 110 ° C. for 8 hours. The mixture was stirred at 80 ° C. for 4 hours to obtain a 10% by mass pulp solution. Add 8 wt% lithium chloride / dimethylacetamide solution to 12.5 times equivalent to the obtained 10 wt% pulp solution, infiltrate lightly, let stand for half a day, and further increase 8 times with dimethylacetamide. By diluting, a cellulose solution (0.1% by mass solution) was obtained. The obtained cellulose solution was filtered through a filter, and the molecular weight distribution was measured under the following conditions. The obtained results are shown in Table 1.
  • Example 1-2 A cellulose solution was obtained in the same manner as in Example 1-1 except that papermaking pulp having a polymerization degree of 300 to 800 was used. The obtained cellulose solution was filtered through a filter, and the molecular weight distribution was measured under the following conditions. The obtained results are shown in Table 1.
  • Paper pulp with a polymerization degree of 1000 to 1500 was washed with distilled water, acetone and dimethylacetamide solvents, stirred and immersed (1 day), desolvated, and vacuum dried at 60 ° C for 40 hours to prepare a sample. did. A few drops of 8% by mass lithium chloride / dimethylacetamide solution were added to the obtained sample and stirred for several days to obtain a 0.8% by mass cellulose solution. The obtained 0.8 mass% pulp solution was diluted 8 times with a dimethylacetamide solution to obtain a 0.1 mass% cellulose solution, and the molecular weight distribution was measured in the same manner as in Example 1. The obtained results are shown in Table 1.
  • Example 1-2 A cellulose solution was obtained in the same manner as in Example 1-1 except that papermaking pulp having a polymerization degree of 300 to 800 was used. The obtained cellulose solution was filtered through a filter, and the molecular weight distribution was measured under the following conditions. The obtained results are shown in Table 1.
  • Example 2-1 1-n-Butyl-3-methylimidazolium chloride
  • Example 2-2 1-allyl-3-methylimidazolium chloride
  • Example 2-3 1-ethyl-3-methylimidazolium chloride
  • Example 2-4 1-n-butyl-3-methylimidazolium chloride / dimethylacetamide (75/25: mass ratio)
  • Example 2-5 1-allyl-3-methylimidazolium chloride / dimethylacetamide (75/25: mass ratio)
  • Example 2-6 1-ethyl-3-methylimidazolium chloride / dimethylacetamide (75/25: mass ratio)
  • Comparative Example 2-1 1-n-butyl-3-methylimidazolium acetate / dimethylacetamide (75/25: mass ratio)
  • Comparative Example 2-2 1-n-butyl-3-methylimidazolium diethyl phosphate / dimethylacetamide (75/25: mass ratio)
  • Comparative Example 2-3 Methyltribut
  • a cellulose solution can be prepared in one day.
  • a high-polymerization degree pulp could not produce a cellulose solution by the same technique as a low-polymerization degree pulp (Table 1).
  • the cellulose dissolution method of the present invention since the cellulose solution is prepared through a solvent using an ionic liquid, the cellulose solution can be prepared using either a high polymerization degree pulp or a low polymerization degree pulp. It was. Thereby, it turns out that the dissolution method of the cellulose of this invention is applicable regardless of pulp kind.
  • the cellulose dissolution method of the present invention can prepare a cellulose solution easily and in a short time compared to the conventional method, and can be applied to the measurement of molecular weight distribution of cellulose. I know that there is.
  • Table 2 also shows that in the cellulose dissolution method of the present invention, the combination of an ionic liquid halogen salt having a methylimidazolium skeleton and a lithium halide is excellent as a combination of an ionic liquid and a lithium complex salt. .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur un procédé pour la dissolution de cellulose et sur un procédé pour la mesure de la distribution de la masse moléculaire de la cellulose, ayant une plus courte durée, une plus grande polyvalence et une rentabilité supérieure par comparaison avec l'état de la technique. Le procédé pour la dissolution de cellulose comprend une étape de dissolution de cellulose dans un liquide ionique. Les anions du liquide ionique sont des ions d'halogène et la solution de cellulose dissoute ainsi obtenue est diluée par une solution de sel complexe du lithium. Les ions d'halogène sont de préférence des ions chlorures et le sel complexe du lithium est de préférence un halogénure de lithium.
PCT/JP2011/078601 2010-12-10 2011-12-09 Procédé pour la dissolution de cellulose et procédé pour la mesure de la distribution de la masse moléculaire de la cellulose WO2012077798A1 (fr)

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JP2010-276424 2010-12-10
JP2010276424A JP2012126755A (ja) 2010-12-10 2010-12-10 セルロースの溶解方法およびセルロースの分子量分布の測定方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276591A (zh) * 2018-03-01 2018-07-13 南京林业大学 一种纤维素溶液及其制备方法

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CN104520477A (zh) * 2012-08-07 2015-04-15 日东纺绩株式会社 纤维素纤维的制造方法
TWI580829B (zh) * 2012-08-28 2017-05-01 Nitto Boseki Co Ltd Manufacture of Cellulose Fibers
JP2016098313A (ja) 2014-11-21 2016-05-30 セイコーエプソン株式会社 セルロース系材料、液状組成物、造形物および造形物の製造方法
JP6550727B2 (ja) * 2014-11-21 2019-07-31 セイコーエプソン株式会社 液状組成物、造形物および造形物の製造方法
JP6582485B2 (ja) 2015-03-27 2019-10-02 セイコーエプソン株式会社 組成物、造形物の製造方法および造形物
JP2016188283A (ja) 2015-03-30 2016-11-04 セイコーエプソン株式会社 組成物セット、造形物の製造方法および造形物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06109715A (ja) * 1992-09-30 1994-04-22 Shimadzu Corp 高分子物質の分子量分布分析法
JPH09255701A (ja) * 1996-03-22 1997-09-30 Daicel Chem Ind Ltd セルロース・エステルの製造方法
JP2008050595A (ja) * 2006-07-27 2008-03-06 Sanyo Chem Ind Ltd セルロース類の溶解溶剤およびセルロース類の溶解方法
JP2009203467A (ja) * 2008-01-31 2009-09-10 Kri Inc セルロースを溶解する溶媒及びセルロース溶液からの成形体
JP2010510405A (ja) * 2006-11-24 2010-04-02 コンバテック・テクノロジーズ・インコーポレイテッド セルロースの溶解および加工

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06109715A (ja) * 1992-09-30 1994-04-22 Shimadzu Corp 高分子物質の分子量分布分析法
JPH09255701A (ja) * 1996-03-22 1997-09-30 Daicel Chem Ind Ltd セルロース・エステルの製造方法
JP2008050595A (ja) * 2006-07-27 2008-03-06 Sanyo Chem Ind Ltd セルロース類の溶解溶剤およびセルロース類の溶解方法
JP2010510405A (ja) * 2006-11-24 2010-04-02 コンバテック・テクノロジーズ・インコーポレイテッド セルロースの溶解および加工
JP2009203467A (ja) * 2008-01-31 2009-09-10 Kri Inc セルロースを溶解する溶媒及びセルロース溶液からの成形体

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108276591A (zh) * 2018-03-01 2018-07-13 南京林业大学 一种纤维素溶液及其制备方法
CN108276591B (zh) * 2018-03-01 2021-05-11 南京林业大学 一种纤维素溶液及其制备方法

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