WO2023084650A1 - リグノセルロース誘導体組成物及びその製造方法 - Google Patents

リグノセルロース誘導体組成物及びその製造方法 Download PDF

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Publication number
WO2023084650A1
WO2023084650A1 PCT/JP2021/041399 JP2021041399W WO2023084650A1 WO 2023084650 A1 WO2023084650 A1 WO 2023084650A1 JP 2021041399 W JP2021041399 W JP 2021041399W WO 2023084650 A1 WO2023084650 A1 WO 2023084650A1
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WO
WIPO (PCT)
Prior art keywords
lignocellulose
lignin
hemicellulose
skeleton
containing compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/041399
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English (en)
French (fr)
Japanese (ja)
Inventor
浩 上高原
健司 北山
優 宮内
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daicel Corp
Kyoto University NUC
Original Assignee
Daicel Corp
Kyoto University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daicel Corp, Kyoto University NUC filed Critical Daicel Corp
Priority to JP2023559267A priority Critical patent/JPWO2023084650A1/ja
Priority to PCT/JP2021/041399 priority patent/WO2023084650A1/ja
Priority to EP21963481.3A priority patent/EP4431569A4/en
Priority to US18/709,261 priority patent/US20250002697A1/en
Priority to CN202180104048.5A priority patent/CN118202002A/zh
Publication of WO2023084650A1 publication Critical patent/WO2023084650A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/14—Hemicellulose; Derivatives 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/14—Hemicellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers

Definitions

  • Non-Patent Document 1 Green Chem., 2020, 22, 2909-2928
  • methylated cellulose, lignin and hemicellulose are produced by methylating coniferous sawdust in a solvent using a methylating agent.
  • a method of generating is disclosed.
  • the lignocellulose derivative composition according to the present disclosure contains either or both of a lignin skeleton-containing compound and a hemicellulose skeleton-containing compound.
  • This composition may further contain a cellulose derivative in which some or all of the hydroxyl groups in cellulose are etherified with alkyl groups having 2 or more carbon atoms.
  • the lignin skeleton-containing compound is lignin or a lignin derivative in which some or all of the hydroxyl groups in lignin are etherified with alkyl groups having 2 or more carbon atoms.
  • the hemicellulose skeleton-containing compound is hemicellulose or a hemicellulose derivative in which some or all of the hydroxyl groups in hemicellulose are etherified with alkyl groups having 2 or more carbon atoms.
  • the lignocellulose derivative composition of the present disclosure may have any of the following aspects.
  • a cellulose derivative in which some or all of the hydroxyl groups in cellulose are etherified with alkyl groups having 2 or more carbon atoms, and a lignin skeleton-containing compound, wherein the lignin skeleton-containing compound is lignin or in lignin is a lignin derivative in which some or all of the hydroxyl groups are etherified with alkyl groups having 2 or more carbon atoms, and the number average molecular weight Mn obtained by gel permeation chromatography is 30,000 or more and 120,000 or less.
  • a lignocellulose derivative composition can be obtained in one step using woody biomass as a raw material without going through a process with a high environmental load.
  • lignin and hemicellulose which have conventionally been discarded, can be effectively used as raw materials.
  • alkali The type of alkali is not particularly limited as long as the effects of the present disclosure can be obtained.
  • hydroxides of alkali metals such as sodium and potassium are preferably used. It may be added to the raw material biomass as an alkaline aqueous solution. From the viewpoint of facilitating alkali treatment, the amount of alkali to be added is preferably 600 parts by weight or more, more preferably 630 parts by weight or more, and more preferably 650 parts by weight or more in terms of solid content with respect to 100 parts by weight of raw biomass. More preferred.
  • alkyl esters such as toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid may be used as the alkylating agent as long as the effects of the present disclosure are not impaired.
  • Fractionation means separating a mixture into individual components using the differences in the physical properties of the constituent components.
  • the method for fractionating lignocellulose after alkylation is not particularly limited.
  • cellulose and cellulose derivatives, lignin and lignin derivatives, and hemicellulose and hemicellulose derivatives can be fractionated by sedimentation fractionation, dialysis treatment, fractional extraction, etc. by utilizing differences in solubility in solvents. .
  • the lignocellulose derivative composition of the present disclosure is obtained by the production method described above. Specifically, this lignocellulose derivative composition is obtained by fractionating alkylated lignocellulose by utilizing the difference in solvent solubility of constituent components. In a preferred embodiment, alkylated lignocellulose is fractionated into a lignocellulose derivative composition according to the following aspects.
  • the molecular weight distribution Mw/Mn obtained from the weight average molecular weight Mw and the number average molecular weight Mn of the lignocellulose derivative composition of Embodiment 1 is preferably 1.0 or more, more preferably 1.5 or more. Preferably, 1.6 or more is more preferable. From the viewpoint of improving the strength of the resulting molded article, the molecular weight distribution Mw/Mn is preferably 7.0 or less, more preferably 6.0 or less, even more preferably 4.0 or less, and particularly preferably 2.8 or less.
  • the molding temperature may be 120° C. or higher, 140° C. or higher, 180° C. or higher, and 280° C. or lower. °C or lower, and may be 230 °C or lower.
  • the thermal decomposition temperature exceeds 300° C., thermal deterioration due to thermoforming in this temperature range is avoided.
  • drying treatment may be performed before and/or after molding the lignocellulose derivative composition.
  • composition E3 was obtained by harvesting and freeze-drying.
  • the yield (% by weight) of each composition in Experimental Example 1 is shown in Table 1 below.
  • a 2 A*7/3 Integrated value of methylene protons
  • Integral value C 2 of one proton in the pentose ring [(CA 2 -B 1 )/6]*(1.0/10.8)
  • Lignin content (%) A 1 / (A 1 + C 1 + C 2 ) x 100
  • compositions E2 and E3 As shown in Figures 6 and 7, in compositions E2 and E3, no melting point was observed, only the glass transition point was observed. According to the literature, the Tg of hemicellulose and lignin in a dry state is 130-230° C., so it is considered that the ethyl substitution greatly lowered the Tg. Moreover, it was confirmed that all compositions E3 were thermally decomposed at 200° C. or higher.
  • compositions E1 and E2 of the present disclosure have comparable molecular weights to commercially available ethyl cellulose, yet exhibit excellent thermal properties. Moreover, it was confirmed that the composition E3 of the present disclosure has a high surfactant ability compared to commercially available methylcellulose. From this evaluation result, the superiority of the present disclosure is clear.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2021/041399 2021-11-10 2021-11-10 リグノセルロース誘導体組成物及びその製造方法 Ceased WO2023084650A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2023559267A JPWO2023084650A1 (https=) 2021-11-10 2021-11-10
PCT/JP2021/041399 WO2023084650A1 (ja) 2021-11-10 2021-11-10 リグノセルロース誘導体組成物及びその製造方法
EP21963481.3A EP4431569A4 (en) 2021-11-10 2021-11-10 COMPOSITION DERIVED FROM LIGNOCELLULOSE AND PROCESS FOR ITS PRODUCTION
US18/709,261 US20250002697A1 (en) 2021-11-10 2021-11-10 Composition containing a lignocellulose and method for producing same
CN202180104048.5A CN118202002A (zh) 2021-11-10 2021-11-10 木质纤维素衍生物组合物及其制造方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2021/041399 WO2023084650A1 (ja) 2021-11-10 2021-11-10 リグノセルロース誘導体組成物及びその製造方法

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WO2023084650A1 true WO2023084650A1 (ja) 2023-05-19

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EP (1) EP4431569A4 (https=)
JP (1) JPWO2023084650A1 (https=)
CN (1) CN118202002A (https=)
WO (1) WO2023084650A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025063308A1 (ja) * 2023-09-22 2025-03-27 株式会社ダイセル リグノセルロース誘導体組成物及びその製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008500426A (ja) 2004-05-26 2008-01-10 ダウ グローバル テクノロジーズ インコーポレイティド 低分子量エチルセルロースの製造
JP2017520692A (ja) * 2014-07-10 2017-07-27 リーフ サイエンシーズ プロプライエタリー リミテッドＬｅａｆ Ｓｃｉｅｎｃｅｓ Ｐｔｙ Ｌｔｄ リグノセルロース系材料の加工方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014208803A (ja) * 2013-03-29 2014-11-06 ロイス・ドットコム株式会社 リグニン回収方法
JP7024953B2 (ja) * 2017-03-10 2022-02-24 国立大学法人京都大学 化学修飾リグノセルロースの熱圧成形体、及びその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008500426A (ja) 2004-05-26 2008-01-10 ダウ グローバル テクノロジーズ インコーポレイティド 低分子量エチルセルロースの製造
JP2017520692A (ja) * 2014-07-10 2017-07-27 リーフ サイエンシーズ プロプライエタリー リミテッドＬｅａｆ Ｓｃｉｅｎｃｅｓ Ｐｔｙ Ｌｔｄ リグノセルロース系材料の加工方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GREEN CHEM., vol. 22, 2020, pages 2909 - 2928
See also references of EP4431569A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025063308A1 (ja) * 2023-09-22 2025-03-27 株式会社ダイセル リグノセルロース誘導体組成物及びその製造方法

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US20250002697A1 (en) 2025-01-02
EP4431569A1 (en) 2024-09-18
EP4431569A4 (en) 2025-10-15
JPWO2023084650A1 (https=) 2023-05-19
CN118202002A (zh) 2024-06-14

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