Functionalization of cellulosic materials by TEMPO-mediated oxidation under aqueous media

水介质下 TEMPO 介导的氧化对纤维素材料进行功能化

• 批准号: 11660160
• 负责人: ISOGAI Akira
• 金额: $ 2.24万
• 依托单位: THE UNIVERSITY OF TOKYO
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11660160/
• 关键词: Cellulose; Chitin; TEMPO; Biodegradability; Oxidation; Functionalization; Biometabolizability; Polyuronic acid; セロウロン酸; カルボキシル基; グルクロン酸

A.Depolymerization of cellulose during the TEMPO-mediated oxidation must be controlled as possible in order to prepare water-soluble cellouronic acid (β-1, 4-linked polyglucuronic acid) having various molecular weights. Then depolymerization mechanism of cellouronic acid during the oxidation was studied under various conditions by changing combinations of the reagents added. Molecular weights of the products were determined by size exclusion chromatography using aqueous GPC columns and 0.1N NaCl as an eluent. The results showed that some radicals formed in the oxidation medium consisting of TEMPO and NaBrO during the oxidation were likely to bring about remarkable depolymerization. β-Elimination had little influence on the depolymerization.B.The addition of t-butylphenol as a radical scavenger to the oxidation medium could avoid the depolymerization to some extent, although neither MgCl_2 nor sodium dithonite had the effect.C.When higher molecular weight regenerated celluloses, such as hollow fibers prepared from linters by cupriammonium solutions, were used as the starting materials for the TEMPO-mediated oxidation, correspondingly higher molecular weight cellouronic acids were prepared.D.α-Chitin, β-chitin, amylose, amylopectin, curdlan and pullulan were selectively oxidized at their C6 primary hydroxyl groups to give the corresponding water-soluble polyuronic acids quantitatively by the TEMPO-mediated oxidation.E.Cellouronic acid was hydrolyzed to glucuronic acid by crude cellulase treatments, and thus cellouronic acid had both biodegradability and biometabolizability.

A.在速度介导的氧化过程中纤维素的聚合必须尽可能控制，以制备具有各种分子量的水溶性纤维素酸（β-1，4-连接的聚葡萄糖酸）。然后在各种条件下通过更改添加的试剂组合来研究纤维素酸在氧化过程中的沉积机理。产品的分子量是通过使用GPC柱和0.1N NaCl作为洗脱液的尺寸排除色谱法确定的。结果表明，在氧化过程中由速度和纳布罗组成的氧化培养基中形成的一些自由基可能会导致显着的沉积。 β-静脉对沉积几乎没有影响。制备氧化，相应地提高分子量的铜含量。D。α-chitin，β-胰蛋白，淀粉蛋白，淀粉蛋白链氨基蛋白，凝血蛋白，凝乳素和丙烷在其C6原发性羟基上被选择性地氧化，以通过温度介导的氧化氧化氧化氧化，从粗纤维素酶处理，因此生物降解性和生物代表性均具有生物降解性。

项目成果

Isogai, Kato, Y., Kitaoka, T.and Onabe, F.: "TEMPO-mediated oxidation of cellulose"Proceedings of the 10^<th> ISWPC, Yokohama, June. 640-643 (1999)

Isogai，Kato，Y.，Kitaoka，T.和Onabe，F.：“TEMPO介导的纤维素氧化”第10届ISWPC会议记录，横滨，6月。

Kitaoka, T., Isogai, A.: "Rosin sizing of pulps modified by TEMPO-mediated oxidation"Nordic Pulp and Paper Research Journal. 15(発表予定). (1999)

Kitaoka, T., Isogai, A.：“TEMPO 介导的氧化改性的松香施胶”Nordic Pulp and Paper Research Journal 15（待出版）。

Kitaoka,T., et al.: "Rosin sizing of pulps modified by TEMPO-mediated oxidation"Nordic Pulp and Paper Research Journal. 15. 177-182 (2000)

Kitaoka,T., et al.：“通过 TEMPO 介导的氧化改性的纸浆松香施胶”Nordic Pulp and Paper Research Journal。

Kato,Y., et al.: "Biodegradation of β-1,4-linked polyglucuronic acid (cellouronic acid)"Cellulose. 8(in press). (2001)

Kato, Y. 等人：“β-1,4-连接的聚葡萄糖醛酸（纤维醛酸）的生物降解”纤维素 8（出版中）。

Kitaoka,T., et al.: "Chemical modification of pulp fibers by TEMPO-mediated oxidation"Norbic Pulp and Paper Research Journal. 14. 274-279 (1999)

Kitaoka,T., et al.：“通过 TEMPO 介导的氧化对纸浆纤维进行化学改性”Norbic 纸浆和造纸研究杂志。