Rapid Benzylation of Cellulose in Tetra-n-butylphosphonium Hydroxide Aqueous Solution at Room Temperature

被引：19

作者：

Abe, Mitsuru ^{[1
,2
]}

Sugimura, Kazuki ^{[1
]}

Nishiyama, Yoshiharu ^{[2
]}

Nishio, Yoshiyuki ^{[1
]}

机构：

[1] Kyoto Univ, Grad Sch Agr, Div Forest & Biomat Sci, Sakyo Ku, Kyoto 6068502, Japan

[2] Joseph Fourier Univ Grenoble, CNRS, Ctr Rech Macromol Vegetales, BP 53, F-38401 Grenoble 9, France

来源：

ACS SUSTAINABLE CHEMISTRY & ENGINEERING | 2017年 / 5卷 / 06期

基金：

日本学术振兴会;

关键词：

Cellulose; Etherification; Benzylation; Tetra-n-butylphosphonium hydroxide; Rapid reaction; ETHERS;

D O I：

10.1021/acssuschemeng.7b00492

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We found a very fast benzylation of cellulose in a tetraalkylonium hydroxide solvent system, 47% tetra-n-butylphosphonium hydroxide aqueous solution. Benzyl cellulose (BC) with a degree of substitution (DS) above 2.5 was obtained within 10 min at ambient temperature (20-25 degrees C) using similar to 9 mol equiv of benzyl bromide to the anhydroglucose unit. The highly efficient benzylation proceeded in the transiently stabilized emulsion state of the reaction system, and the product precipitated out as a solid sediment in the liquid medium. At 20 degrees C, the benzyl DS was 1.92 after 2 min, and reached 2.40 and 2.53 after 5 and 10 min, respectively. The reaction temperature had a negative correlation with the maximum DS in the explored range of 10-50 degrees C. No significant degradation of the cellulosic main chain was observed for highly substituted BCs (DS > 2.5). The solubility of BC in common organic solvents was also examined for products with various DSs.

引用

页码：4505 / 4510

页数：6

共 28 条

[1] Regioselectivity in Acetylation of Cellulose in Ionic Liquids [J].

Abe, Mitsuru ;

Sugimura, Kazuki ;

Nishio, Yoshiyuki .

CHEMISTRYSELECT, 2016, 1 (10) :2474-2478

[2] Maintenance-Free Cellulose Solvents Based on Onium Hydroxides [J].

Abe, Mitsuru ;

Kuroda, Kosuke ;

Ohno, Hiroyuki .

ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 2015, 3 (08) :1771-1776

[3] Fast and facile dissolution of cellulose with tetrabutylphosphonium hydroxide containing 40 wt% water [J].

Abe, Mitsuru ;

Fukaya, Yukinobu ;

Ohno, Hiroyuki .

CHEMICAL COMMUNICATIONS, 2012, 48 (12) :1808-1810

[4] Phosphorylated cellulose propionate derivatives as thermoplastic flame resistant/retardant materials: influence of regioselective phosphorylation on their thermal degradation behaviour [J].

Aoki, Dan ;

Nishio, Yoshiyuki .

CELLULOSE, 2010, 17 (05) :963-976

[5]

Diamantoglou M., 1992, Patent No. [U.S. Patent 1992/5171444, 19925171444]

[6] Advances in cellulose ester performance and application [J].

Edgar, KJ ;

Buchanan, CM ;

Debenham, JS ;

Rundquist, PA ;

Seiler, BD ;

Shelton, MC ;

Tindall, D .

PROGRESS IN POLYMER SCIENCE, 2001, 26 (09) :1605-1688

[7] Benzyl ethers of carbohydrates [J].

Gomberg, M ;

Buchler, CC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1921, 43 :1904-1911

[8] Unconventional methods in cellulose functionalization [J].

Heinze, T ;

Liebert, T .

PROGRESS IN POLYMER SCIENCE, 2001, 26 (09) :1689-1762

[9] PREPARATION OF TRI-O-BENZYLCELLULOSE BY THE USE OF NONAQUEOUS CELLULOSE SOLVENTS [J].

ISOGAI, A ;

ISHIZU, A ;

NAKANO, J .

JOURNAL OF APPLIED POLYMER SCIENCE, 1984, 29 (06) :2097-2109

[10] PREPARATION OF TRI-O-SUBSTITUTED CELLULOSE ETHERS BY THE USE OF A NONAQUEOUS CELLULOSE SOLVENT [J].

ISOGAI, A ;

ISHIZU, A ;

NAKANO, J .

JOURNAL OF APPLIED POLYMER SCIENCE, 1984, 29 (12) :3873-3882

← 1 2 3 →