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Simplified hydrolysis of cellulose and substituted cellulose: Observations on trifluoroacetic acid hydrolyses
Author(s) -
Rowland Stanley P.,
Howley Phyllis S.
Publication year - 1989
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1989.070370825
Subject(s) - trifluoroacetic acid , hydrolysis , sulfuric acid , chemistry , cellulose , acid hydrolysis , organic chemistry , polymer chemistry , chromatography
Abstract Hydrolyses of selected soluble polysaccharides (e.g., polyoses) and disordered and crystalline celluloses, each bearing 2‐diethylaminoethyl (DEAE) substituents at low degree of substitution (DS < 0.05) were explored in 100% and 2 N trifluoroacetic acid (TFA). Analyses were evaluated relative to hydrolysis with 72% sulfuric acid. DEAE–polyoses hydrolyzed readily in 100% and 2 N TFA during extended reaction periods with complete liberation of DEAE–glucoses. Hydrolyses of cellulose and DEAE–celluloses in 100% TFA were critically dependent upon cautious incremental dilution of the TFA during stepwise reaction to avoid precipitation of incompletely hydrolyzed products. DEAE–celluloses were partially solubilized and hydrolyzed in heterogeneous reaction in 2 N TFA at 121°C. Complete liberation of DEAE‐glucoses in the solubilized components was achieved after supplementary hydrolysis at 121°C. In all hydrolyses, including those with 72% sulfuric acid, extended hydrolyses were essential for complete liberation of the 2‐O‐ and 6‐O‐DEAE–glucoses. Under optimum conditions, results of hydrolyses in 100% TFA were comparable to those in 72% sulfuric acid. Ease of release of DEAE‐glucopyranoses in hydrolyses of DEAE‐cellulose in 2 N TFA was in the same order (3‐O‐ > 6‐O‐> 2‐O‐) as in homogeneous hydrolyses in sulfuric acid and in 100% TFA. Differences in release of isomeric DEAE–glucoses were greater in the heterogenous system. Degradation of glucose and DEAE–glucopyranoses occurred in extended periods of reaction in all acidic media. Rates of degradation of glucose and DEAE–glucopyranoses in dilute acid at 100°C were similar for glucose and 6‐O‐DEAE–glucose. The rates were about half as fast for 3‐O‐DEAE–glucose and an order of magnitude lower for 2‐O‐DEAE–glucose.