Viscometric determination of dialdehyde content in periodate oxycellulose Part II. Topochemistry of oxidation

被引:65
作者
Calvini, Paolo
Conio, Giuseppina
Princi, Elisabetta
Vicini, Silvia
Pedemonte, Enrico
机构
[1] SBAP, Minist Beni Culturali, I-16126 Genoa, Italy
[2] CNR, Ist Studio Macromol, Sezione Genova, I-16149 Genoa, Italy
[3] Univ Genoa, Dipartimento Chim & Chim Ind, I-16146 Genoa, Italy
关键词
archaeometry; kinetics; low-temperature alkaline degradation; mechanism; periodate oxycellulose;
D O I
10.1007/s10570-005-9035-y
中图分类号
TB3 [工程材料学]; TS [轻工业、手工业、生活服务业];
学科分类号
0805 ; 080502 ; 0822 ;
摘要
The kinetics of periodate oxidation of cellulose was followed through the alkaline degradation of the dialdehyde groups by measuring the viscometric degree of polymerisation and the alkali consumption. The obtained results show that a fast but limited attack of periodate occurs in the amorphous region of cellulose, causing the decrease of degree of polymerisation to its levelling-off value. The alkali consumption indicates at least two further slower reactions, that lead to the asymptotic complete oxidation of cellulose units. With the pseudo first-order approximation, the oxidation half-time of these three reactions can be calculated, corresponding to 1.2, 20 and 854 h respectively. In spite of the high oxidation of the analysed samples (up to about 46%), the residue after alkaline degradation shows a relatively high value of degree of polymerisation rather than the narrow molecular weight distribution of oligomers expected from a random oxidation, thus indicating that periodate oxidises cellulose in isolated domains. The sequence of analyses over the same sample utilised in this work (titrimetry, weight loss and viscometry), performed at room temperature in mild conditions, makes it possible to investigate the topochemistry of oxidation of paper and textiles of historic and artistic value with microdistructive techniques on a single, very small fragment of material.
引用
收藏
页码:571 / 579
页数:9
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