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

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Abstract

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.

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Abbreviations

α:

fractional weight loss

DAU:

dialdehyde units

DP:

viscosity average degree of polymerisation (with suffixes ac – acidity degraded samples; hmw – high molecular weight fraction; lmw – low molecular weight fraction; ox – oxidised samples; oxred – oxidised and reduced samples)

S:

number of β-alkoxy scissions

t 0.5 :

oxidation half-time

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Authors and Affiliations

  1. Ministero Beni Culturali, S.B.A.P., Via Balbi 10, Genova, I-16126, Italy

    Paolo Calvini

  2. CNR - Istituto per lo Studio delle Macromolecole, Sezione di Genova, Via De Marini 6, Genova, I-16149, Italy

    Giuseppina Conio

  3. DCCI Dipartimento di Chimica e Chimica Industriale, Università di Genova, Via Dodecaneso 31, Genova, I-16146, Italy

    Elisabetta Princi, Silvia Vicini & Enrico Pedemonte

Authors
  1. Paolo Calvini
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  2. Giuseppina Conio
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  3. Elisabetta Princi
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  4. Silvia Vicini
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  5. Enrico Pedemonte
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Correspondence to Paolo Calvini.

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Calvini, P., Conio, G., Princi, E. et al. Viscometric determination of dialdehyde content in periodate oxycellulose Part II. Topochemistry of oxidation. Cellulose 13, 571–579 (2006). https://doi.org/10.1007/s10570-005-9035-y

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  • DOI: https://doi.org/10.1007/s10570-005-9035-y

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