Mechanism of accelerated hydrolysis of chemically modified cellulose is developed. It was found cellulose chemically modified by some compounds such as reactive dyes are more prone to acid hydrolysis. Since the discovery, the mechanism is not well investigated. Understanding the mechanism of accelerated hydrolysis of chemically modified cellulose could not only improve mechanical strength cellulosic materials but also promote the conversion of cellulosic materials into various fine chemicals. With molar ratio of substitution on cellulose less than 1%, the overall hydrolysis rate of substituted cellulose is as 10 folds fast as that of unsubstituted cellulose. Through hydrolysis experiments and computer modeling, we believe the increased hydrolysis of cellulose is caused by lowered activation energy of hydrolysis, resulted from that negative charges on substituents stabilize intermediate of hydrolysis, oxocarbenium ions, through electrostatic interaction. Rate of hydrolysis was affected by both of distances between charged atoms or groups on substituents and oxocarbenium ions and amount of the negative charges on substituents. When the distance between charged groups and oxocarbenium ion is smaller than 5 A, negative charges on substituents have great impact on hydrolysis rate of cellulose. When such distance is between 5 A and 10 A, impact of negative charges on rate of hydrolysis decreases. When this distance exceeds 10 A, negative charges have little effect on rate of hydrolysis. Hydrolysis rates of cellulose could be tuned according to different purposes through slight modification of the constitutions of substituents.<br/>

Investigation of accelerated hydrolysis of cellulose after chemical modification

255th National Meeting (2018)

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