Browsing by Author "Masuelli, Frank John"

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    Solubility of cellulose nitrate as a function of the degree of polymerization
    Masuelli, Frank John (Virginia Polytechnic Institute, 1948)
    A sample of cellulose nitrate was to be fractionated into a series of fractions differing from each other with respect to the degree of polymerization. The method chosen was to be one which would give a large number of fractions, each one attaining as high a degree of homogeneity with respect to chain length as could be reached without too great refinement of procedure. The degree of polymerization of the fractions was to be determined by viscosity measurements using the Staudinger viscosity equation (109) and then using a suitable solvent, a quantitative determination of the solubility of each fraction was to be attempted. From any solubility data obtained an attempt was to be made to determine if any relationship existed between the degree of polymerization and the solubility. Solubility is dependent upon the nitrogen content of the nitrate. Therefore, the nitrogen content of each fraction was to be determined, in order to draw valid conclusions from the solubility data.
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    A study of the reaction of cellulose nitrate with various reducing agents
    Masuelli, Frank John (Virginia Polytechnic Institute, 1953)
    Cellulose nitrate does not react with diphenyl or diethyl zinc dissolved in toluene, nor does it react with diethyl tin in liquid ammonia solution. In the latter case the cellulose nitrate is converted to cellulose amine by the ammonolytic effect of the ammonia. Powdered sodium borohydride added to a dilute solution of cellulose nitrate in acetone causes immediate gelation of the ester. The gel is presumed to be formed by the reaction of the hydride with the nitrate groups of cellulose nitrate. Hydrolysis of the complex with water or glacial acetic acid yields a boron and nitrogen free derivative the nature of which is unknown. Cellulose nitrate reacts with ammonia either in the gaseous or liquid state to form cellulose monoamine. The mechanism of the process is the same in all reactions and is independent of the experimental conditions. When the reaction is carried out in the presence of ammono bases such as sodium amide the cellulose amine is considerably degraded and is soluble in water; in all other cases the amine is water insoluble. Cellulose amine in glacial acetic acid solution may be diazotized and coupled with aromatic intermediates to form stable mono-azo derivatives whose properties are independent of the physical properties of the amine. Cellulose amine is deaminated by the action of hypophosphorous acid on the cellulose diazonium salt to a desoxy cellulose containing between one and two per cent amino nitrogen. Several theories are advanced to account for the fact that complete deamination is not realized. The reaction between cellulose nitrate and di-n-butyl amine yields a cellulose di-n-butyl amine of degree of substitution between one and two. The mechanism of the reaction is presumed to be the same as that for the formation of cellulose amine. The cellulose di-n-butyl amine could not be dealkylated.