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The principal complication arising out of free radical‐initiated polymerizations involving vinyl acetate has been the chain transfer to monomer and polymer which results in a highly branched polymer chain. Some evidence has also been presented to show that the degree of branching in polyvinyl esters increases with an increasing number of carbon atoms in the vinyl ester. It was of interest, therefore, to obtain a relative measure of the chain transfer constants for successive members of the homologous series of vinyl esters and to relate the constants to the actual structure of the respective polyvinyl ester. Accordingly, the study of the chain transfer in the benzoyl peroxideinitiated polymerizations of vinyl acetate in the presence of a homologous series of ethyl esters of fatty acids was made. Chain transfer constants versus number of carbon atoms in the carboxylate portion of the fatty acid ester resulted in a linear relationship which can be expressed as where n is the number of non‐α‐methylene groups in the side chain. A concurrent study of the influence of monomer chain lengths of selected vinyl esters on molecular weight of the derived homopolymer was also carried out. The results obtained provide a basis for predicting the trends for changes in branching and degree of polymerization within the homologous series of vinyl esters.

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The degradation of cellulose in wheat straw during aqueous ethanol organosolv (AEO) treatment under different pulping conditions was investigated. For this purpose, molecular weight distribution (MWD) and degree of polymerization (DP) of the resulting cellulose pulp were determined using high performance size exclusion chromatography (HPSEC). The most pronounced effects regarding cellulose degradation were observed when varying the ethanol-to-water ratio. UV detection in HPSEC indicated that residual lignin in wheat straw fibers from organosolv treatments does not occur in free form, but rather is associated with hemicellulose (xylan) and to a minor extent also with cellulose. The established method was suitable for relative comparisons of MWD of variously treated wheat straw fibers and hence for obtaining information regarding the severity of organosolv treatment in terms of cellulose degradation. In summary, AEO treatment at a low ethanol-to-water ratio favours the efficient delignification and removal of xylan from wheat straw, but this occurs at the price of a greatly reduced fiber quality in terms of DP.

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