Determination of copolymer composition by combustion analysis for carbon and hydrogen

A detailed description is given of the method of combustion analysis for carbon and hydrogen to determine the composition of a copolymer from its carbon-hydrogen ratio. The apparatus and procedures have been developed at the National Bureau of Standards over a period of years. The method has been applied chiefly to determine what fraction of a styrene-butadiene copolymer is derived from styrene. Minor ingredients are removed by extraction, with the exception of the bound mercaptan residue for which correction must be made. The amount of bound mercaptan residue is determined from measurements of the sulfur content of the copolymer by the Carius method. Measurements are made of the oxygen content and the ash content, although these do not enter into the calculations. The standard deviation of a measurement of carbon-hydrogen ratio is approximately 0.0010 and is independent of styrene content. This corresponds to a standard deviation of about 0.036-percent bound styrene for polymers of low styrene content and 0.018 percent for polymers of high styrene content. The accuracy of the method is demonstrated by the fact that observations of carbon-hydrogen ratio for four out of five samples of polybutadiene differed by less than one standard deviation from the theoretical value.