Physico-chemical aspects of polyethylene processing in an open mixer. Part 24: Experimental kinetics of aldehyde and carboxylic acid formation

The experimental kinetics for carboxylic acids shows more complexity than that for ketones. The fitting of the experimental results for the initial stages to the equation consisting of a linear and a quadratic term in processing time accounts well for the ketone data but not for the acid data. Instead of that, the data for the acids show fair fit to an equation containing a linear term and another term that is cubic in processing time. In the temperature range of the experiments the linear term is practically constant. The cubic term increases strongly with temperature. The combination of a linear and a quadratic term can account for the advanced stages of processing. The corresponding quadratic term shows strong increase if the processing temperature passes from 150 to 160 °C. However, for higher processing temperatures it remains constant within experimental error. The difference carbonyl absorbance measured after treatment of the polyethylene films with ammonia corresponds to the sum of the acids and aldehydes. It shows similarly complex kinetics. Some of the difficulties encountered with the experimental kinetics cannot be resolved with the data available. It is only the comparison with the formal kinetics based on potential mechanisms of product formation that allows for better understanding of the experimental results.