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Abstract  

Vinylidene chloride copolymers containing a predominance of vinylidene chloride (85-90%) have long been important barrier polymers widely used in the plastics packaging industry. These materials display excellent barrier to the ingress of oxygen and other small molecules (to prevent food spoilage) and to the loss of food flavor and aroma constituents (to prevent flavor scalping on the supermarket shelf). While these polymers have many outstanding characteristics, which have made them commercial successes, they tend to undergo thermally-induced degradative dehydrohalogenation at process temperatures. The dehydrochlorination occurs at moderate temperatures (120-200C) and is a typical chain process involving initiation, propagation and termination phases. Defect structures, namely internal unsaturation (allylic dichloromethylene groups), serve as initiation sites for the degradation. These may be introduced during polymerization or during subsequent isolation and drying procedures. If uncontrolled, sequential dehydrohalogenation can lead to the formation of conjugated polyene sequences along the polymer mainchain. If sufficiently large, these polyenes absorb in the visible portion of the electromagnetic spectrum, and give rise to discoloration of the polymer. The dehydrochlorination process may be conveniently monitored by thermogravimetric techniques. Both initiation and propagation rate constants may be readily obtained.

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Abstract  

Thermogravimetry is often used to study polymer degradation. Most often the information obtained may have some practical application but is of limited value for the determination of fundamental processes which may be occurring. A kinetic expression or activation parameters for a complex process which may involve consecutive or parallel reactions provides almost no information about any of the reactions that might be occurring. However, for single, well-defined processes, thermogravimetry, in conjugation with other analytical methods, can be effectively utilized in the determination of reaction mechanism. The thermal degradation of vinylidene chloride barrier polymers corresponds to the elimination of hydrogen chloride initiated at an allylic dichloromethylene unit in the mainchain. This process is uncomplicated by competing reactions. Thermogravimetry may be utilized to obtain meaningful rate constants and activation parameters for the degradation. This in conjunction with mass spectral analysis of evolved gas, characterization of both the polymer and degradation residue by ultraviolet, infrared and 1H and 13C NMR spectroscopy, and the study of model compounds has permitted a detailed description of the degradation process. General purpose poly(styrene) is a commodity polymer widely used in the food packaging industry as well as many others. If processed at excessively high temperature, it undergoes thermal degradation to expel styrene monomer which can impart negative flavor and aroma characteristics to packaged food items. The degradation reaction has been fully detailed using thermogravimetry in conjugation with evolved gas analysis, size exclusion chromatography and NMR spectroscopy.

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