Chemical oxidative degradation polypropylene

Oxidative degradation of polypropylene chemically incorporates oxygen to the polymeric chains. Why would an isotactic polypropylene be less susceptible to this type of degradation than one that is atactic ... 

The chemical structure of the polyolefins determines their susceptibility to oxidative degradation. Linear polyethylene, in the absence of additives, is more resistant to oxidation that polypropylene that oxidizes rather readily due to the presence of labile tertiary hydrogens. It was demonstrated, for instance, that the molecular weigh of polypropylene sheets in a 138°C oven can drop from 250,000 to approximately 10,000 in 3 h [522]. The process of oxidation was shown to take place according to the following scheme [522] ... 

Molecular oxygen, O2, readily reacts with free radicals, and since free radicals play a dominant role in the radiolysis of polymers, O2 can significantly affect radiation-induced chemical alterations. For instance, it enhances the radiation-induced degradation of most polymers. Linear polymers, including polyethylene, polypropylene, polystyrene and poly(vinyl chloride), that crosshnk in the absence of oxygen undergo predominantly main-chain scission in its presence. As a typical example, a free-radical-based reaction mechanism proposed for the oxidative degradation of polyethylene is shown in Scheme 5.16. 

Polypropylene differs from polyethylene in its chemical reactivity because of the presence of tertiary carbon atoms occurring alternately on the chain backbone. Of particular significance is the susceptibility of the polymer to oxidation at elevated temperatures. Some estimate of the difference between the two polymers can be obtained from Figure 1J.7, which compares- the rates of oxygen uptake of eaeh polymer at 93°C. Substantial improvements can be made by the inclusion of antioxidants and such additives are used in all commercial compounds. Whereas polyethylene cross-links on oxidation, polypropylene degrades to form lower molecular weight products. Similar effects are noted... 

Metal oxide semiconductor chemical sensors in combination with MDA have been shown to be useful to estimate the oxidative stability of polypropylene during processing instead of traditional melt flow index analysis (50). An array of sensors was used to receive a detailed analysis of volatiles. At quality measurements of different poly(butylene adipate)s the use of indicator products has been proven better than analyses of the decrease in molecular weight or mass loss for early degradation detection. Adipic acid, quantified using gas chromatography, was then used as the indicator product [51]. 

Mahoney et a/.87 have described the reaction of polyurethane foam and superheated water at 200 °C for 15 min, which leads to toluene diamines and polypropylene oxide. Hydrolysis of polyurethane and rubber mixtures has been used as a method not only of recovering valuable chemicals from the polyurethane fraction, but also to separate the polymers because rubber is inert to hydrolysis.89 The degradation takes place by contact with saturated steam at 200 °C for 12 h. This process may find particular applications in the treatment of rubber/polyurethane laminations. 

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