Polyolefins thermally degradable polyethylene

For both polyethylene and its many copolymeric variants and polypropylene, the main thermal degradative routes follow initial random chain scission. These reactions are only slightly affected by the differences in the physical structure such as crystallinity, but are influenced by the presence of impurities. However, it is largely true that while these may influence the proces-sibility and long-term stability of respective polyolefins, they may have little or no effect on the flammability. 

Thermal processes are mainly used for the feedstock recycling of addition polymers whereas, as stated in Chapter 2, condensation polymers are preferably depolymerized by reaction with certain chemical agents. The present chapter will deal with the thermal decomposition of polyethylene, polypropylene, polystyrene and polyvinyl chloride, which are the main components of the plastic waste stream (see Chapter 1). Nevertheless, the thermal degradation of some condensation polymers will also be mentioned, because they can appear mixed with polyolefins and other addition polymers in the plastic waste stream. Both the thermal decomposition of individual plastics and of plastic mixtures will be discussed. Likewise, the thermal coprocessing of plastic wastes with other materials (e.g. coal and biomass) will be considered in this chapter. Finally, the thermal degradation of rubber wastes will also be reviewed because in recent years much research effort has been devoted to the recovery of valuable products by the pyrolysis of used tyres. 

Shebani et al. [20] noted that removing extractives improved the thermal stability of different wood species. Therefore, using extracted wood for the production of wood-plastic composite (WPCs) would improve the thermal stability of WPCs. Because wood and other bio-fibres easily undergo thermal degradation beyond 200°C, thermoplastic matrix used in the composites is mainly limited to low-melting-temperature commodity thermoplastics like polyethylene (PE) and polypropylene (PP). However, the inherently unfavourable thermomechanical and creep properties of the polyolefin matrix limit some structural applications of the materials. 

Polyolefin melts under excessive loads are subject to mechanically and oxidatively activated chain cleavage. Polyolefins do not depolymerize. Polyethylene and polypropylene are relatively insensitive to purely thermal degradation, but react easily with oxygen and radicals. Under mild conditions and the presence of oxygen, oxidation is preferred to thermal degradation due its lower level of activation energy (oxidation PE approx. 96 kj/mol vs. thermal degradation PE approx. 264 kj/mol) [20]. 

Polymers, particularly polyolefins, start to decompose at significantly lower temperatures under the same conditions because some weak sites, such as unsaturated groups and branching points, deaease the dissociation energy of C-C bonds." As an example, the thermal degradation of linear polyethylene in ox5 en-firee environment starts with random scission of the polymer chains preferentially in allylic positions... 

Recently the pyrolysis of polymer mixtures has become a focus of interest due to the increasing role of plastics recycling. Many researchers have investigated the thermal decomposition of various polymers in the presence of PVC. Kniimann and Bockhom [25] have studied the decomposition of common polymers and concluded that a separation of plastic mixtures by temperature-controlled pyrolysis in recycling processes is possible. Czegfny et al. [31] observed that the dehydrochlorination of PVC is promoted by the presence of polyamides and polyacrylonitrile however, other vinyl polymers or polyolefins have no effect on the dehydrochlorination. PVC generally affects the decomposition of other polymers due to the catalytic effect of HCI released. Even a few per cent PVC has an effect on the decomposition of polyethylene (PE) [32], HCI appears to promote the initial chain scission of PE. Day et al. [33] reported that PVC can influence the extent of degradation and the pyrolysis product distribution of plastics used in the... 

N.S. Allen, A. Parkinson, F.F. Loffelman, and P.V. Susi, Photo-stabilizing action of a p-hydroxybenzoate compound in polyolefins. Part II. Thermal and photochemical behavior in high density polyethylene film, Polym. Degrad. Stab. 1984, 6, 65-79. 

Though there are metals other than copper (such as iron, manganese and cobalt) that can accelerate thermal oxidation of polyolefins and related polymers such as EPDM, in practice, however, the inhibition of copper-catalyzed degradation of polyolefins is of paramount importance because of the steadily increasing use of polyolefin insulation over copper conductors. Among polyolefins, polyethylene is still the most common primary insulation material for wire and cable. In the United States, high-density polyethylene and ethylenepropylene copolymers are used in substantial amounts for communications wire insulation. 

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