Fire retardants, thermal decomposition products

Electrical and electronic devices are made utilizing several various types of plastic materials, thus when discarded their waste is difficult to recycle. The plastics employed in housing and other appliances are more or less homogeneous materials (among others PP, PVC, PS, HIPS, ABS, SAN, Nylon 6,6, the pyrolysis liquids of which have been discussed above). However, metals are embedded in printed circuit boards, switches, junctions and insulated wires, moreover these parts contain fire retardants in addition to support and filler materials. Pyrolysis is a suitable way to remove plastics smoothly from embedded metals in electrical and electronic waste (EEW), in addition the thermal decomposition products of the plastics may serve as feedstock or fuel. PVC, PBT, Nylon 6,6, polycarbonate (PC), polyphenylene ether (PPO), epoxy and phenolic resins occur in these metal-containing parts of EEW. 

Fires involving materials treated with anti-ChEs or bulk pesticides stores (CM and OP) may release both the unaltered anti-ChE and thermal decomposition products. Also, certain phosphorus-based fire retardants that arc subjected to heat and flame in a fire may result in the generation of anti-ChEs and other toxic materials. Thus, although fire retardants may slow the rate of fire progression, their involvement in a conflagration may result in an increase in the toxic potency of combustion products (Purser, 1992). For example, polyurethane foams treated with a trimethylol propane polyol base containing phosphoms-based retardants formed a highly neurotoxic combustion product [irimethylolpropane phosphate (TMPP) Petajan et at., 19751. 

Sakai, T., and A. Okukubo. 1979. Application of a test for estimating the relative toxicity of thermal decomposition products. In Eire Retardant Proceedings of the European Conference on Flammability and Fire Retardants, ed. V. M. Bhatnagar, pp. 147-53. Westport, CT Technomic. 

Solutions of these fire retardant formulations are impregnated into wood under fliU cell pressure treatment to obtain dry chemical retentions of 65 to 95 kg/m this type of treatment greatly reduces flame-spread and afterglow. These effects are the result of changed thermal decomposition reactions that favor production of carbon dioxide and water (vapor) as opposed to more flammable components (55). Char oxidation (glowing or smoldering) is also inhibited. 

Mechanism. No single mechanism explains the action of all fire retardants, so they probably work through a combination of several mechanisms. The mechanisms of fire retardants in wood involve a complex series of simultaneous reactions whose products may affect subsequent reactions. Pyrolysis of cellulose involves dehydration, depolymerization, decarbonylation, decomposition of smaller compounds, condensation, and other reactions. These pyrolysis reactions occur both in the solid phase and vapor phase. Addition of fire retardants will alter the reactions however, this alteration will depend on the additives, the material, and the thermal-physical environment. The presence of oxygen adds subsequent and competitive oxidation reactions to the above series. These oxidative reactions can take place in both the solid and vapor phases. Evidence indicates that most fire retardants reduce combustible volatiles production and limit combustion to the solid phase. The best retardants also inhibit solid-phase oxidation to effectively remove the fuel from the fire. 

Since polyurethanes are frequently used in household objects, their thermal degradation and products generated during burning were studied frequently [3-5]. Among these can be included studies on polyester-urethanes [6], polyether-urethanes [7], phenol-formaldehyde urethane [8], studies on the influence of fire retardants on polyurethane decomposition [9, 10], generation of isocyanates during decomposition [11], and other studies [12-17]. Some reports on thermal decomposition of polyurethanes are summarized in Table 14.1.1. 

The thermal decomposition, combustion, and fire retardancy of PU materials have been reviewed. " Upon heating, the polymer decomposes primarily by regenerating the precursor moieties polyols, isocyanates, and amines. Complete volatilization of the resulting products is prevented by the formation of thermally stable isocyanurate rings (produced by trimerization of isocyanates) and the formation of substituted ureas (produced by the reaction of hydroxy compounds with the carbodiimides generated by dimerization of isocyanates). ... 

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