Thermal degradation depolymerization

Thermal degradation occurs when a polymer is exposed to an elevated temperature in an inert atmosphere under exclusion of other compounds. The resistance against such degradation depends on the nature and the inherent thermal stability of the polymer backbone. There are three main types of thermal degradation depolymerization, random chain scission, and unzipping of substituent groups. 

The mass spectrum of polymeric sulfur S, prepared from either liquid sulfur or by extraction of commercial flowers of sulfur , has been measured and interpreted in terms of Ss, Sy, and Ss molecules leaving the polymer on heating and depolymerization [203]. This result is in agreement with depolymerization studies in solution which also show Ss and Sy as the major thermal degradation products [174]. 

The addition of heat shifts the equilibrium concentrations away from the products and back towards the reactants, the monomers. This is one reason why processing these types of polymers is often more difficult than processing products of chain growth mechanisms. The thermal degradation process can be dramatically accelerated by the presence of the low molecular weight condensation products such as water. Polyester, as an example, can depolymerize rapidly if processed in the presence of absorbed or entrained water. 

Depolymerization can result in backbone degradation and/or in the formation of cyclic or other products. The thermal degradation of PVA and PVC occurs with the splitting of water... 

Zn(R-dtp)2 complexes have been characterized and their thermal stabilities investigated 173,184,190,297-299,301-305) Zn(R-dtp)2 compounds are thermally degraded to volatile olefins and non-volatile residues and this serves as the basis for gas chromatographic determination of the compounds 304,30s) Several papers describing pyrolyses of Zn(R-dtp>2 complexes have discussed mechanisms for formation of olefins, sulfides, and other products 173,184,190,298,299, 304) Dakternieks and Graddon i8s,283)35 mentioned earlier, have reported thermodynamic measurements for depolymerization and adduct formation reactions of zinc, cadmium and mercury R-dtp compounds. 

Depolymerization is a special case of thermal degradation. It can be observed particularly in polymers based on a, a -disubstituted monomers. In these, degradation is a reversal of the synthesis process. It is a chain reaction during which the monomers are regenerated by an unzipping mechanism. This is due to the low polymerization enthalpy of these polymers. For the thermal fission of polymers with secondary and tertiary C-atoms, higher energies are required. In these cases elimination reactions occur. This can be seen very clearly in PVC and PVAC. 

Pyrolysis is the process of thermal degradation of a substance into smaller, less complex molecules. Many processes exist to thermally depolymerize tires to salable products. Almost any organic substance can be decomposed this way, including rice hulls, polyester fabric, nut shells, coal and heavy crude oil. Pyrolysis is also known as destructive distillation, thermal depolymerization, thermal cracking, coking, and carbonization. 

TABLE 15.1 List of Polymers That Depolymerize during Thermal Degradation"... 

In cases where no additional oxygen is present, polystyrene can undergo nearly pure thermal degradation. The two prevalent mechanisms are sequential elimination of monomer units, which is called unzipping or depolymerization. In this case, styrene monomer is formed. Random chain scission can also occur. It is sometimes combined with unzipping at the reactive broken chain ends. At temperatures approaching 300 °C, up to 40 % of a polystyrene molecule can be converted to styrene monomer. 

While condensation polymers such as PET and polyamides can be broken down into their monomer nnits by thermal depolymerization processes, vinyl (addition) polymers snch as polyethylene and polypropylene are very difficnlt to decompose to monomers. This is becanse of random scission of the carbon-carbon bonds of the polymer chains during thermal degradation, which prodnces a broad prodnct range. 

Thermal degradation of plastics can be classified as depolymerization, random decomposition and mid chain degradation [54, 55], In the process of depolymerization, the conjunction bonds between monomers are broken up, which leads to the forming of monomers. Depolymerization type plastics mainly include a-polymethyl styrene, polymethyl methacrylate and polytetrachloroethylene. In the random decomposition process, scission of carbon chains occurs randomly, and low-molecular hydrocarbons are produced. Random-decomposition-type plastics include PP, PVC and so on. In most cases, both decompositions take place. To be more specific, the degradation of polyolefins can be classified as the following three types ... 

Diffusion of solutions of Cr, Co and Mn ions through a PTFE membrane allows for separation of Cr from the remaining ions. Thermal stability of polymeric materials is a significant consideration in many poly(phosphazene) applications. The kinetics of the thermal degradation of PTFE are best fit with a model requiring a two step initiation for depolymerization. These steps involve formation of defect units, such as =P(0)NH- and =P(0)N(CH2CFj)-, which become active centers for depolymerization. Mixed... 

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