Mechanisms of Degradation Step Growth Polymers

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. 

The chemical nature of the main-chain linkages of step-growth polymers makes this class of polymers particularly reactive to a wide variety of chemical species. Solvolysis reactions break the C-X bond at the polymer linkage bonds. These types of reactions are often pH-dependent, so the stability of the polymer is highly dependent on the acidity or basicity of the prodegradant. 

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