Pyrolysis after polymer derivatization

Analytical pyrolysis of certain polymers and copolymers do not provide too much relevant information because of the rapid decomposition of the groups specific to that polymer. For example, the copolymers with maleic anhydride (see e.g. Sections 5.1 and 5.9) generate mainly CO2 from the maleic anhydride units. For the identification and for other studies on these types of polymers or copolymers, a polymer derivatization prior to pyrolysis can be applied [71]. For example, poly(allylamine) can be derivatized with acetonylacetone in a water solution by adding a NaOH. The reaction leads to the formation of poly(N-allyl-2,5-dimethylpyrrole) as shown below  

Pyrolysis of the resulting polymer provides more information on the initial polymer structure than the pyrolysis of the underivatized polymer. 

Another example where polymer derivatization prior to pyrolysis provides benefits regarding structural information is that of poly(ethylene-a/f-carbon monoxide) (see Section 5.8). This copolymer can be derivatized with methyl amine in a reaction as follows  

Pyrolysis of the resulting polymer generates a series of pyrrole derivatives diagnostic for the nature of the copolymer. Similar derivatization with methylamine can be performed on copolymers containing maleic anhydride [72]. 

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