Abstract
The mechanisms of thermal degradation of poly(ether‐ketone) (PEK) and four poly(ether‐ketone)/poly(ether‐sulfone) copolymers (PEK/PES) have been investigated by direct pyrolysis‐mass spectrometry (DPMS). Several families of pyrolysis compounds with H, OH and CHO end‐groups have been identified in the pyrolysis mass spectra of PEK. All these pyrolysis compounds can arise from degradation mechanisms involving cleavages of the bridged groups (diphenyl ether and dibenzophenone units). Our data show that the main degradation products of PEK are aldehydes, most likely formed by an intramolecular thermal cleavage of benzophenone units. Compounds containing dibenzofuran units have also been observed in the DCI mass spectrum of PEK. The thermal decomposition of a low molecular weight PEK sample occurs in two stages with the maxima of decomposition at 390°C and 490°C, respectively. This fact indicates the occurrence of an end‐group initiated thermal decomposition in the early degradation stage which is not present in the case of the high molecular weight PEK sample. The pyrolysis of PEK does not produce compounds containing biphenyl units, indicating that extrusion of carbonyls or recominbation processes are not involved. The thermal degradation compounds of the PEK/PES copolymers originate from the thermal cleavage of the bridge groups (diphenyl ether, benzophenone and diphenyl sulfone). The pyrolysis mass spectra of 1:1 (alt.), 1:1 (random), 3:1 and 1:3 PEK/PES copolymers appear essentially identical (apart for obvious differences in peak intensities), indicating that the molecular rearrangements (SO~2~ extrusion, transesterification, cleavage of bridges) which occur at higher temperatures and/or in the pyrolysis processes are able to randomize the distribution of comonomer units originally present in the copolymers. Differences in peak intensities have been found to reflect almost quantitatively the molar composition of the copolymers.