Thermal reactions of amphotropic copolymers studied by thermogravimetry and temperature-resolved pyrolysis-field ionization mass spectrometry

The thermal degradation mechanisms of amphiphilic acrylic copolymers containing mesogenic pyrimidine side chains and hydrophilic 2‐hydroxyethyl acrylate (HEA) main‐chain spacer units were investigated by thermogravimetry (TG) and pyrolysis‐field ionization mass spectrometry (Py‐FIMS). The degradation behaviour of these polymers depends on the amount of HEA incorporated. Thermogravimetry revealed that the main decomposition occurs in a single step for the pyrimidine homopolymer, whereas with increasing HEA content a two‐step process evolves. The major products identified by Py‐FIMS are two alcohols and one olefin split from the aromatic side chains. Depolymerization is only a minor degradation pathway. The rather complex thermal behaviour can be explained by three different reaction mechanisms: (a) alcohol formation via reaction of the HEA hydroxyl groups with ester groups in the side chains, (b) intramolecular cis‐elimination forming a volatile olefin and carboxylic acid groups remaining at the polymer backbone, and (c) the reaction of these acid groups with ester bonds forming the alcohols. Steps (b) and (c) are dominant for the pyrimidine homopolymer. With increasing HEA content in the copolymers step (a) becomes more important and, in addition, chemical crosslinking occurs. The mesogenic monomer, which was also examined, polymerized under the experimental conditions and showed essentially the thermal features of the pyrimidine homopolymer.