| Abstract: | The surface chemical structures of a series of novel poly(ortho ester) homopolymer and copolymer films prepared using N-methyl- and N-phenyl-ethanolamine (MDE and PDE) have been investigated using time-of-flight secondary ion mass spectrometry (ToF-SIMS). Systematic fragmentation patterns were observed within the ToF-SIMS spectra up to m/z = 1600, which were readily interpreted in terms of the polymer structures. Cations were detected which could be assigned to structures arising from the diols, the ortho ester species and diads, triads etc. of the monomer, from both the homopolymer and the random portion of the copolymer chains. The analysis of the proposed ion structures suggested two major mechanisms of fragmentation based on the cleavage of the ortho ester bonds involving either the exocyclic or the endocyclic alkoxy group. The Tof-SIMS peak area ratios for ions diagnostic of the diols and the ortho ester species reflected the bulk copolymer composition in a semi-quantitative fashion. The observation of such relationships for high mass cations (up to m/z = 500) is particularly noteworthy and has not been reported previously. These studies allow a dramatic insight into the surface chemical structure of these poly(ortho esters), information which has formed the foundation of current investigations on the mechanisms of the acid-catalysed surface degradation of these polymers. |
