A series of 2,2-bis(hydroxymethyl)propionic acid (Bis-MPA) hyperbranched aliphatic polyesters with different molecular weights (generations) is analysed for the first time by time-of-flight secondary ion mass spectrometry (ToF-SIMS). The main negative and positive low-mass fragments are identified in the fingerprint part of the spectra (m/z < 400) and are principally assigned to fragmentation of the Bis-MPA repeating units. In addition, it is shown that the fragmentation pattern is highly affected by the functional end-groups. This is illustrated for a phthalic acid end-capped hyperbranched polymer and for an acetonide-terminated dendrimer analog. Also, typical fragments assigned to the ethoxylated pentaerythritol core molecule are detected. These ions show decreasing intensities with increasing molecular weight. This intensity dependency on the generation is used to calibrate the molecular weight of hyperbranched polyesters on the surface. To obtain quantitative information, a principal component analysis WCA) multivariate statistical method is applied to the ToF-SIMS data. The influence of different normalization procedures prior to PCA calculation is tested, e.g. normalization to the total intensity, to the intensities of ions assigned to the Bis-MPA repeating unit or to intensities of fragments due to the core molecule. It is shown that only one principal component (PC1) is needed to describe most of the variance between the samples. In addition, PC1 takes into account the generation effect. However, different relationships between the PC1 scores and the hyperbranched mass average molecular weights are observed depending on the normalization procedure used. Normalization of data set ion intensities by ion intensities from the core molecule allows linearization of the SIMS intensities versus the molecular weight and allows the hyperbranched polymers to be discriminated up to the highest generations. In addition, PCA applied to ToF-SIMS data provides an extended interpretation of the spectra leading to further identification of the correlated mass peaks, such as those of the Bis-MPA repeating unit (terminal, dendritic and linear) and those of the core molecule. Finally, the work presented demonstrates the extreme potential of the static ToF-SIMS and PCA techniques in the analysis of dendritic molecules on solid surfaces. Copyright (C) 2003 John Wiley Sons, Ltd.
