Structurally highly uniform poly(butyl acrylate) macromonomers are conveniently synthesized via autoinitiated free‐radical polymerization at high temperatures in solution of butyl or hexyl acetate without the need to employ any mediating agent. ESI‐MS analysis reveals that neither the primary initiating radical nor the empoyed solvent has a large impact on the product distribution. It is further demonstrated that the mechanism of their formation relies on complex addition‐fragmentation equilibria not unlike the RAFT mechanism effectively resulting in a self‐organization of the reaction. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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The products of the thermal degradation at 95 °C over 10 months of ω‐saturated and non‐saturated poly(methyl methacrylate) (pMMA) model compounds were identified with high accuracy via quadrupole ion trap and quadrupole ion trap‐time of flight (Q‐ToF) mass spectrometry. Analysis of the samples taken via these techniques indicated that degradation of vinyl terminated pMMA proceeds via the incorporation of oxygen via the formation of ethylene oxide type end groups, which subsequently rearrange under the expulsion of formaldehyde and 2‐oxo‐propionic acid methyl ester. The corresponding saturated model compounds were demonstrated to be stable over the same time period. The present findings highlight for the first time that poly(methyl methacrylate) degradation does not necessarily and exclusively proceed via radical intermediates.