Synthesis of a Macromonomer Library from High-Temperature Acrylate Polymerization

The auto‐initiated high temperature acrylate polymerization represents a versatile route for the synthesis of macromonomer building blocks. Various macromonomers were synthesized via this route based on methyl, ethyl, n‐butyl, t‐butyl, 2‐ethylhexyl, isobornyl and 2‐[[(butylamino)carbonyl]oxy]ethyl acrylate. The synthesis requires a temperature of 140 °C and is carried out in a 5 wt.‐% solution of hexyl acetate. The macromonomer library is fully characterized via electrospray ionization mass spectrometry (ESI‐MS). The amount of macromonomers containing the geminal double bond lies in between 82 and 95%, depending on the monomer type. The achievable molecular weight of the macromonomers is located between 800 and 2 000 g·mol−1 with a polydispersity of close to 1.6. In addition, it is demonstrated that radical initiators are useful add‐ons (to circumvent the inhibition time observed during initiator‐free synthesis) without interfering in the actual polymerization as no initiator‐fragment containing products are identified via high resolution mass spectrometry. A library of acrylate based macromonomers is synthesized via a facile high temperature one pot – on step procedure. The purity of the obtained macromonomers is assessed via electrospray ionization mass spectrometry (ESI‐MS) and shown to be close to 90% in all cases.