Self-directed formation of uniform unsaturated macromolecules from acrylate monomers at high temperatures

An approach to self-directed formation of uniform unsaturated macromonomers (MM) from acrylate monomers at high temperature has been discussed. On the basis of a procedure to generate MM of high purities directly from the monomer without the need for endgroup modification, it was demonstrated that the growing radicals in acrylate polymerization at temperatures well above 120°C undergo a series of transfer and β-scission reactions, which are interconnected through complex dynamic equilibria. High temperature autoinitiated free radical polymerization of butyl acrylate resulted into a highly ordered product that consisted almost quantitatively of uniform macromonomeric structures. Autoinitiation provided a low radical flux aiding the MM synthesis, without requiring any initiator. This self-organized synthesis approach is highly efficient, simple, and cost and time effective as no purification and isolation steps are required, except high temperature.