Rauhut–Currier Polyaddition: Self-Polymerization of Divalent Aryl Vinyl Ketones for Unsaturated Polyketones

The self-polyaddition of divalent vinyl ketones (VKs) by the Rauhut–Currier (RC) reaction is investigated to synthesize polymers composed of a carbon backbone. 2,7-Diacryloyl-9,9-dimethylfluorene is treated with 1,4-diazabicyclo[2.2.2]octane (DABCO) (20 mol %) and phenol (20 mol %), resulting in an improved degree of polymerization (Mn = 13800, Đ = 4.21). The polymerization is under kinetic control, probably due to the excellent electrophilicity of the VKs. RC polyaddition is also applicable to other divalent aromatic vinyl ketones if the corresponding polymers have sufficient solubility. For example, methylenebis(4-acryloylbenzene) is a suitable monomer for RC polyadditions. Quantitative modification of the unsaturated ketone skeletons of the polymers via thiol–ene click chemistry effectively prevents thermal curing.