Soluble polymers with pendant 3‐en‐1‐yne groups (R) on a —[CH2—C(Me)R]n— skeleton by anionic polymerization of 2,5‐dimethylhexa‐1,5‐dien‐3‐yne

The anionic homopolymerization of 2,5‐dimethylhexa‐1.5‐dien‐3‐yne (DMDEY) was investigated by utilizing butyllithium, sec‐butyllithium, diphenylmethylsodium, and naphthalene/sodium as initiators. Soluble polymers with molecular weights up to 50 000 g/mol corresponding to M_w/M_n of 1.05 were obtained through homopolymerization with diphenylmethylsodium as initiator in THF at low temperatures. The homopolymers consist of 1,2‐linked monomer units with pendant 3‐methylbut‐3‐en‐1‐yne groups.