Solid-State Olefin Metathesis: ADMET of Rigid-Rod Polymers and Ring-Closing Metathesis

Solid-state olefin metathesis of rigid-rod acyclic diene metathesis (ADMET) polymers and ring-closing metathesis (RCM) have been investigated. 1,4-Dipropoxy-2,5-divinylbenzene (4) was synthesized and used in a bulk ADMET polymerization to produce oligomers of dialkoxy poly(phenylene vinylene). The reaction was continued in the solid state, effectively doubling the molecular weight. Solid-state RCM was investigated with a variety of solid dienes and metathesis catalysts, and demonstrated in low conversions using amide diene 5 with catalysts 9, 13, and 14.