Acyclic Diene Metathesis Polymerization of Divinylarenes and Divinylferrocenes with Grubbs-Type Olefin Metathesis Catalysts

1,4-Di(2-ethylhexyl)2,5-divinylbenzene, 1,4-di(2-ethylhexyloxy)-2,5-divinylbenzene, and 9,9-di(2-ethylhexyl)-2,7-divinylfluorene were synthesized from the respective dialdehydes and ADMET polymerized using Grubbs II or Grubbs−Hoveyda−Grela-type olefin metathesis catalysts. The continuous removal of ethene under a dynamic vacuum of 20 mbar at elevated temperatures in high boiling solvents (1,2-dichlorobenzene) resulted in the formation of long-chain poly[2,5-di(2-ethylhexyl)- p -phenylenevinylene] ( M n > 100 kDa, P n = 330, M w / M n = 3.1) and poly[9,9-di(2-ethylhexyl)fluorenyl-2,7-vinylene] ( M n > 70 kDa, P n = 178). The PPV forms a free-standing film after evaporation of a toluene solution. 1,3-(Diisopropenyl)ferrocene could not be polymerized in this manner; ferrocene-containing polymers were obtained with 1,1′-di(4-vinylphenyl)-3,3′,4,4′-tetramethylferrocene.