High molecular weight trans‐poly(9,9‐di‐n‐octylfluorene‐2,7‐vinylene) was prepared under reduced pressure in the presence of a well‐defined Schrock‐type catalyst, Mo(CHCMe2Ph)(N‐2,6‐Me2C6H3)[OCMe(CF3)2]2, in toluene. The effect of initial monomer concentration was found to be an important factor for preparing high molecular weight polymers with unimodal molecular weight distributions. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2463–2470, 2001

Factors affecting the syntheses of high‐molecular‐weight poly(2,5‐dialkyl‐1,4‐phenylene vinylene) by the acyclic diene metathesis polymerization of 2,5‐dialkyl‐1,4‐divinylbenzenes [alkyl = n‐octyl (2) and 2‐ethylhexyl (3)] with a molybdenum or ruthenium catalyst were explored. The polymerizations of 2 by Mo(N‐2,6‐Me2C6H3) (CHMe2 Ph)[OCMe(CF3)2]2 at 25 °C was completed with both a high initial monomer concentration and reduced pressure, affording poly(p‐phenylene vinylene)s with low polydispersity index values (number‐average molecular weight = 3.3–3.65 × 103 by gel permeation chromatography vs polystyrene standards, weight‐average molecular weight/number‐average molecular weight = 1.1–1.2), but the polymerization of 3 was not completed under the same conditions. The synthesis of structurally regular (all‐trans), defect‐free, high‐molecular‐weight 2‐ethylhexyl substituted poly(p‐phenylene vinylene)s [poly3; degree of monomer repeating unit (DPn) = ca. 16–70 by 1H NMR] with unimodal molecular weight distributions (number‐average molecular weight = 8.30–36.3 × 103 by gel permeation chromatography, weight‐average molecular weight/number‐average molecular weight = 1.6–2.1) and with defined polymer chain ends (as a vinyl group, CHCH2) was achieved when Ru(CHPh)(Cl)2(IMesH2)(PCy3) or Ru(CH‐2‐OiPr‐C6H4)(Cl)2(IMesH2) [IMesH2 = 1,3‐bis(2,4,6‐trimethylphenyl)‐2‐imidazolidinylidene] was employed as a catalyst at 50 °C. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6166–6177, 2005