The chain behavior in a precursor solution and its condensation process are still key issues that have been paid close attention to but have not been solved yet for semirigid conjugated polymers. In this research, the chain condensation process from a dilute to a concentrated solution and the transformation of the chain conformation from a solution to a film for the conjugated polymer poly(9,9'-dioctylfluorene) (PFO) were investigated by a scaling law method obtained from rheological measurements. By establishing a scaling relationship between specific viscosity and concentration, it was found that the motion of molecular chains conformed to the Zimm model in dilute solution, and the motion of molecular chains conformed to the Rouse model in semidilute unentangled solution as well as conformed to the Edwards tube model in semidilute entangled solution. Furthermore, it was also found that toluene is a θ solvent for PFO at 25 °C. Some important physical parameters in connection with PFO intrinsic properties were also obtained here, such as intrinsic viscosity [η] = 136.84 mL g-1, root-mean-square end-to-end distance R = 41.4 nm, and Kuhn segment length b = 6.28 nm. In particular, this was the first time that the effect of the film-forming process of spin coating on the transformation proces of the PFO chain conformation from the precursor solution to a film was studied, and the spin-coating time (t) was found to be several orders of magnitude longer than the PFO chain relaxation time (τ Z(τ R)). This research enriches knowledge and understanding of the chain behavior in the precursor solution for semirigid conjugated polymers and reveals the correlation of chain behaviors in solution with the film's condensed state structure in the process of chain dynamic evolution from a solution to a film.
© 2022 The Authors. Published by American Chemical Society.