Macromolecules, Vol.49, No.7, 2731-2740, 2016
Structure and Dynamics of Dendronized Polymer Solutions: Gaussian Coil or Macromolecular Rod?
We investigate the conformation of well-defined dendronized polymers (denpols) based on poly(norborene) (PNB) and poly(endo-tricyde[4.2.2.0]deca-3,9-diene) (PTD) backbones employing static and dynamic light scattering. Their synthesis by ring-opening metathesis polymerization (ROMP) led to fully grafted and high molecular weight denpols with narrow polydispersity. In dilute solutions, the persistence lengths were estimated by static (radius of gyration) and dynamic (translational diffusion) chain conformational properties of the denpols and were compared to their homologue precursor PNB. The conformation of denpols with a third generation side dendron conforms to a semiflexible chain with a persistence length of about 6-8 run, virtually independent of the contour length. In the semidilute regime, the thermodynamics and cooperative diffusion of denpols resemble the behavior of the precursor solutions as described by the scaling theory of flexible polymers above the crossover concentration. The assumption of extremely high chain rigidity for this class of polymers is clearly not supported, at least for the third generation dendron.