Experimental and Monte Carlo data for the dilute-solution properties of "lightly branched" polymers (stars, combs, rings,...) are compared with the renormalization group predictions of Douglas and Freed. The comparisons focus on "universal" dimensionless ratios of the mean dimensions of lightly branched polymers, relative to those of linear polymers having the same molecular weight. Complications associated with hydrodynamic solution properties and with the effect of ternary interactions are briefly discussed. Dimensionless ratios involving the polymer second virial coefficient, A%, are also tabulated and compared with theory.
collected by filtration without cooling and washed with hot toluene twice. The product, having the composition of 9,10-bis(diphenylphosphino)phenanthrene monosulfide, was obtained in a
We present a detailed, systematic study of the linear rheological response of model comb
homopolymers consisting of linear backbone chains on which branches of the same polymer are grafted.
By using polymers of different molecular weights of backbone and branches, different number of branches,
and different chemistries, we explore the relaxation mechanisms of these polymers and find their universal
features. We apply a tube model theoretical analysis, originally developed by McLeish and co-workers,
which has been appropriately modified in order to account for the effects of the fluctuations of the free
ends of the backbone (due to the grafting procedure during synthesis) and the polydispersity on the
rheology. The satisfactory fitting of the data with the model indicates that the latter is capable of providing
a quantitative understanding of the rheology of branched polymers. More specifically, comb polymers
exhibit two distinct relaxation processes, assigned to the branches and the backbone. Relaxation proceeds
hierarchically with the grafted branches moving first. The free backbone ends contribute as extra
asymmetric branches moving via fluctuations. Finally, important issues relating to the number of grafted
branches and the possible tube dilation breakdown (which may explain the physics of the only adjustable
parameter p
2) are discussed.
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