Abstract
The theoretical study of dendrimers is reviewed, considering both analytical approaches and molecular simulation methods. We discuss the effect of molecular symmetry on the degeneracy of the relaxation times, and then the calculation of observable quantities, in particular the intrinsic viscosity, and then the viscoelastic complex modulus and the dynamic structure factor, in comparison with the available experimental data. In particular, the maximum intrinsic viscosity with increasing molar mass is analyzed in some detail. The approximations and/or assumptions of the adopted methods are also described in connection with analogous results for polymer of a different topology, in particular linear and star polymers.
Highlights
Dendrimers can be topologically described as being formed by concentric shells, or generations g growing from a central core, or branch point, with an f functionality, comprising f dendra of order m; here, m are the branches stemming from each trunk, while p bonds are present between the adjacent branch points, which have an m + 1 functionality
We briefly mention the basic features of the current analytical theories and simulations methods relevant to study the intramolecular dynamics of polymers, and we review the results obtained by these methods
In his seminal paper on the intramolecular dynamics of dendrimers, La Ferla calculated the better understand the discussion we report in Figure 3 the calculated results for a viscoelastic complex modulus for dendrimers modelled as described previously [19]
Summary
Dendrimers are a relatively new class of macromolecules that can be prepared with extremely accurate control of architecture and molecular weight, being essentially monodisperse [1,2]. Their highly branched monodisperse structures with a well-defined and highly symmetrical geometry provide stringent tests for analytical theories and molecular simulations to be compared with experimental data. Much emphasis will be placed on the intrinsic viscosity, since in dendrimers it has been found to show a maximum when plotted as a function of g This behavior is present in poly(amidoamine), or PAMAM, dendrimers emanating from two functional groups instead of a single core (usually a diethylamino, or DEA, moiety) [1,2,7], in tri-polybenzylether, or Tri-PBzE, dendrimers [8] and in phosphorous-containing dendrimers having [OC6 H4 P(Ph)2 = N-P(S)] repeat units [9]. We provide a summary and an outlook on the possible future theoretical and experimental work in this area
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