Statistical properties of linear-hyperbranched graft copolymers prepared via "hypergrafting" of AB(m) monomers from...

The reaction of ABm monomers (m = 2, 3) with a multifunctional Bf-type polymer chain ("hypergrafting") is studied by coarse-grained molecular dynamics simulations. The ABm monomers are hypergrafted using the slow monomer addition strategy. Fully dendronized, i.e., perfectly branched polymers are also simulated for comparison. The degree of branching of the molecules obtained with the "hypergrafting" process critically depends on the rate with which monomers attach to inner monomers compared to terminal monomers. This ratio is more favorable if the ABm monomers have lower reactivity, since the free monomers then have time to diffuse inside the chain. Configurational chain properties are also determined, showing that the stretching of the polymer backbone as a consequence of the "hypergrafting" procedure is much less pronounced than for perfectly dendronized chains. Furthermore, we analyze the scaling of various quantities with molecular weight M for large M (M > 100). The Wiener index scales as M(2.3), which is intermediate between linear chains (M(3)) and perfectly branched polymers (M(2)ln(M)). The polymer size, characterized by the radius of gyration Rg or the hydrodynamic radius Rh, is found to scale as Rg,h ∝ M(ν) with ν ≈ 0.38, which lies between the exponent of diffusion limited aggregation (ν = 0.4) and the mean-field exponent predicted by Konkolewicz and co-workers [Phys. Rev. Lett. 98, 238301 (2007)] (ν = 0.33).