Effect of sticker clustering on the dynamics of associative networks

Recent experimental and theoretical work has shown that sticker clustering can be used to enhance properties such as toughness and creep resistance of polymer networks. While it is clear that the changes in properties are related to a change in network topology, the mechanistic relationship is still not well understood. In this work, the effect of sticker clustering was investigated by comparing the dynamics of random copolymers with those where the stickers are clustered at the ends of the chain in the unentangled regime using both linear mechanics and diffusion measurements. Copolymers of N,N-dimethyl acrylamide (DMA) and pendant histidine groups were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. The clustered polymers were synthesized using a bifunctional RAFT agent, such that the midblock consisted of PDMA and the two end blocks were random copolymers of DMA and the histidine-functionalized monomer. Upon addition of Ni ions, transient metal-coordinate crosslinks are formed as histidine-Ni complexes. Combined studies of rheology, neutron scattering and self-diffusion measurements using forced Rayleigh scattering revealed changes to the network topology and stress relaxation modes. The network topology is proposed to consist of aggregates of the histidine-Ni complexes bridged by the non-associative midblock. Therefore, stress relaxation requires the cooperative dissociation of multiple bonds, resulting in increased relaxation times. The increased relaxation times, however, were accompanied by faster diffusion. This is attributed to the presence of defects such as elastically inactive chain loops. This study demonstrates that the effects of cooperative sticker dissociation can be observed even in the presence of a significant fraction of loop defects which are known to alter the nonlinear properties of conventional telechelic polymers.