Abstract
The vast differences in material properties accessible via crosslinking of sidechain-functionalized polymers are driven by topology. For example, vulcanized rubbery networks feature intermolecular connections and loop topologies of various orders while single-chain nanoparticles (SCNPs) are comprised, in principle, entirely of primary loops. Despite this fact, precise quantification of loops in sidechain crosslinked polymers has not been accomplished. Here, it is demonstrated that by introducing cleavable linkers and mass labels onto the pendant functional groups of reactive polymers, the number of primary loops in sidechain crosslinked materials ranging from rubbery networks (gels) to soluble SCNPs can be precisely quantified. This study sheds new light on the topology of sidechain-crosslinked networks, providing design principles for augmenting the properties of this industrially and academically important class of materials through topological control.
Highlights
Junpeng Wang,a Rui Wang,b Yuwei Gu,a Alexandra Sourakov,a Bradley D
It is demonstrated that by introducing cleavable linkers and mass labels onto the pendant functional groups of reactive polymers, the number of primary loops in sidechain crosslinked materials ranging from rubbery networks to soluble single-chain nanoparticles (SCNPs) can be precisely quantified
The difference between vulcanized rubber, which is an elastic solid that is insoluble in solvents, and SCNPs, which are nano-scale soluble materials, is one of topology:[19] vulcanized rubber is formed via mostly intermolecular reactions (Fig. 1b), while SCNPs are, in principle, comprised of only primary (1) loops (i.e., “self-crosslinking” or “internal crosslinking”[20] where both ends of the A2 crosslinker are connected to the same Bf macromolecule, Fig. 1b)
Summary
Junpeng Wang,a Rui Wang,b Yuwei Gu,a Alexandra Sourakov,a Bradley D. The vast differences in material properties accessible via crosslinking of sidechain-functionalized polymers are driven by topology.
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