Linear‑, Cyclic‑, and Multiblock Amphiphilic Polyelectrolytes as Surfactants in Emulsion Polymerization: Role of Topological Structure

Combining atom transfer radical polymerization (ATRP) and “click” chemistry, a set of well-defined amphiphilicblock copolymers poly(n-butyl acrylate)-b-poly(acrylic acid) (PnBA20-PAA85) with a similar chemical component, but differenttopological structures, i.e., linear-, cyclic-, and multiblock structures, were successfully prepared, characterized (size exclusionchromatography (SEC), FT-IR and 1H NMR), and used as surfactants in emulsion polymerization. Our further transmissionelectron microscopy (TEM) and laser light scattering (LLS) characterization of the resultant latex particles demonstrates all thesurfactants with different topologies can effectively stabilize the latex particles but no significant difference among the solidscontents was observed. Moreover, we have, for the f irst time, experimentally established the quantitative relation between the finalnumber of latex particles (Np) and the concentration of polymeric surfactant with different topologies (C), i.e., Np = kCα, and theorder of our measured exponent α is as follows: αmulti(1.10) > αlinear(0.81) ≥ αcyclic(0.73), indicating cyclic surfactant moleculesbehave more like small-molecule surfactants attributed to its strongest unimers extraction and diffusion ability; in contrast,multiblock surfactant molecules can act as seeds to directly nucleate to create latex particles. In addition, Np,multi > Np,linear ≥Np,cyclic at higher concentration, and Np,linear > Np,cyclic ≥ Np,multi at lower concentration was observed. Similar results (αmulti(1.02)> αlinear(0.65) ≥ αcyclic(0.58)) were also observed when polystyrene-b-poly(acrylic acid) (PS9−PAA60) copolymers were used assurfactants. Further aqueous SEC characterization shows the broad size distribution of our micellar solution has no effect onobtaining narrowly distributed latex particles. Finally, interfacial tension measurement of the micellar solution indicates,compared to multiblock structure, the rate of adsorption at a hydrophobic interface is much faster for linear and cyclic-blockstructures, agreeing with our observed order of exponent α.