Synthesis and Shape Control of Uniform Polymer Microparticles by Tailored Adsorption of Poly(ethylene oxide)-b-Poly(ε-caprolactone) Copolymer

This paper introduces a straightforward and robust polymerization method for the synthesis of uniform polymer microparticles having controlled surface chemistry as well as tailored particle shapes. Uniform polystyrene (PS) microparticles are produced by dispersion polymerization, in which amphiphilic poly(ethylene oxide)‐b‐poly(ε‐caprolactone) (PEO‐b‐PCL) copolymers anchor on to the growing polymer particles and stabilize them by steric repulsion. We have observed that, when PEO‐b‐PCL copolymers are incorporated at the proper concentration range, the total number of particles remains unchanged after the formation of primary particles, which is essential for maintaining size uniformity. Otherwise, nonuniform PS microparticles are produced mainly as a result of the coagulation or secondary formation of particles. To show the diversity of our particle synthesis technology, shape‐controlled microparticles, such as dimples and Janus particles, are also produced by using temperature‐mediated swelling and phase separation. Finally, we show that PEO‐b‐PCL copolymers play a key role in regulating the surface wettability of the seed particles, thereby facilitating the formation of anisotropic microparticles.