A novel shortened electrospun nanofiber modified with a 'concentrated' polymer brush

We report the fabrication of shortened electrospun polymer fibers with a well-defined concentrated polymer brush. We first prepared electrospun nanofibers from a random copolymer of styrene and 4-vinylbenzyl 2-bromopropionate, with number-average molecular weight M_n=105 200 and weight-average molecular weight M_w=296 700 (M_w/M_n=2.82). The fibers had a diameter of 593±74 nm and contained initiating sites for surface-initiated atom transfer radical polymerization (SI-ATRP). Then, SI-ATRP of hydrophilic styrene sodium sulfonate (SSNa) was carried out in the presence of a free initiator and the hydrophobic fibers. Gel permeation chromatography confirmed that M_n and M_w/M_n values were almost the same for free polymers and graft polymers. M_n agreed well with the theoretical prediction, and M_w/M_n was relatively low (<1.3) in all the examined cases, indicating that this polymerization proceeded in a living manner. Using the values of the graft amount measured by Fourier transform infrared spectroscopy, the surface area, and M_n, we calculated the graft density σ as 0.22 chains nm^-2. This value was nearly equal to the density obtained on silicon wafers (σ=0.24 chains nm^-2), which is categorized into the concentrated brush regime. Finally, we mechanically cut the fibers with a concentrated poly(SSNa) brush by a homogenizer. With increasing cutting time, the fiber length became shorter and more homogenous (11±17 μm after 3 h). The shortened fibers exhibited excellent water dispersibility owing to the hydrophilic poly(SSNa) brush layer.