Core/Shell and Hollow Ultra High Molecular Weight Polyethylene Nanofibers and Nanoporous Polyethylene Prepared by Mesoscopic Shape Replication Catalysis

Abstract

Polyvinyl alcohol (PVA) nanofibers, produced by electrospinning, represent attractive high‐surface‐area supports for olefin polymerization catalysts. Tethered with metal alkyls, PVA nanofibers immobilize a great variety of transition metal compounds, thus producing highly active nanofiber‐supported Ziegler‐, metallocene‐, and post‐metallocene catalysts. Whereas most conventional heterogeneous polymerization catalysts form particles, PVA‐nanofiber‐supported catalysts enable polyolefin nanofiber and nanostructure formation by mesoscopic shape replication using electrospun nanofibers as templates. At low ethylene pressure, linear correlation between average PE/PVA core/shell fiber diameter and polymerization time are made. At elevated pressure, this control is lost, accounting for the formation of reactor blends consisting of PE granules and built‐in PE/PVA nanofibers. Whereas conventional catalysts produce micrometer‐sized particles of ultrahigh molecular weight PE (UHMWPE), PVA‐nanofiber supported chromium catalysts afford new families UHMWPE materials. They range from UHMWPE/PVA core/shell nanofibers and nonwovens to hollow UHMWPE fibers and nanoporous UHMWPE, obtained by removing the PVA component.