New polymer architectures: Recent results with polyrotaxanes

Recent results from our laboratory have shown that the formation of polyester and polyurethane rotaxanes by polymerization in the presence of crown ethers is driven by hydrogen bonding of the OH groups with the oxygen atoms of the macrocycles. Here we summarize these findings. Then we describe the application of this type of self assembly for the production of polyrotaxanes by threading preformed macromolecules and for the controlled synthesis of branched and crosslinked systems. These latter protocols comprise a new and novel way to prepare mechanically linked, elastomeric materials. Rheological properties of main chain polyrotaxanes are compared to simple linear backbones; the rotaxanes display higher intrinsic viscosities and lower melt viscosities, reflecting larger hydrodynamic volumes and less entanglement, respectively; these are potentially useful aspects in terms of processability of this new class of polymeric materials.