Cocrystallization of a Poly(ethylene−butene) Random Copolymer with C24 in n-Decane

Amorphous−crystalline random copolymers containing ethylene and butene (PEB) segments are known to self-assemble in solution to yield one-dimensional micellar structures, i.e., rodlike aggregates. This behavior stands in contrast with the amorphous−crystalline diblock polymers, where self-assembly leads to a core consisting of a rough textured plate of polyethylene cloaked by the amorphous component; either alternating poly(ethylene−propylene) or random poly(ethylene−butene). These materials serve as nucleation platforms for wax crystal size control in commercial formulations for middle distillate fuels. Here, we present small-angle neutron-scattering results to evaluate the influence of C 24 wax in the presence of the PEB random copolymer upon the self-assembly event. In stark contrast to the rodlike micelles the random copolymers cocrystallize with the wax in thin sheets consisting of a single paraffin layer surrounded by amorphous polymer hairs on both plate sides. Such structures have not been seen before. The polymer brush is well-defined, indicating a homogeneous distribution of the polymer in the wax-stabilized plate. It can be conjectured that this behavior may prove to be a viable mechanism regarding the development of flow improvers for waxy crude stocks.