Several samples of a recently developed olefin multiblock copolymer were studied by means of rheology, differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS). The synthesis involves a chain shuttling agent (CSA) that switches the growing chain between two catalysts, one that favors the incorporation of an R-olefin comonomer and one that suppresses incorporation. The data were used to determine the effect of octene comonomer content and CSA level on rheological behavior and the occurrence of mesophase separation transition (MST) in the melt. To distinguish between crystallization and MST, we made calorimetry scans and measured the density and rheological properties over a range of temperatures. Small angle X-ray scattering analysis of a sample that had undergone planar extensional flow revealed strong alignment of lamellar mesodomains, which maintained their alignment after annealing. This result confirmed the hypothesis based on rheological evidence that a lamellar mesophase is present in the melt at temperatures well above the melting point.
The structural details of a set of highly entangled H-shaped polybutadienes (PBDs) prepared by anionic polymerization were examined in detail by three reputable laboratories using size exclusion chromatography (SEC) and temperature gradient interaction chromatography (TGIC). While SEC data indicated that samples having the desired structures (i.e., nearly monodisperse H-shaped polymer) had been produced, additional SEC data from other laboratories showed that the samples were structurally more complex than originally thought. TGIC data revealed that while the samples did not contain high molecular weight byproducts, they did contain low molecular weight byproducts. To discern these structural details of the branched PBDs, small amounts of sample were fractionated by TGIC. By combining knowledge of the polymerization process with the TGIC data of fractionated samples, it was possible to work out the detailed compositions of the samples and the branching structures of each component.
Two tube-based molecular models, the hierarchical 3.0 model and the branch-on-branch model were evaluated for their abilities to predict the behavior of a series of polydisperse, H-shaped, 1,4-polybutadienes. The samples had been synthesized using a novel technique designed to suppress the generation of high molar mass by-products. While size exclusion chromatography data indicated that the samples were monodisperse, low molar mass by-products were later revealed by temperature gradient interaction chromatography. Viscoelastic data were obtained at temperatures ranging from −75 °C to 25 °C, and the samples were found to be thermorheologically simple. Sensitivity and uncertainty analyses revealed that among the model parameters, the value of plateau modulus has the strongest effect on model predictions. As molecular models improve, it will become ever more essential to evaluate them using accurate data on materials whose microstructures have been reliably established. This is especially important for materials that are structurally polydisperse.
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