Coupling Kinetic Modelling with SAOS and LAOS Rheology of Poly(n-butyl acrylate).

A kinetic model based on fundamentals of radical polymerization and literature known rate parameters for the polymerization of n-butyl acrylate is validated against molecular analysis and rheological data. The model is used to predict conversion, molar mass distribution, and branching densities in form of short and long chain branching. Rheological measurements of synthesized model polymers are evaluated along the Carreau-Yasuda and Van Gurp-Palmen presentations, allowing to detect small differences in the degree of long chain branching. Contributions of anharmonics to viscoelastic response in large amplitude oscillations are small and differences between the products are dominated by the differences in molar mass.

Connecting the complex microstructure of LDPE to its rheology and processing properties via a combined fractionation and modelling approach.

Well-defined mini-plant low density polyethylene samples were fractionated preparatively according to their crystallizability via preparative temperature rising elution fractionation and according to molecular weight via preparative solvent gradient fractionation (pSGF). Rheology of the fractions was measured in both the small amplitude oscillatory shear (SAOS) and the non-linear extension regimes. The linear and non-linear rheology of the pTREF fractions were dominated by molecular weight effects, while the impact of the higher degree of long chain branching for the pSGF fractions with higher molecular weights was observed in van Gurp-Palmen plots and in strain hardening behavior in the extensional rheology measurements. Additionally, the experimental fractionation process was mimicked via modelling. The branching topologies of the bulk samples were obtained by coupled kinetic and Monte Carlo calculations. These topologies were fractionated computationally and the result were used to predict the rheological behavior of the individual fractions by applying the BoB algorithm with no parameter adjustment. The experimental observed trends were predicted by the model and the overall agreement was acceptable. This study demonstrates, that polymer fractionation is possible on a preparative scale and allows for the polymer flow properties characterization of the individual fractions, a method that is highly relevant during processing. Moreover, the fractionation process is followed and understood from the modelling point of view.