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

Abstract

Dedicated to Professor Rudolf Zentel-a dedicated scientist and loving father 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.

Understanding and Modeling Polymers: The Challenge of Multiple Scales

“…The microscopic simulations are used to generate a representative sample of branched polymers, which are then fed into the theoretical machinery. The method was applied successfully by Read et al commercial Low density polyethylene (LDPE), and recently by Zentel and co-workers to predict the rheological properties of LDPE and polybutyl acrylate (PBA) from the reaction conditions in a miniplant. − …”

Kinetic Monte Carlo Simulations as a Tool for Unraveling the Impact of Solvent and Temperature on Polymer Topology for Self‐Initiated Butyl Acrylate Radical Polymerizations at High Temperatures

“…This data was used to validate first principles model for BA radical polymerizations. [ 75 ] In the future, this type of additional experimental data could be very valuable for expanding the available experimental database in order to test existing kMC models as well as for further development and refinement of kMC models.…”

Designing acrylic latexes for pressure‐sensitive adhesives: a review

“…Propagation from the midchain radical that results from inter molecular chain transfer to polymer leads to the formation of long chain branches which can also influence the rheological behavior 55 . If intermolecular chain transfer to polymer is followed by termination by combination, the molecular weight of the chains can significantly increase 56–58 .…”

“…54 Propagation from the midchain radical that results from intermolecular chain transfer to polymer leads to the formation of long chain branches which can also influence the rheological behavior. 55 If intermolecular chain transfer to polymer is followed by termination by combination, the molecular weight of the chains can significantly increase. [56][57][58] As the probability that a hydrogen atom is abstracted by intermolecular chain transfer to polymer increases as the length of the chain increases, this leads to a snowball effect where the large chains tend to get even larger, often reaching an upper limit that is dependent on particle size.…”