Generation of well relaxed all atom models of stereoregular polymers: a validation of hybrid particle-field molecular dynamics for polypropylene melts of different tacticities

ABSTRACT The tacticity of vinyl polymer chains strongly affects the physical properties of polymeric materials, as example the chain conformations and stiffness. In the present work we tested how the hybrid Particle-Field Molecular Dynamics (PF-MD) technique is capable to describe conformational differences of polymer chains as function of the tacticity. In particular, we focus on tacticity effect of atactic, isotactic, and syndiotactic polypropylene (PP) homopolymer melts. We found that PF-MD simulations exhibit dependence of Flory’s Characteristic Ratio from the fraction of racemo diads along the PP chains in qualitative agreement with Small Angle Neutron Scattering (SANS) experiments and theoretical previsions. Finally, we calculated and compared the packing length parameter on very high stereoregular syndiotactic PP systems with rheological measurements. A qualitative agreement between the calculated and experimental packing length is found.