In this contribution, olefin block copolymers were produced via chain shuttling polymerization (CSP), using a new combination of catalysts and a chain shuttling agent (CSA) diethylzinc (ZnEt2). The binary catalyst system included nonbridged half-titanocene catalyst, Cp*TiCl2(O-2,6-iPr2C6H3) (Cat A) and bis(phenoxy-imine) zirconium, {η 2-1-[C(H)=NC6H11]-2-O-3-tBu-C6H3}2ZrCl2 (Cat B), as well as co-catalyst methylaluminoxane (MAO). In contrast to dual-catalyst system in the absence of CSA, the blocky structure was obtained in the presence of CSA and rationalized from rheological studies. The binary catalyst system could cause the CSP reaction to occur in the presence of CSA ZnEt2, which yielded broad distribution ethylene/1-octene copolymers (M w/M n: 35.86) containing block polymer chains with high M w. The presented dual-catalytic system was applied for the first time in CSP and has a potential to be extended to produce a library of olefin block copolymers that can be used as advanced additives for thermoplastics.

The beneficial use of computer simulations to track the microstructural evolution of individual species is highlighted in view of macromolecular engineering and design, considering two case studies on catalytic polymerization, and both \"low\" (<100) and \"high\" (>100) chain lengths, that is, i) atom transfer radical copolymerization of n-butyl acrylate and styrene aiming at the synthesis of functional macrospecies of \"identical\' chain length; and ii) chain shuttling polymerization of ethylene and 1-octene toward the production of segmented block copolymers with \"soft\" and \"hard\" segments. Model parameters are validated and/or tuned based on literature data. The modeling strategy supports the future identification of chemical structure-polymer property relationships and is based on the combination of principles from polymer reaction engineering, chemistry, and physics.