Extending the High-Throughput Experimentation (HTE) Approach to Catalytic Olefin Polymerizations: From Catalysts to Materials

Abstract

In this study, a state-of-the-art high-throughput experimentation (HTE) workflow for catalytic olefin polymerization, covering an unprecedented wide part of the polymer knowledge and value chains from catalytic synthesis all the way down to "engineering" microrheology, was thoroughly assessed with respect to its ability to prepare new materials and produce large and accurate databases for the investigation of quantitative structure−property relationships (QSPRs). Olefin blocks copolymers (OBCs) produced under chain-shuttling polymerization conditions were used as a demonstration case. The results of a thorough microstructural, structural, mechanical, morphological, and rheological characterization of OBC replicas prepared with the HTE synthetic platform and a commercial sample, chosen as a benchmark, demonstrate the robustness of the approach. The proposed workflow can become a paradigm for the high-throughput synthesis and investigation of novel materials, thus reducing the time to market of new products. In our opinion, this opens the door to integrated HTE and artificial intelligence approaches to QSPR problem solving in the numerous cases for which a thorough understanding of the theory is not sufficient to deterministically unravel the complexity of practical applications.

Molecular Architecture of Multiblock Copolymers Synthesized by the Chain Shuttling Technology

“…[56] The state of the melt before crystallization was directly probed resorting to rheological measurements. [52,55,65,121,122] Due to the low contrast in electron density between soft and hard blocks, indeed, small angle X-ray scattering is unable to probe concentration fluctuations at nanometric length scale due to phase separation in the melt, being merely sensitive to fluctuations of density. As an example, the results of rheological measurements are shown in Figure 14A for an MBC sample with mass average molecular mass of 250 kDa, dispersity index Ð = 3.4, C8 content in the hard and soft blocks equal to ≈2 and 36 mol%, respectively (ΔC8 ≈ 34 mol%), and hard block content of 18 wt%.…”

Coordinative Chain Transfer and Chain Shuttling Polymerization

“…Thus, olefin multiblock copolymers are valuable thermoplastic elastomers with remarkable properties, such as high melting temperature and low glass transition temperature, low density and degree of crystallinity, and good elasticity even at elevated temperatures. Several research groups thoroughly investigated these materials in terms of their microstructure and mechanical properties to provide a library of structure–property relationships. − …”

Ring Repeating Unit: An Upgraded Structure Representation of Linear Condensation Polymers for Property Prediction

“…Traditional design of high-performance polymers is often based on experience and trial and error to narrow structure spaces and adjust performance parameters by repeated experiments and characterizations. Benefiting from the development of polymer informatics, − data-centric approaches such as quantitative structure–property relationship (QSPR) modeling, − machine learning (ML) algorithms, − and polymer genome approach − have dramatically accelerated polymer property predictions and the discovery of new high-performance polymers . As one of the prevalent approaches, QSPR modeling implicitly correlates the molecular structure with the physicochemical properties, further contributing to predict the relevant properties of interest in the context of computer-aided design of polymeric materials .…”