Synthesis and Properties of Ethylene/propylene and Ethylene/propylene/5-ethylidene-2-norbornene Copolymers Obtained on Rac-Et(2-MeInd)2ZrMe2/Isobutylaluminium Aryloxide Catalytic Systems

Ethylene/propylene (E/P) and ethylene/propylene/5-ethylidene-2-norbornene (E/P/ENB) copolymers were obtained on rac-Et(2-MeInd)2ZrMe2 activated by a number of isobutylaluminium aryloxides: (2,6-tBu2PhO-)AliBu2 (1-DTBP) (2,6-tBu2,4-Me-PhO-)AliBu2 (1-BHT), (2,4,6-tBu2PhO-)AliBu2 (1-TTBP), (2,6-tBu2,4-Me-PhO-)2AliBu (2-BHT), (2,6-tBu2PhO-)2AliBu (2-DTBP), [(2-Me,6-tBu-C6H3O)AliBu2]2 (1-MTBP), [(2,6-Ph2-PhO)AliBu2]2 (1-DPP). This study shows how the structure of an activator influences catalytic activity and polymer properties, such as the copolymer composition, molecular weight characteristics, and thermophysical and mechanical properties. It has been shown that both the introduction of a bulky substituent in the para-position of the aryloxy group and the additional aryloxy group in the structure of an activator lead to a significant decrease in activity of the catalytic system in all studied copolymerization processes. Moreover, activation by bulkier aryloxides leads to lower levels of comonomer insertion and gives rise to higher molecular weight polymers. Broad or multiple endothermic peaks with different values of melting points are observed on the DSC curves of the copolymers obtained with different catalytic systems. The DSC of the thermally fractionated samples makes it possible to reveal the heterogeneity of the copolymer microstructure, which manifests itself in the presence of a set of lamellar crystallites of different thickness. The results also present the mechanical properties of the copolymers, such as the tensile strength (σ), elongation at break (ε), and engineering strain (EL). The synthesized E/P and E/P/ENB copolymers contain about 1–4 wt.% of the sterically hindered phenols obtained in situ as a residue of the hydrolyzed activators in the course of reaction quenching. This determines the increased thermooxidative stability of the copolymers

The Impact of Backbone Fluorination and Side-Chain Position in Thiophene-Benzothiadiazole-Based Hole-Transport Materials on the Performance and Stability of Perovskite Solar Cells

Perovskite solar cells (PSCs) currently reach high efficiencies, while their insufficient stability remains an obstacle to their technological commercialization. The introduction of hole-transport materials (HTMs) into the device structure is a key approach for enhancing the efficiency and stability of devices. However, currently, the influence of the HTM structure or properties on the characteristics and operational stability of PSCs remains insufficiently studied. Herein, we present four novel push-pull small molecules, H1-4, with alternating thiophene and benzothiadiazole or fluorine-loaded benzothiadiazole units, which contain branched and linear alkyl chains in the different positions of terminal thiophenes to evaluate the impact of HTM structure on PSC performance. It is demonstrated that minor changes in the structure of HTMs significantly influence their behavior in thin films. In particular, H3 organizes into highly ordered lamellar structures in thin films, which proves to be crucial in boosting the efficiency and stability of PSCs. The presented results shed light on the crucial role of the HTM structure and the morphology of films in the performance of PSCs