Vitrimers are a new class of polymeric materials that simultaneously offer the desired physical properties of thermosets and malleability/reprocessability of thermoplastics. Despite significant progress being made in the field of vitrimers, there exists a critical need for the development of robust dynamic covalent chemistries for the production of strong and thermally stable vitrimers. In this work, we discovered a new silyl ether metathesis reaction and used it for the preparation of vitrimers with exceptional thermal stability. In small-molecule model studies, we observed that silyl ether motifs directly exchange under anhydrous conditions catalyzed by a Brønsted or Lewis acid catalyst. For initial vitrimer demonstration, a commodity polymer, poly­(ethylene-co-vinyl alcohol) (PEOH), was silylated with trimethylsilyl (TMS) groups followed by cross-linking with a bis-silyl ether cross-linker. The resulting thermoset showed exceptional thermal stability while maintaining malleability/reprocessability at elevated temperatures. The vitrimer properties such as recyclability and stress relaxation at various temperatures were carefully investigated. The material was reprocessable at 150 °C while also exhibiting good creep resistance at temperatures below its melting transition (T m). This work demonstrates the silyl ether metathesis reaction as a new, robust dynamic covalent chemistry to introduce plasticity, reprocessability, and recyclability to thermosets.

The instruction of high enrollment general and organic chemistry laboratories at a large public 10 university always have curricular, administrative, and logistical challenges. Herein, we describe how we met these challenges in the transition to remote teaching during the COVID-19 pandemic. We discuss the reasoning behind our approach, the utilization of our existing web-based course content, the additions and alterations to our curriculum, replacement of experimental work with videos, the results of both student and TA surveys, and lessons learned for iterations of these courses in the near 15 future. File list (3) download file view on ChemRxiv CHEMRXIV_REVISED-Online in No Time.pdf (1.34 MiB) download file view on ChemRxiv Online in No Time Supporting Information.pdf (181.10 KiB) download file view on ChemRxiv bigbrother_python_code.py (3.15 KiB)

A postpolymerization modification strategy based on ambient temperature nucleophilic chemical deblocking of polymer scaffolds bearing N-heterocycle-blocked isocyanate moieties is reported. Room temperature RAFT polymerization of three azole-N-carboxamide methacrylates, including 3,5-dimethylpyrazole, imidazole, and 1,2,4-triazole derivatives, afforded reactive polymer scaffolds with well-defined molecular weights and narrow dispersities ( Đ < 1.2). Model analogues possessing the same N-heterocycle blocking agents with varied leaving group abilities were synthesized to determine optimal deblocking conditions. The reactivity of the azole-N-carboxamide moieties toward nucleophiles can be tuned simply by varying the structure of the azole blocking agents (reactivity order: pyrazole < imidazole < triazole). DBU-catalyzed reactions of thiols with imidazole- and 1,2,4-triazole-blocked isocyanate scaffolds were shown to occur rapidly and quantitatively under ambient conditions. Differences in reactivity of 1,2,4-triazole- and 3,5-dimethylpyrazole-blocked isocyanate copolymers with various nucleophiles at room temperature facilitated sequential and postpolymerization modification. This strategy advances the utility of blocked isocyanates and promotes the chemistry as a powerful postmodification tool to access multifunctional polymeric materials.

The instruction of high enrollment general and organic chemistry laboratories at a large public 10 university always have curricular, administrative, and logistical challenges. Herein, we describe how we met these challenges in the transition to remote teaching during the COVID-19 pandemic. We discuss the reasoning behind our approach, the utilization of our existing web-based course content, the additions and alterations to our curriculum, replacement of experimental work with videos, the results of both student and TA surveys, and lessons learned for iterations of these courses in the near 15 future.

Sustainable development of new technologies requires materials having advanced physical and chemical properties while maintaining reprocessability and recyclability. Vitrimers are designed for this purpose; however, their dynamic covalent chemistries often have drawbacks or are limited to specialized polymers. Here, fluoride-catalyzed siloxane exchange is reported as an exceptionally robust chemistry for scalable production of high-performance vitrimers through industrial processing of commodity polymers such as poly(methyl methacrylate), polyethylene, and polypropylene. The vitrimers show improved resistance to creep, heat, oxidation, and hydrolysis, while maintaining excellent melt flow for processing and recycling. Furthermore, the siloxane exchange between different vitrimers during mechanical blending results in self-compatibilized blends without any compatibilizers. This offers a general, scalable method for producing sustainable high-performance vitrimers and a new strategy for recycling mixed plastic wastes.