Krzysztof Matyjaszewski

Electrochemically mediated atom transfer radical polymerization (eATRP) of methyl methacrylate (MMA) was studied in 1‐butyl‐3‐methylimidazolium triflate ([BMIm][OTf]) and ethanol. When 2‐bromopropionitrile and ethyl 2‐bromoisobutyrate were used as initiators, poorly controlled or uncontrolled polymerizations yielding polymers with molecular weights largely exceeding the theoretical values were obtained. Poor control was attributed to a reactivity mismatch between initiator and dormant species, which was successfully suppressed by combining eATRP with catalytic halogen exchange. Well‐defined polymers (Mn>30000 and Ð<1.2) were obtained in both solvents under optimized conditions. The possibility of using PMDETA as an inexpensive ligand in combination with ethyl α‐bromophenylacetate as initiator was also successful. Good chain‐end fidelity during eATRP was confirmed by chain extension of …

Despite their industrial ubiquity, polyolefin‐polyacrylate block copolymers are challenging to synthesize due to the distinct polymerization pathways necessary for respective blocks. This study utilizes MILRad, metal–organic insertion light‐initiated radical polymerization, to synthesize polyolefin‐b‐poly(methyl acrylate) copolymer by combining palladium‐catalyzed insertion–coordination polymerization and atom transfer radical polymerization (ATRP). Brookhart‐type Pd complexes used for the living polymerization of olefins are homolytically cleaved by blue‐light irradiation, generating polyolefin‐based macroradicals, which are trapped with functional nitroxide derivatives forming ATRP macroinitiators. ATRP in the presence of Cu(0), that is, supplemental activators and reducing agents , is used to polymerize methyl acrylate. An increase in the functionalization efficiency of up to 71% is demonstrated in this study by …

Poly(vinylidene fluoride) (PVDF) is commonly used in membranes, lithium-ion battery binders, and coatings due to its thermal and chemical robustness. Nevertheless, PVDF-based copolymers can broaden the application scope and performance capabilities of pristine PVDF. PVDF has been modified via grafting-from reactions. However, grafting density and graft length, two important properties of graft copolymers, cannot be accurately determined. Herein, we used grafting-onto thiol-ene reactions as a method to modify PVDF. The molar mass of pre-synthesized, thiol-terminated polymers were accurately determined, and grafting densities were calculated. Unsaturated sites were generated through dehydrofluorination and dehydrochlorination in PVDF and P(VDF-co-chlorotrifluoroethylene) (PVDF-CTFE). Various conditions were studied, including the molar mass and chemical structure of grafts, the degree of thiol …

In this study, some copper catalysts used for atom transfer radical polymerization (ATRP) were explored as efficient anti‐tumor agents. The aqueous solution of copper‐containing nanoparticles with uniform spheric morphology was in situ prepared through a copper‐catalyzed activator generated by electron transfer (AGET) ATRP in water. Nanoparticles were then directly injected into tumor‐bearing mice for antitumor chemotherapy. The copper nanodrugs had prolonged blood circulation time and enhanced accumulation at tumor sites, thus showing potent antitumor activity. This work provides a novel strategy for precise and large‐scale preparation of copper nanodrugs with high antitumor activity.

Radical ring-opening (co)polymerization (RROP) provides an accessible method for synthesizing main chain degradable vinyl polymers. Although the applications of reversible deactivation radical polymerization (RDRP) into RROP have been reported, the use of photo-mediated RDRP methods has received less attention than the thermal process. Here, photo-RROP of the thionolactone dibenzo[c,e]-oxepine-5(7H)-thione (DOT) and methyl acrylate (MA) was studied using photo-iniferter (PI) reversible addition-fragmentation(chain) transfer (RAFT) polymerization at ambient temperature without external radical initiators or photocatalysts. Despite the occurrence of some side reactions including desulfurization-oxygenation and O-S isomerization of DOT promoted by photoexcited thiocarbonyl groups, polymers with thioester linkages in the backbone were prepared, which degraded in the presence of amines and bleach.

In-space additive manufacturing is of growing interest owing to a variety of advantages across logistics, maintenance, repair, and modularity. Recent efforts have included demonstrations of polymer printing and additive metal processes. Here, we add to the in-space materials currently being explored by developing a multifunctional, space-grade polymer and liquid metal material system compatible with printing. We investigate the use of Viton fluoroelastomer and liquid metal eutectic gallium-indium to create a multifunctional and highly thermally stable material system. The Viton and liquid metal composites demonstrate superior thermo-mechanical stability compared to conventional liquid metal embedded elastomer composites. Notably, the Viton composites demonstrate a mechanical toughening effect after exposures to high temperatures. Mechanical and electrical properties are comprehensively characterized …

(RDRPs) that have been recognized by IUPAC among ten chemical innovations that could change our world as emerging technologies with the potential to make our planet more sustainable. 1 ATRP is a synthetic macromolecular procedure employing controlled radical polymerization to produce welldefined tailored-made polymers. ATRP has been instrumental in the development of advanced materials, including bioconjugates and nanocomposites, with precisely designed controlled macromolecular architecture. This short editorial will focus mostly on current trends and the future of ATRP related to materials chemistry but will also cover trends in the development of powerful and selective catalytic systems operating under benign conditions.

‘Self-healing’(SH) describes the ability of materials to recover functional performance after incurring structural damage. To impart SH ability to engineering polymers promises a path towards reduced waste production and increased functional lifetime of polymer parts. Strategies to realize SH polymer materials encompass the introduction of monomer reservoirs or reversible primary or secondary bond network structures. However, despite the recent progress made in the field of SH polymers, a major challenge remains the realization of SH capability in polymers with sufficiently high modulus (> 1 GPa) to be suitable for engineering applications. This is because the mechanism of SH relies on sufficient chain mobility to enable structure reformation.This contribution explores a new templating approach to realize high-modulus polymer hybrid materials with SH ability. The approach comprises the dissolution of linear …