Degradable thermosets via orthogonal polymerizations of a single monomer.

Crosslinked thermosets are highly durable materials, but overcoming their petrochemical origins and inability to be recycled poses a grand challenge. Many strategies to access crosslinked polymers that are bioderived or degradable-by-design have been proposed, but they require several resource-intensive synthesis and purification steps and are not yet feasible alternatives to conventional consumer materials. Here we present a modular, one-pot synthesis of degradable thermosets from the commercially available, biosourced monomer 2,3-dihydrofuran (DHF).

Multimaterial Thermoset Synthesis: Switching Polymerization Mechanism with Light Dosage.

The synthesis of polymeric thermoset materials with spatially controlled physical properties using readily available resins is a grand challenge. To address this challenge, we developed a photoinitiated polymerization method that enables the spatial switching of radical and cationic polymerizations by controlling the dosage of monochromatic light. This method, which we call Switching Polymerizations by Light Titration (SPLiT), leverages the use of substoichiometric amounts of a photobuffer in combination with traditional photoacid generators.

Hydrazine-Catalysed Ring-Opening Metathesis Polymerization Of Cyclobutenes.

Materials formed by the ring-opening metathesis polymerization (ROMP) of cyclic olefins are highly valued for industrial and academic applications but are difficult to prepare free of metal contaminants. Here we describe a highly efficient metal-free ROMP of cyclobutenes using hydrazine catalysis. Reactions can be initiated via in situ condensation of a [2.

Direct Functionalization of Polyethylene Surfaces with High-Density Polymer Brushes.

Introducing functionality onto PE surfaces is a longstanding challenge in polymer science, driven by the need for polymer materials with improved adhesion and antifouling properties. Herein, we report surface-initiated hydrogen atom transfer-reversible addition-fragmentation chain transfer (SI HAT-RAFT) as a robust method to grow high-density brush polymers from PE surfaces. We demonstrate that, under mild conditions, direct initiation from the C-H bonds of PE surfaces allows for the graft polymerization of a variety of (meth)acrylate monomers.

Closing the loop on thermoset plastic recycling.

A bio-based plastic advances recycling.

Comparing Ammonium and Tetraaminophosphonium Anion-Exchange Membranes Derived from Vinyl-Addition Polynorbornene Copolymers.

Herein, we systematically examined how composition influenced the properties of vinyl addition polynorbornene anion exchange membranes (AEMs) prepared from 5-hexyl-2-norbornene and 5-(4-bromobutyl)-2-norbornene. Copolymerization kinetics revealed that 5-hexyl-2-norbornene is consumed faster than 5-(4-bromobutyl)-2-norbornene, leading to a portion of the chain being richer in bromoalkyl groups. The alkyl halide pendants can then be converted to either trimethylammonium or tetrakis(dialkylamino)phosphonium cations through straightforward substitution with trimethylamine or a tris(dialkylamino)phosphazene.

Selective Electrocatalytic Degradation of Ether-Containing Polymers.

Leveraging electrochemistry to degrade robust polymeric materials has the potential to impact society's growing issue of plastic waste. Herein, we develop an electrocatalytic oxidative degradation of polyethers and poly(vinyl ethers) via electrochemically mediated hydrogen atom transfer (HAT) followed by oxidative polymer degradation promoted by molecular oxygen. We investigated the selectivity and efficiency of this method, finding our conditions to be highly selective for polymers with hydridic, electron-rich C-H bonds.

Differential Impact of the COVID-19 Pandemic on Female Graduate Students and Postdocs in the Chemical Sciences.

Over the past two and a half years, the COVID-19 pandemic severely disrupted almost all aspects of life as people throughout the world were instructed to work-from-home. Scientific researchers, whose work is reliant on access to laboratory equipment, have been acutely impacted by these global changes. In this study, we surveyed graduate students and postdocs in the chemical sciences at a selected number of academic institutions in the United States.

Chemical Recycling of Thiol Epoxy Thermosets via Light-Driven C-C Bond Cleavage.

Epoxy thermosets are high-volume materials that play a central role in a wide range of engineering applications; however, technologies to recycle these polymers remain rare. Here, we present a catalytic, light-driven method that enables chemical recycling of industrially relevant thiol epoxy thermosets to their original monomer at ambient temperature. This strategy relies on the proton-coupled electron transfer (PCET) activation of hydroxy groups within the polymer network to generate key alkoxy radicals that promote the fragmentation of the polymer through C-C bond β-scission.

Direct Insertion Polymerization of Ionic Monomers: Rapid Production of Anion Exchange Membranes.

The limited number of methods to directly polymerize ionic monomers currently hinders rapid diversification and production of ionic polymeric materials, namely anion exchange membranes (AEMs) which are essential components in emerging alkaline fuel cell and electrolyzer technologies. Herein, we report a direct coordination-insertion polymerization of cationic monomers, providing the first direct synthesis of aliphatic polymers with high ion incorporations and allowing facile access to a broad range of materials. We demonstrate the utility of this method by rapidly generating a library of solution processable ionic polymers for use as AEMs.

Safer Polyurethane Foams with Cyclic Carbonates.

Polyurethanes (PUs) are a class of materials usually synthesized from isocyanates, diols, and water. Water is essential for producing carbon dioxide (CO ) which is used for the self-blowing of the foams. Due to safety concerns with the production of isocyanates, alternative chemistries have been evaluated and cyclic carbonate systems have shown great promise.

Poly(2,3-Dihydrofuran): A Strong, Biorenewable, and Degradable Thermoplastic Synthesized via Room Temperature Cationic Polymerization.

Creation of strong and tough plastics from sustainable and biorenewable resources is a significant challenge in polymer science. This challenge is further complicated when attempting to make these materials using an economically viable process, which is often hindered by the production and availability of chemical feedstocks and the efficiency of the monomer synthesis. Herein, we report the synthesis and characterization of a strong thermoplastic made from 2,3-dihydrofuran (DHF), a monomer made in one step from 1,4-butanediol, a bioalcohol already produced on the plant scale.

Photoredox Catalysis in Photocontrolled Cationic Polymerizations of Vinyl Ethers.

Advances in photocontrolled polymerizations have expanded the scope of polymer architectures and structures that can be synthesized for various applications. The majority of these polymerizations have been developed for radical processes, which limits the diversity of monomers that can be used in macromolecular design. More recent developments of photocontrolled cationic polymerizations have taken a step toward addressing this limitation and have expanded the palette of monomers that can be used in stimuli-regulated polymerizations, enabling the synthesis of previously inaccessible polymeric structures.

Metal-Free Ring-Opening Metathesis Polymerization with Hydrazonium Initiators.

The ring-opening metathesis polymerization (ROMP) of cyclopropenes using hydrazonium initiators is described. The initiators, which are formed by the condensation of 2,3-diazabicyclo[2.2.

Reversible C-C Bond Formation, Halide Abstraction, and Electromers in Complexes of Iron Containing Redox-Noninnocent Pyridine-imine Ligands.

The exploration of pyridine-imine (PI) iron complexes that exhibit redox noninnocence (RNI) led to several interesting discoveries. The reduction of (PI)FeX species afforded disproportionation products such as (dmpPI)FeX (dmp = 2,6-Me-CH, X = Cl, Br; -X) and (dippPI)FeX (dipp = 2,6-Pr-CH, X = Cl, Br; -X), which were independently prepared by reductions of (PI)FeX in the presence of PI. The crystal structure of -Br possessed an asymmetric unit with two distinct electromers, species with different electronic GSs: a low-spin ( = 1/2) configuration derived from an intermediate-spin = 1 core antiferromagnetically (AF) coupled to an = 1/2 PI ligand, and an = 3/2 center resulting from a high-spin = 2 core AF-coupled to an = 1/2 PI ligand.

Photoswitching Cationic and Radical Polymerizations: Spatiotemporal Control of Thermoset Properties.

The ability to fabricate polymeric materials with spatially controlled physical properties has been a challenge in thermoset manufacturing. To address this challenge, this work takes advantage of a photoswitchable polymerization that selectively incorporates different monomers at a growing chain by converting from cationic to radical polymerizations through modulation of the wavelength of irradiation. By regulating the dosage and wavelength of light applied to the system, the mechanical properties of the crosslinked material can be temporally and spatially tuned.

Reversible redox controlled acids for cationic ring-opening polymerization.

Advancements in externally controlled polymerization methodologies have enabled the synthesis of novel polymeric structures and architectures, and they have been pivotal to the development of new photocontrolled lithographic and 3D printing technologies. In particular, the development of externally controlled ring-opening polymerization (ROP) methodologies is of great interest, as these methods provide access to novel biocompatible and biodegradable block polymer structures. Although ROPs mediated by photoacid generators have made significant contributions to the fields of lithography and microelectronics development, these methodologies rely upon catalysts with poor stability and thus poor temporal control.

Depolymerization of Hydroxylated Polymers via Light-Driven C-C Bond Cleavage.

The accumulation of persistent plastic waste in the environment is widely recognized as an ecological crisis. New chemical technologies are necessary both to recycle existing plastic waste streams into high-value chemical feedstocks and to develop next-generation materials that are degradable by design. Here, we report a catalytic methodology for the depolymerization of a commercial phenoxy resin and high molecular weight hydroxylated polyolefin derivatives upon visible light irradiation near ambient temperature.

Hydrogen Bond Donor Catalyzed Cationic Polymerization of Vinyl Ethers.

The synthesis of high-molecular-weight poly(vinyl ethers) under mild conditions is a significant challenge, since cationic polymerization reactions are highly sensitive to chain-transfer and termination events. We identified a novel and highly effective hydrogen bond donor (HBD)-organic acid pair that can facilitate controlled cationic polymerization of vinyl ethers under ambient conditions with excellent monomer compatibility. Poly(vinyl ethers) of molar masses exceeding 50 kg mol can be produced within 1 h without elaborate reagent purification.

Photocontrolled Radical Polymerization from Hydridic C-H Bonds.

Given the ubiquity of carbon-hydrogen bonds in biomolecules and polymer backbones, the development of a photocontrolled polymerization selectively grafting from a C-H bond represents a powerful strategy for polymer conjugation. This approach would circumvent the need for complex synthetic pathways currently used to introduce functionality at a polymer chain end. On this basis, we developed a hydrogen-atom abstraction strategy that allows for a controlled polymerization selectively from a hydridic C-H bond using a benzophenone photocatalyst, a trithiocarbonate-derived disulfide, and visible light.

Cross-linking Effects on Performance Metrics of Phenazine-Based Polymer Cathodes.

Developing cathodes that can support high charge-discharge rates would improve the power density of lithium-ion batteries. Herein, the development of high-power cathodes without sacrificing energy density is reported. N,N'-diphenylphenazine was identified as a promising charge-storage center by electrochemical studies due to its reversible, fast electron transfer at high potentials.

Cardiac left ventricular ejection fraction in men and women with schizophrenia on long-term antipsychotic treatment.

Patients with schizophrenia exhibit a higher cardiovascular mortality compared to the general population which has been attributed to life-style factors, genetic susceptibility and antipsychotic medication. Recent echocardiographic studies have pointed to an association between clozapine treatment and reduced left ventricular ejection fraction (LVEF), a measure that has been inversely associated with adverse outcomes including all-cause mortality. Cardiovascular magnetic resonance (CMR) is considered the reference method for LVEF measurement.

Controlling the Shape of Molecular Weight Distributions in Coordination Polymerization and Its Impact on Physical Properties.

High-density polyethylene (HDPE) is utilized in a multitude of commercial products worldwide due to its broad spectrum of physical properties and low production costs. Molecular weight and dispersity () are known to affect the tensile and rheological properties of HDPE, but little is known about the influence of the molecular weight distribution (MWD) shape on these properties. In this work, we investigate this matter through the temporal regulation of initiation in a living coordination-insertion polymerization of ethylene.