Using Near-Infrared Irradiation for Heating Mechanochemical Reactions in Organic-Dye-Doped Epoxy Milling Jars.

Albeit mechanochemistry is a novel promising technology that gives access to reactivity under solvent-free conditions, heating such reactions is sometimes compulsory to obtain satisfactory results in terms of conversion, selectivity and/or yield. In this work, we developed a novel approach using a dye that absorbs NIR photons and release the energy as heat. Hence, de novo milling jars in epoxy resin doped with the dye were thus produced to obtain reactors that would produce heat upon irradiation at 850 nm.

An Optimized and Universal Protocol for the Synthesis of Morpholine-2,5-Diones from Natural Hydrophobic Amino Acids and Their Mixture.

Morpholine-2,5-diones (MDs) are increasingly attractive compounds that can be produced using amino acid (AA) as a starting material. These compounds can undergo polymerization to produce biodegradable materials, namely, polydepsipeptides, that hold the potential to be used in medicinal applications. In this study, a simplified yet high-yield MD synthesis procedure was developed and applied to produce a range of MDs derived from hydrophobic AAs including Leu, Ile, Val, Phe, Asp(OBzl), Lys(Z), and Ser(tBu).

Understanding associative polymer self-assembly with shrinking gate fluorescence correlation spectroscopy.

The self-assembly of polymers is integral to their role in liquid formulations. In this study, we combine a dye whose lifetime is sensitive to the nanoviscosity of its local environment with shrinking gate fluorescence correlation spectroscopy (sgFCS) to study the self-assembly of a model telechelic polymer, hydrophobically modified ethoxylated urethane (HEUR). Fluorescence lifetime measurements show a monotonic increase in average lifetime with increasing HEUR concentration driven by a small fraction of dye (<1%) with long lifetimes strongly bound to HEUR.

Paving the Way towards Sustainability of Polyurethanes: Synthesis and Properties of Terpene-Based Diisocyanate.

Due to growing concerns about environmental issues and the decline of petroleum-based resources, the synthesis of new biobased compounds for the polymer industry has become a prominent and timely topic. P-menthane-1,8-diamine (PMDA) is a readily available compound synthesized from turpentine, a cheap mixture of natural compounds isolated from pine trees. PMDA has been extensively used for its biological activities, but it can also serve as a source of valuable monomers for the polymer industry.

One Step Closer to Coatings Applications Utilizing Self-Stratification: Effect of Rheology Modifiers.

Self-stratification of model blends of colloidal spheres has recently been demonstrated as a method to form multifunctional coatings in a single pass. However, practical coating formulations are complex fluids with upward of 15 components. Here, we investigate the influence of three different rheology modifiers (RMs) on the stratification of a 10 wt % 7:3 w:w blend of 270 and 96 nm anionic latex particles that do not stratify without RM.

Simple and Rapid Mechanochemical Synthesis of Lactide and 3S-(Isobutyl)morpholine-2,5-dione-Based Random Copolymers Using DBU and Thiourea.

There is a growing interest surrounding morpholine-2,5-dione-based materials due to their impressive biocompatibility as well as their capacity to break down by hydrolytic and enzymatic pathways. In this study, the ring-opening (co)polymerization of leucine-derived 3S-(isobutyl)morpholine-2,5-dione (MD) and lactide (LA) was performed via ball-milling using a catalytic system composed of 1,8-diazabicyclo[5.4.

Insight into the Alcohol-Free Ring-Opening Polymerization of TMC Catalyzed by TBD.

We report herein a study on the alcohol-free, ring-opening polymerization of trimethylene carbonate (TMC) in THF, catalyzed by 1,5,7-triazabicyclo [4.4.0] ec-5-ene (TBD) with ratios n/n ranging between 1/20 and 1/400.

Combining a ligand photogenerator and a Ru precatalyst: a photoinduced approach to cross-linked ROMP polymer films.

Although metathesis photoinduced catalysis is now well established, there is little development in thin film preparation using photochemically activated ring-opening metathesis polymerization (ROMP). Herein, a N-heterocyclic carbene (NHC) photogenerator (1,3-bis(mesityl)imidazolium tetraphenylborate) is combined with an inactive metathesis catalyst ([RuCl(-cymene)]) to generate under UV irradiation an active catalyst (-cymene)RuCl (NHC), that is capable of producing in a single step cross-linked copolymer films by ROMP of norbornene with dicyclopentadiene. The study shows that the photoinitiated catalytic system can be optimized by increasing the yield of photogenerated NHC through a sensitizer (2-isopropylthioxanthone), and by choosing [RuI(-cymene)] as precatalyst to provide a long-term photolatency.

Photoreduction of triplet thioxanthone derivative by azolium tetraphenylborate: a way to photogenerate N-heterocyclic carbenes.

Although N-heterocyclic carbenes (NHCs) have brought profound changes in catalytic organic synthesis, their generation generally requires an inert atmosphere and harsh conditions. To overcome these limitations, an air-stable NHC photogenerator has been developed involving two mild components: 1,3-bis(mesityl)imidazolium tetraphenylborate (IMesHBPh) and electronically excited isopropylthioxanthone (ITX). In this study, the photochemical mechanism is investigated via the accurate identification of the transient species and photoproducts.

Mixture of Azolium Tetraphenylborate with Isopropylthioxanthone: A New Class of N-Heterocyclic Carbene (NHC) Photogenerator for Polyurethane, Polyester, and ROMP Polymers Synthesis.

In the search of smarter routes to control the conditions of N-heterocyclic carbene (NHCs) formation, a two-component air-stable NHC photogenerating system is reported. It relies on the irradiation at 365 nm of a mixture of 2-isopropylthioxanthone (ITX) with 1,3-bis(mesityl)imidazoli(ni)um tetraphenylborate. The photoinduced liberation of NHC is evidenced by reaction with a mesitoyl radical to form an NHC-radical adduct detectable by electron spin resonance spectroscopy.

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization.

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes and determine the corresponding photochemical mechanism. Then, we describe a protocol to perform ring-opening metathesis polymerization (ROMP) in solution and in miniemulsion using this NHC-photogenerating system. To photogenerate IMes, a system comprising 2-isopropylthioxanthone (ITX) as the sensitizer and 1,3-dimesitylimidazolium tetraphenylborate (IMesHBPh4) as the protected form of NHC is employed.

UV-Initiated Ring Opening Polymerization of l-Lactide Using a Photobase Generator.

Photoinitiated ring-opening polymerization of l-lactide (L-LA) using a photobase generator (PBG) able to release 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) is reported.

In Situ Generated Ruthenium-Arene Catalyst for Photoactivated Ring-Opening Metathesis Polymerization through Photolatent N-Heterocyclic Carbene Ligand.

1,3-Bis(mesityl)imidazolium tetraphenylborate (IMesH BPh ) can be synthesized in one step by anion metathesis between the corresponding imidazolium chloride and sodium tetraphenylborate. In the presence of 2-isopropylthioxanthone (sensitizer), an IMes N-heterocyclic carbene (NHC) ligand can be photogenerated under irradiation at 365 nm through coupled electron/proton transfer reactions. By combining this tandem NHC photogenerator system with metathesis inactive [RuCl (p-cymene)] precatalyst, the highly active RuCl (p-cymene)(IMes) complex can be formed in situ, enabling a complete ring-opening metathesis polymerization (ROMP) of norbornene in the matter of minutes at room temperature.

N-Heterocyclic carbenes (NHCs) as organocatalysts and structural components in metal-free polymer synthesis.

The chemistry of N-heterocyclic carbenes (NHCs) has witnessed tremendous development in the past two decades: NHCs have not only become versatile ligands for transition metals, but have also emerged as powerful organic catalysts in molecular chemistry and, more recently, in metal-free polymer synthesis. To understand the success of NHCs, this review first presents the electronic properties of NHCs, their main synthetic methods, their handling, and their reactivity. Their ability to activate key functional groups (e.

2-(Diethyl)aminoethyl Methacrylate as a CO-Switchable Comonomer for the Preparation of Readily Coagulated and Redispersed Polymer Latexes.

CO stimuli-responsive polystyrene latexes having a solids content of 27% were prepared in a surfactant-free emulsion polymerization (SFEP) under a CO atmosphere, employing only commercially available chemical compounds: styrene, the initiator VA-061, and 0.54 mol % of the CO-switchable comonomer DEAEMA. The resulting polymer particles are 230-300 nm in diameter and are monodisperse (PDI ≤ 0.

Imidazol(in)ium hydrogen carbonates as a genuine source of N-heterocyclic carbenes (NHCs): applications to the facile preparation of NHC metal complexes and to NHC-organocatalyzed molecular and macromolecular syntheses.

Anion metathesis of imidazol(in)ium chlorides with KHCO(3) afforded an easy one step access to air stable imidazol(in)ium hydrogen carbonates, denoted as [NHC(H)][HCO(3)]. In solution, these compounds were found to be in equilibrium with their corresponding imidazol(in)ium carboxylates, referred to as N-heterocyclic carbene (NHC)-CO(2) adducts. The [NHC(H)][HCO(3)] salts were next shown to behave as masked NHCs, allowing for the NHC moiety to be readily transferred to both organic and organometallic substrates, without the need for dry and oxygen-free conditions.