Renewable Beta-Elemene Based Cyclic Carbonates for the Preparation of Oligo(hydroxyurethane)s.

Conversion of ß-elemene into new ß-elemene dicarbonates through epoxidation and halide salt-catalyzed CO2 cycloaddition reactions is reported. Step-growth polyaddition of this dicarbonate to five different, commercial diamines was investigated under neat conditions at 150 °C yielding non-isocyanate-based low molecular weight oligo(hydroxyurethane)s with 1.3≤Mn ≤6.3 kDa and 1.3≤Ð≤2.1, and with glass transition temperatures ranging from -59 to 84 °C. The preparation of one selected polyhydroxyurethane material, obtained in the presence of Jeffamine® D-2010 was scaled-up to 43 g. The latter, when combined in a formulation using Irgacure® 2100 and Laromer® LR 9000 allowed the preparation of coatings that were analyzed with several techniques showing the potential of these biobased oligourethanes towards the preparation of commercially relevant materials.

Catalytic Ring-Opening Copolymerization of Fatty Acid Epoxides: Access to Functional Biopolyesters.

Fatty acid epoxies serve as valuable starting materials for the development of bio-based polyesters. Here we present a new and efficient catalytic process that allows for the copolymerization of fatty acid-based epoxides and various cyclic anhydrides under attractive process conditions affording functional polyesters. The degree of functionalization and the nature of the polymer backbone can be modulated via monomer design. Postpolymerization cross-linking processes were examined to create rigid macromolecular networks that build on orthogonal polyester functionality, creating possible entries for materials with switchable thermal and mechanical properties.

Unlocking the Potential of Substrate-Directed CO2 Activation and Conversion: Pushing the Boundaries of Catalytic Cyclic Carbonate and Carbamate Formation.

The unparalleled potential of substrate-induced reactivity modes in the catalytic conversion of carbon dioxide and alcohol or amine functionalized epoxides is discussed in relation to more conventional epoxide/CO2 coupling strategies. This conceptually new approach allows for a substantial extension of the substitution degree and functionality of cyclic carbonate/carbamate products, which are predominant products in the area of nonreductive CO2 transformations. Apart from the creation of an advanced library of CO2 -based heterocyclic products and intermediates, also the underlying mechanistic reasons for this novel reactivity profile are debated with a prominent role for the design and structure of the involved catalysts.

A Novel [OSSO]-Type Chromium(III) Complex as a Versatile Catalyst for Copolymerization of Carbon Dioxide with Epoxides.

A new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO2 and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers.

Cyclic Polyester Formation with an [OSSO]-Type Iron(III) Catalyst.

The efficient formation of cyclic polyesters from the ring-opening polymerization of lactide, ϵ-caprolactone, and ß-butyrolactone catalyzed by a 1,4-dithiabutanedyl-2,2'-bis(4,6-dicumylphenol) [OSSO]-FeCl complex activated with cyclohexene oxide was achieved. The catalyst was very active (initial turnover frequency up to 2718 h-1 ), robust, and worked with a monomer/Fe ratio up to 10 000. The formation of cyclic polymers was supported by using high-resolution matrix-assisted laser desorption ionization (MALDI) MS, and the average ring size (≈5 kDa for cyclic polylactide) independent of the reaction conditions. A monometallic ring-opening polymerization/cyclization mechanism was proposed from the results of a kinetic investigation.

Phenylene-Bridged OSSO-Type Titanium Complexes in the Polymerization of Ethylene and Propylene.

The dichloro titanium complexes (OSSO tBu)TiCl2 (1) and (OSSOCum)TiCl2 (2) bearing o-phenylene-bridged OSSO-type ligands [OSSO tBu-H = 6,6'-((1,2-phenylenebis(sulfanediyl))bis(methylene))bis(2,4-di-tert-butyphenol) and OSSOCum-H = 6,6'-((1,2-phenylenebis(sulfanediyl))bis(methylene))bis(2,4-bis(2-phenylpropan-2-yl)phenol)] were prepared and characterized. The X-ray structure of 1 revealed that Ti atom has an octahedral coordination geometry with an fac-fac wrapping of the [OSSO] ligand. In solution at 25 °C, 1 mainly retains the C 2 symmetric structure, whereas 2 shows an equilibrium between C 2- and C 1-symmetric stereoisomers. Activation of 2 with (Ph3C)[B(C6F5)4] led to a highly active catalytic system with an activity of 238 kgPE·molcat -1·bar-1·h-1; linear polyethylene with a T m of 122 °C and M w of 107 kDa were obtained under these conditions. Catalyst 1 displayed the moderate activity of 59 kgPE·molcat -1·bar-1·h-1. Gel permeation chromatography analysis revealed the formation of high-molecular-weight polyethylenes with very large distributions of the molecular weights, indicating a low control of the polymerization process, probably becaue of the presence of different active species in solution. Density functional theory investigation provides a rational for the relative high-molecular-weight polymers obtained with these complexes. The precatalyst 2 was also active in propylene polymerization producing atactic oligomers terminated with unsaturated end groups.

Glycidol: an Hydroxyl-Containing Epoxide Playing the Double Role of Substrate and Catalyst for CO2 Cycloaddition Reactions.

Glycidol is converted into glycerol carbonate (GC) by coupling with CO2 in the presence of tetrabutylammonium bromide (TBAB) under mild reaction conditions (T=60 °C, PCO2 =1 MPa) in excellent yields (99 %) and short reaction time (t=3 h). The unusual reactivity of this substrate compared to other epoxides, such as propylene oxide, under the same reaction conditions is clearly related to the presence of a hydroxyl functionality on the oxirane ring. Density functional theory calculations (DFT) supported by 1 H NMR experiments reveal that the unique behavior of this substrate is a result of the formation of intermolecular hydrogen bonds into a dimeric structure, activating this molecule to nucleophilic attack, and allowing the formation of GC. Furthermore, the glycidol/TBAB catalytic system acts as an efficient organocatalyst for the cycloaddition of CO2 to various oxiranes.

Thioether-triphenolate bimetallic iron(III) complexes as robust and highly efficient catalysts for cycloaddition of carbon dioxide to epoxides.

The selective and effective synthesis of organic carbonates under mild conditions, starting from carbon dioxide and oxiranes, catalyzed by metal complexes is currently a focus of interest for both industrial and academic researchers. We recently developed a novel thioether-triphenolate iron(III) catalyst (Ct-BU) that has proven to be highly active for the coupling of CO2 with epoxides, resulting in cyclic organic carbonates under solvent-free conditions. In the current work, the properties of this novel class of catalysts were extensively investigated. In particular, the steric properties of the ligand were modulated by changing the substituents of the aromatic rings in order to obtain a deeper knowledge of the relationship between the complex structure and catalytic performance/selectivity for these iron complexes. Notably, the less steric demanding iron(III) CH complex synthesized shows, when activated by n-tetrabutylammonium bromide, an impressive turnover frequency (TOF) of 3800 h(-1) for the formation of propylene carbonate and glycerol carbonate which are, by far, the highest reported for an iron based catalyst and compares well with the most active catalyst based on other metals.