Greener and sustainable method for alkene epoxidations by polymer-supported Mo(VI) catalysts

A polybenzimidazole supported Mo(VI) (PBI.Mo) catalyst has been prepared and characterised. The catalytic activities of the PBI.Mo catalyst in epoxidation of alkenes with tert-butyl hydroperoxide (TBHP) as an oxidant have been studied under different reaction conditions in a batch reactor. As alkene representatives we have chosen cyclohexene, limonene, α-pinene and 1-octene (a less reactive terminal alkene). The order of reactivity of the alkenes was found to be: cyclohexene>limonene>α-pinene>1-octene. The stability of each polymer catalyst was assessed by recycling a sample in batch reaction using conditions that will form the basis of the continuous process. The loss of Mo from each support has been investigated by isolating any residue from the reaction supernatant solutions, following removal of the heterogeneous polymer catalyst, and then using the residues as potential catalysts in epoxidation reactions

Facile synthesis of branched pol(vinyl alcohol)s

Poly(vinyl alcohol) (PVOH) is a ubiquitous synthetic polymer that finds widespread application in biological and medical products through to personal, domestic, and industrial products. The currently available range of materials all have linear backbone architectures with interesting solubility, rheological, and interfacial properties. The latter might be significantly broadened if complementary polymers with branched backbone architectures could be synthesized, especially if the methodology involved only minor changes from that currently practiced. We have now synthesized branched PVOHs via conventional free radical copolymerization of vinyl acetate (VAc) and triallyl-triazine-trione (TTT), in 2-isopropoxy ethanol (IPE) solvent in the presence of appropriate thiol free radical chain transfer agents, followed by alcoholysis of the so-formed branched poly(vinyl acetates)s (PVAc)s with methanol. Balancing the mole ratio of TTT to thiol allows high conversion to branched materials to be achieved while inhibiting cross-linking and gelation of the products. The branch points derived from the TTT comonomer have been shown to be conserved during the alcoholysis step, and extensive characterization of the PVAc precursors and the derived PVOHs using multiple detector size exclusion chromatographic (SEC) instrumentation has confirmed the highly branched nature of both groups of polymers. Final confirmation of the branched architecture of the PVOH samples has been made by reacetylation of some samples, in effect to regenerate their PVAc precursors. SEC analysis of the latter has indeed shown these to be architecturally very similar to the original precursor PVAcs. This novel methodology for synthesizing branched PVOHs involves relatively minor adjustments to the currently used industrial process for linear PVOHs and so offers good prospects for scale-up and exploitation

Weak anion-exchange hypercrosslinked sorbent in on-line solid-phase extraction-liquid chromatography coupling to achieve automated determination with an effective clean-up

A mixed-mode polymeric sorbent was on-line coupled to liquid chromatography (LC) for the first time and applied it to the selective solid-phase extract a group of pharmaceuticals in complex environmental water samples. The mixed-mode polymeric sorbent is a high-specific surface area hypercrosslinked polymer resin (HXLPP) in the form of monodisperse microspheres further modified with 1,2-ethylenediamine (EDA) moieties. These properties allows its application as a weak anion-exchange (WAX) sorbent in the on-line solid-phase extraction (SPE) coupling. The on-line SPE-LC method developed using the HXLPP-WAX sorbent was successfully applied to percolate a large volume of ultrapure (500 ml), river (250 ml) and effluent sewage (100 ml) water samples. In all the cases, the HXLPP-WAX resin provided near total recoveries of the most acidic compounds studied and clean chromatograms. This is because the ion-exchange interactions enable a washing step to be added to the SPE protocol that removes the compounds with weak acidic, neutral and basic properties from the sample matrix

Synthesis and application of hypercrosslinked polymers with weak cation-exchange character for the selective extraction of basic pharmaceuticals from complex environmental water samples

The synthesis of high specific surface area sorbents (HXLPP-WCX) in the form of hypercrosslinked polymer microspheres with narrow particle size distributions, average particle diameters around 6 µm, and weak cation exchange (WCX) character, is described. The WCX character arises from carboxylic acid moieties in the polymers, derived from the comonomer methacrylic acid. A novel HXLPP-WCX sorbent with an attractive set of chemical and physical properties was then used in an off-line solid-phase extraction (SPE) protocol for the selective extraction of a group of basic compounds from complex environmental samples, a priority being the clean separation of the basic compounds of interest from acidic compounds and interferences. The separation power of the new sorbent for basic pharmaceuticals was compared to two commercially available, mixed-mode sorbents, namely Oasis WCX and Strata X-CW. Under identical experimental conditions, HXLPP-WCX was found to deliver both higher capacity and better selectivity in SPE than either of the two commercially available materials. In an optimised SPE protocol, the HXLPP-WCX sorbent gave rise to quantitative and selective extractions of low µg l-1 levels of basic pharmaceuticals present in 500 ml of river water and 250 ml of effluent waste water

Hydrophilic hypercrosslinked polymeric sorbents for the solid-phase extraction of polar contaminants from water

Three new hypercrosslinked polymers with hydrophilic character arising from hydroxyl moieties in their skeletons have been prepared in microsphere format and applied to the off-line solid-phase extraction (SPE) of polar compounds from water samples. For sample volumes of 1000 ml, the recoveries of various polar pesticides, such as oxamyl, methomyl, selected phenolic compounds, as well as some pharmaceuticals, were close to 90%. The HXLPP-polar polymer with the best performance characteristics was applied to real samples. Its performance was also compared to commercially available sorbents, such as LiChrolut EN (hydrophobic, hypercrosslinked), Oasis HLB (hydrophilic, macroporous) and Isolute ENV+ (hydrophilic, hypercrosslinked); the new sorbent out-performed the commercially available sorbents. The polymer was applied successfully in off-line SPE of river water samples followed by liquid chromatography and ultraviolet detection, providing a good linear range and detection limits of 0.2 μg l-1 for the majority of the compounds, with the exception of oxamyl, methomyl, guaiacol and salicylic acid where the detection limit was 0.5 μg l-1

Investigation of macrocyclisation routes to 1,4,7-triazacyclononanes : efficient syntheses from 1,2-ditosylamides

Two routes to the synthesis of a cyclohexyl-fused 1,4,7-triazacyclononane involving macrocyclisations of tosamides have been investigated. In the first approach, using a classic Richman-Atkins-type cyclisation of a cyclohexyl-substituted 1,4,7-tritosamide with ethylene glycol ditosylate, afforded the cyclohexyl-fused 1,4,7-triazacyclononane in 5.86% overall yield in four steps. The second, more concise, approach involving the macrocyclisation of trans-cyclohexane-1,2-ditosamide with the tritosyl derivative of diethanolamine initially gave poor yields (< 25%). The well-documented problems with efficiencies in macrocyclisations using 1,2-ditosamides led to the use of a wider range of 1,2-ditosamides including ethane-1,2-ditosamide and propane-1,2-ditosamide. These extended studies led to the development of an efficient macrocyclisation protocol using lithium hydride. This new method afforded 1,4,7-tritosyl-1,4,7-triazacyclononanes in good yield (57-90%) from 1,2-ditosamides in a single step. These efficient methods were then applied to the preparation of a chiral cyclohexyl-fused 1,4,7-tritosyl-1,4,7-triazacyclononane (65-70%). This key chiral intermediate was then converted into a copper(II) complex following detosylation and N-methylation. The resulting chiral copper(II) complex catalysed the aziridination of styrene but it did so in a racemic fashion

Synthesis of ultra-high surface area monodisperse polymer nanoparticles

Synthesis of vinyl benzyl chloride (VBC)/divinylbenzene (DVB) copolymers via surfactant-free emulsion polymerization yields near monodisperse chloromethylated polystyrene precursor nanospheres 400 nm in diameter. These are analogous to gel-type suspension polymerized particles typically of 100-500 ím in diameter and are essentially nonporous in the dry state having only a very nominal surface area (10 m2 g-1). Cross-linking of appropriate dichloroethane swollen precursors with a high content of VBC residues in the presence of FeCl3 (i.e., using a Davankov-type strategy) yields near monodisperse porous hyper-cross-linked nanoparticles with extremely high surface areas up to 1200 m2 g-1. The latter display all the characteristics of Davakov-type resins in terms of their ability to sorb both thermodynamically “poor” and “good” solvents and in particular despite their superficial hydrophobic makeup are able to sorb significant quantities of water (up to 2.5 g/g). By adjusting the content of VBC in the precursor particles, the surface area of the near monodisperse nanoparticles can be adjusted in the range 15-1300 m2 g-1