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

High-temperature study of radiation cross-linked ethylene-octene copolymers

Three ethylene–octene copolymers (EOC) with a wide range of octene content (17, 30, and 38 wt%) and with the same melt flow index of 1 g/10 min were cross-linked by e-beam radiation (in range 30–120 kGy). The testing methods comprised of rheology, a high-temperature creep test, an analysis of the gel content, and a dynamic mechanical analysis (DMA) test. It was discovered that copolymers with a high octene content attain a higher level of cross-linking density. Cross-linking influenced properties below Tm only marginally as seen from the DMA results. However, the properties above Tm were highly influenced as detected by high-temperature creep and rheology. Above Tm, without the presence of crystals, only the chemical bonds holding the amorphous chains together manifested a gradually decreasing creep at 150 °C with an increasing irradiation level. The loss factor (tanδ at 0.1 Hz) at 150 °C revealed a decreasing trend (or higher cross-linking level) with an increasing octene content. High-temperature results were supported by an increasing gel content with increasing octene content. Samples irradiated to 30 kGy dissolved completely in xylene but showed significantly changed rheological characteristics indicating only an increase in the molecular weight and branching. Analysis according to the Charlesby–Pinner equation revealed increased cross-linking to the scission ratio G(X)/G(S) for EOCs with a higher octene content. While the q0 value which relates to cross-linking changed only slightly, a significant decrease in the p0 value which relates to chain scission was discovered. © 2016, Springer-Verlag Berlin Heidelberg.Internal Grant Agency of the Tomas Bata University in Zlin [IGA/FT/2016/009

Kinetics of hydroformylation of 1-octene in ionic liquid-organic biphasic media using rhodium sulfoxantphos catalyst

Biphasic hydroformylation of 1-octene was performed using rhodium sulfoxantphos catalyst dissolved in [BuPy][BF4] ionic liquid. Preliminary experiments proved this system to retain the catalytic complex within the ionic liquid phase and to maintain a high selectivity towards the linear aldehyde (n:iso ratio of 30) over several cycles. Process parameter investigation showed a first order dependence of the initial rate with respect to the catalyst and 1-octene concentrations, but a more complex behavior with respect to hydrogen (fractional order) and carbon monoxide partial pressures (inhibition at high pressures). Different mathematical models were selected based on the trends observed and evaluated for data fitting. Also, rate models were derived from a proposed mechanism, using Christiansen matrix approach. To calculate concentrations of substrates in the catalytic phase as required by this kinetic modeling, solubility measurements were preformed for the gases (pressure drop technique), as well as for 1-octene and n-nonanal (thermogravimetry analysis)

Effect of mold temperature on the impact behavior and morphology of injection molded foams based on polypropylene polyethylene–octene copolymer blends

Producción CientíficaIn this work, an isotactic polypropylene (PP) and a polyethylene–octene copolymer (POE) have been blended and injection-molded, obtaining solids and foamed samples with a relative density of 0.76. Different mold temperature and injection temperature were used. The Izod impact strength was measured. For solids, higher mold temperature increased the impact resistance, whereas in foams, the opposite trend was observed. In order to understand the reasons of this behavior, the morphology of the elastomeric phase, the crystalline morphology and the cellular structure have been studied. The presence of the elastomer near the skin in the case of high mold temperature can explain the improvement produced with a high mold temperature in solids. For foams, aspects as the elastomer coarsening in the core of the sample or the presence of a thicker solid skin are the critical parameters that justify the improved behavior of the materials produced with a lower mold temperature.Ministerio de Economía, Industria y Competitividad (grant DI-15-07952

Cu and Cu2In nanoparticles supported on amorphised zeolites for the selective reduction of biomass derived carboxylic acids to alcohols

Octanoic acid (OA) was used as reactant with medium chain length to model the aliphatic carboxylic acids which can be produced by catalytic, thermochemical or biological degradation of biomass. A flow through reactor was applied at 21 bar total pressure (in general at 20 bar hydrogen and 1 bar octanoic acid partial pressures) and 330-380 °C. Cu A-, X- and Y-zeolite based catalysts were pretreated in hydrogen flow at 450 °C. During reduction/dehydration A- and X-zeolite structures collapsed and aluminosilicate supported copper catalysts were formed, which contain copper nanoparticles in high dispersion. The catalyst samples were modified by In2O3 co-catalyst. Fatty acid conversion activity of amorphized zeolite supported Cu catalysts and the yield of selectively produced alcohol can be increased drastically by In2O3 addition. Appearance of metallic indium can effectively rein in the step by step catalytic reduction at alkanol formation previous to dehydration of alcohols to alkenes and ethers

Development of covalent triazine frameworks as heterogeneous catalytic supports

Covalent triazine frameworks (CTFs) are established as an emerging class of porous organic polymers with remarkable features such as large surface area and permanent porosity, high thermal and chemical stability, and convenient functionalization that promotes great potential in heterogeneous catalysis. In this article, we systematically present the structural design of CTFs as a versatile scaffold to develop heterogeneous catalysts for a variety of chemical reactions. We mainly focus on the functionalization of CTFs, including their use for incorporating and stabilization of nanoparticles and immobilization of molecular complexes onto the frameworks

n-Aldehydes ( C 6 - C 10 ) in snow samples collected at the high alpine research station Jungfraujoch during CLACE 5

Samples of freshly fallen snow were collected at the high alpine research station Jungfraujoch, Switzerland, during the Cloud and Aerosol Characterization Experiments (CLACE) 5 in February and March 2006. Sampling was carried out on the Sphinx platform. Headspace-solid-phase-dynamic extraction (HS-SPDE) combined with gas chromatography/mass spectrometry (GC/MS) was used to quantify C6–C10 n-aldehydes in the snow samples. The most abundant n-aldehyde was n-hexanal (median concentration 1.324 micro g L -1) followed by n-nonanal, n-decanal, n-octanal and n-heptanal (median concentrations 1.239, 0.863, 0.460, and 0.304 micro g L -1, respectively). A wide range of concentrations was found among individual snow samples, even for samples taken at the same time. Higher median concentrations of all n-aldehydes were observed when air masses reached Jungfraujoch from the north-northwest in comparison to air masses arriving from the southeast-southwest. Results suggest that the n-aldehydes detected most likely are of direct and indirect biogenic origin, and that they entered the snow through the particle phase

A study of the selective hydroconversion of biocarboxylic acids to bioalcohols over novel indium-nickel/zeolite catalysts using octanoic acid as model reactant

Octanoic acid (OA) was hydrotreated in a flow-through reactor at 21 bar total pressure and 240-340 °C over supported metal catalysts prepared from Ni-zeolites (A, X, P) by indium modification. The Ni-zeolites were activated first in H2 flow at 21 bar and 450 °C. While a fraction of the nickel got fully reduced, the zeolite structure became partially destructed. However, some nickel cations remained unreduced, therefore a large fraction of the crystalline zeolite structure was retained. The indium modification of the reduced Ni-zeolites generated bimetallic NiIn/Ni,H-zeolite catalysts having higher stability, hydroconversion activity, octanol selectivity, and lower hydrodecarbonylation activity than the parent partially destructed Ni-zeolite and the Adkins-type catalysts, commercially applied for the conversion of fatty acids to alcohols. © 2013 Akadémiai Kiadó, Budapest, Hungary

Modification of polyoxymethylene for increased thermal resistance

Ternary nanocomposites, composed of polyoxymethylene (POM), ethylene octene copolymer and zinc oxide (ZnO), are prepared by melt compounding. The effects of two types of ethylene-octene copolymers, differing with α-octene content (38% for EOC38 and 17% for EOC17), as well as nanostructured ZnO on thermal behavior of POM are investigated. The content of EOC in the POM based composites is varied between 10 and 50 wt%, while the content of ZnO is 2 wt%. Thermal behavior of POM based systems are studied by using differential scanning calorimetry and thermogravimetric analysis coupled with Fourier transform infrared spectroscopy. Results of thermogravimetric analysis show that, by rising either the elastomer or ZnO content, thermal stability of the investigated POM composites can be increased. The modifying effect of EOC17 in respect of thermal resistance is somewhat greater than that of EOC38. Simultaneous addition of EOC and ZnO to POM is synergistic with respect to thermal stability of the composite material. POLYM. ENG. SCI., 57:772–778, 2017.Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

Foams with enhanced ductility and impact behavior based on polypropylene composites

Producción CientíficaIn this work, formulations based on composites of a linear polypropylene (L-PP), a long-chain branched polypropylene (LCB-PP), a polypropylene–graft–maleic anhydride (PP-MA), a styrene-ethylene-butylene-styrene copolymer (SEBS), glass fibers (GF), and halloysite nanotubes (HNT-QM) have been foamed by using the improved compression molding route (ICM), obtaining relative densities of about 0.62. The combination of the inclusion of elastomer and rigid phases with the use of the LCB-PP led to foams with a better cellular structure, an improved ductility, and considerable values of the elastic modulus. Consequently, the produced foams presented simultaneously an excellent impact performance and a high stiffness with respect to their corresponding solid counterparts.Unión Europea (Evolution project under grant 314744)Ministerio de Ciencia, Innovación y Universidades - Fondo Europeo de Desarrollo Regional (project RTI2018-098749-B-I00)Junta de Castilla y Leon (project VA275P18