Search results for "Alkane"

Nonporous Organic Solids Capable of Dynamically Resolving Mixtures of Diiodoperfluoroalkanes

2009

Halogen bonding has increasingly facilitated the assembly of diverse host-guest solids. Here, we show that a well-known class of organic salts, bis(trimethylammonium) alkane diiodides, can reversibly encapsulate α,ω-diiodoperfluoroalkanes (DIPFAs) through intermolecular interactions between the host's I – anions and the guest's terminal iodine substituents. The process is highly selective for the fluorocarbon that forms an I – ···I(CF 2 ) m I···I – superanion that is matched in length to the chosen dication. DIPFAs that are 2 to 12 carbons in length (common industrial intermediates) can thereby be isolated from mixtures by means of crystallization from solution upon addition of the dissolv…

Catalytic cracking of n-alkane naphtha: The impact of olefin addition and active sites differentiation

2015

An extended dual kinetic model allows to fit the n-heptane cracking results working in a wide range of reaction conditions. The duality of the model is provided by the contribution of monomolecular and bimolecular cracking mechanisms. It takes into account the role played by the olefins formed on the global cracking or added within the feed. Furthermore by means of this model and the kinetic parameters obtained when cracking n-heptane on ZSM-5, it has been observed that, while some characterization techniques show a homogeneous zeolite surface from the point of view of the active sites, rigorous kinetic experiments point to the possibility that the reactant sees a heterogeneous surface with…

On the effect of pressure on the phase transition of polymer blends and polymer solutions: Oligostyrene–n-alkane systems

2001

Critical temperatures of some binary solutions of weakly interacting low molecular weight polystyrenes dissolved in linear alkanes (oligoethylenes) were measured over the range 0.1 to 100 MPa. While (dT/dP)crit along the upper critical solution (UCS) locus for a “typical blend” is positive, and for the “ typical solution” can be either positive or negative (but is usually negative), there is no essential difference between blend and solution. Rather, the difference in sign is a consequence of the location of the hypercritical point (that point in (T,P)crit space where (dT/dP)crit changes sign, [(dT/dP)crit = 0 and (d2T/dP2)crit>0], also called the double critical point, DCP), which is norma…

Organo-catalyzed synthesis of aliphatic polycarbonates in solvent-free conditions

2012

A new efficient and expeditious route to the synthesis of aliphatic polycarbonates, in solvent-free conditions and using 1-n-butyl-3-methylimidazolium-2-carboxylate (BMIM-2-CO2) as a catalyst precursor, is described. The protocol consists of a two-step polymerization process involving the transesterification of dimethyl carbonate (DMC) with linear alkane diols and leading to high molecular weight homopolymers. The reaction went to completion quantitatively with the liberation of methanol as the only by-product. The in situ formation of N-heterocyclic carbene species resulting from BMIM-2-CO2 decarboxylation is suggested to be a key feature of the condensation process. The protocol was then …

Deep oxidation of volatile organic compounds using ordered cobalt oxides prepared by a nanocasting route

2010

Ordered Co3O4 with high surface area (until 173 m2/g) has been successfully obtained through a nanocasting route using mesoporous KIT-6 silica as a hard template and tested in the deep oxidation of a series of representative volatile organic compounds (VOCs): propane as a model of short chain alkane and toluene as a model of monoaromatic hydrocarbon. It has been demonstrated that the catalytic activity for VOC deep oxidation is very elevated and its catalytic stability at moderate temperatures very good. However, the role of the ordered structure in the catalytic performance does not seem to be beneficial. The enhanced catalytic activity has been explained in terms of both the high surface …

Theoretical characterization of iron and manganese porphyrins for catalyzed saturated alkane hydroxylations

1997

Abstract The theoretical characterization of porphin (H2Por), iron and manganese porphyrins MIII(Por) and their chlorine derivatives MIII(Por)Cl has been carried out. This work represents a first step for modelling catalyzed saturated alkane hydroxylations. The chlorine atom is responsible for the existence of a dipole moment of 1.2–2.0 D in the MIII(Por)Cl molecules and for a negative value of the mean quadrupole moment (−16–(−14)DA). The charge of the metal atom (1.8–2.2 e) is rather varied (to 2.1–2.6 e) and the effective polarizability (2.8–2.9 A3) is increased (to 3.5–3.6 A3) by the addition of the chlorine atom. Starting from the porphin molecule, the presence of the metal atom decrea…

Linear chain surfactants at a planar interface: a comparative Monte Carlo study of several lattice models

1993

Linear chain surfactants in a densely packed arrangement (such as alkane chains in lipid monolayers in the “uniform tilt” structures) are described by a crude coarse-grained model where the endgroups grafted on the interface form a regular lattice and the chains are described by the bond fluctuation model with chains containing N = 4 effective monomers only. Square-well interactions between the monomers are studied for both the attractive and repulsive case for three choices of the interaction range. None of these models exhibits a structure with uniform tilt. For attractive interactions the last bond has a strong tendency to fold back thus leading to a very high density close to the interf…

1988

Deviations in the determination of the unperturbed dimensions of polymers arising in ternary polymer systems (solvent (1)/solvent (2)/polymer) can be explained by the inaccurate use of an interaction parameter independent of polymer molecular weight. On this basis, a new formalism for the calculation of the second virial coefficient from intrinsic viscosity is proposed. This formalism was tested (and compared with well established formalisms) for all ternary polymer systems with simultaneous intrinsic viscosity and second virial coefficient data in the literature.

Static and Dynamic Properties of a n-C100H202 Melt from Molecular Dynamics Simulations

1997

We present in this work results from atomistic molecular dynamics simulations of a n-C100H202 melt. This work represents a first effort to simulate a fully equilibrated ensemble of chains of suffic...

Functionalization of CnH2n+2Alkanes: Supercritical Carbon Dioxide Enhances the Reactivity towards Primary Carbon-Hydrogen Bonds

2015

The functionalization of the primary sites of alkanes is one of the more challenging areas in catalysis. In this context, a novel effect has been discovered that is responsible for an enhancement in the reactivity of the primary C-H bonds of alkanes in a catalytic system. The copper complex Cu(NCMe) (=hydrotris{[3,5-bis(trifluoromethyl)-4-bromo]-pyrazol-1-yl}borate) catalyzes the functionalization of CnH2n+2 with ethyl diazoacetate upon inserting the CHCO2Et unit into C-H bonds. In addition, the selectivity of the reaction toward the primary sites significantly increased relative to that obtained in neat alkane upon using supercritical carbon dioxide as the reaction medium. This was attribu…