Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization

Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004     

UV curing of a novel resin derived from poly(ethylene terephthalate)

The synthesis and characterization of photopolymerizable unsaturated polyester resins based on PET waste are described. The resins came from a depolymerization process based on the glycolysis of PET by diethylene glycol (DEG). Different molecular weights of glycolysates were synthesized. Then, the latter was functionalized by a methyl hemiester of maleic acid to obtain unsatured α,ω‐bismaleate PET oligomers. In the presence of an electron donor monomer, such as triethylene glycol divinyl ether, these electron acceptor oligomers were copolymerized by way of charge‐transfer complexes under UV irradiation. The reaction was monitored in situ by real‐time IR spectroscopy to study the kinetics of photopolymerization. This one was studied in relation with the physical and chemical characteristics of oligoesters and the composition of mixtures containing divinyl ethers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1324–1335, 2007     

Fast switching anisotropic networks obtained by in situ photopolymerization of liquid crystal molecules

Lightly cross-linked anisotropic networks with uniaxial and π/2 twisted orientations were produced by photopolymerization of monotropic mixtures containing liquid crystal mono and diacrylates. In this way the polymer backbone was immobilized and became decoupled from the motion of the mesogenic side groups. The networks showed very good reversibility and even after becoming isotropic, upon cooling, the initial orientation was recovered. In the same way, in the presence of electric fields the mesogenic groups could be reoriented in the direction of the electric field, reverting back to the initial orientation on removal of the field at a rate comparable with those observed in the monomeric state. Combining viscoelastic measurements with the dielectric behaviour of the monomeric liquid crystal and the anisotropic network, a comparison between the internal and bulk rotational viscosities was also made.     

On the linear relaxation of a one-dimensional bonded fluid model

The linear relaxation of a one-dimensional bonded fluid model is studied in the dynamical mean field approximation at the pair level. The results are compared with simulation data. Relaxation at low temperatures shows a cooperative character that can be understood in terms of a simple diffusion picture.     

Parametric linear programming techniques for the indefnite quadratic programming problem

In this paper, we discuss a multiparametric technique for findinga global minimum for an indefinite quadratic programming problembased on the spectral decomposition of the matrix of the quadraticform. Special attention is given to the case where this matrixhas only rank 1, where the multiparametric linear program turnsout to be a single-parameter linear program. An extension ofthe traditional linear parametric procedure is introduced whichin general solves this problem efficiently. However, an exampleis presented showing that this technique may take an exponentialnumber of steps.     

Optimal repair-cost limit for a consumer following expiry of a warranty

This paper develops a methodology for obtaining the optimalrepair-cost limit for the repair-replace decision that a consumerfaces on the expiry of a product warranty, where the producthas been minimally repaired on failure during the warranty.Three cases are considered; (i) an exponentially distributedtime to failure with an arbitrary repair-cost distribution,(ii) an exponentially distributed time to failure with a uniformrepair-cost distribution, and (iii) a Weibull-distributed timeto failure with a beta-distributed repair cost. Numerical optimizationsare performed for the third case, and conclusions drawn as tothe sensitivity of the optimal repair-cost limit on the parametervalues of the distributions involved.     

RESTRICTION RESPECTUEUSE ET RECONSTRUCTION DES CHAINES ET DES RELATIONS INFINITES

We show a faithful restriction theorem among infinite chains which implies a reconstructibility conjecture of Halin. This incite us to study the reconstructibility in the sense of Fraïssé and to prove it for orders of cardinality infinite or ≥ 3 and for multirelations of cardinality infinite or ≥ 7, what improves the theory obtained by G. Lopez in the finite case. For this work we had to study the infinite classes of difference which have to be a linear order of type ω, ω* or ω* + ω; this complete the theory made by G. Lopez for the finite case ([13]). We show also Ulam-reconstructibility for linear orders which have a fixed point.     

The automatic conversion of spinor equations to dyad form in MAPLE

A new package in the symbolic algebra system MAPLE is presented for the conversion of complicated spinor equations to their expansions with respect to a normalized spinor dyad. By following a simple index convention, we obtain a powerful computational tool with a straightforward and easy to use syntax. A number of examples, including nontrivial applications of the package to recent research, are provided.     

The use of sulfide cluster-derived catalysts to understand the promotional effect in hydrotreatment catalysis

Sulfide cluster-derived ensembles are promising models of the active sites in commercial hydrotreatment catalysts. A series of sulfide clusters were adsorbed intact onto high-surface-area γ-alumina, magnesium oxide and activated carbon supports, then pretreated to produce highly dispersed catalytic ensembles with sizes similar to those of their precursor clusters. The activities of the bimetallic cluster-derived catalysts were significantly higher than those of the monometallic catalysts. We took this as evidence that direct interactions between molybdenum and the promoter element cause the promotional effect observed in commercial hydrotreatment catalysts. The hydrodesulfurization and hydrodenitrogenation activities correlated with the extent of molybdenum reduction. Our results suggested that the active sites in promoted hydrotreatment catalysts are centered on molecular-scale ensembles containing molybdenum, sulfur and the promoter element.