Microwave Effects Due to Anionic or Cationic Initiators in Emulsion Polymerization Reactions

Summary: Emulsion polymerization reactions were performed under microwave irradiation and conventional heating using anionic or cationic initiators and surfactants. Microwave irradiation promoted higher reaction rates for both initiators and surfactants, in comparison with the conventional heating. The effect of high power microwave irradiation was studied using a method of cycles of heating and cooling, where rapid polymerization reactions were obtained. In the reactions with anionic initiator and surfactant, a decrease in the particle diameters was observed with microwave heating, and even smaller particles were obtained using high power microwave irradiation. Moreover, the decrease in the particle size was acompanied by an increase in the polymer molecular weight. On the other hand, these effects were not observed for reactions with cationic initiator and surfactant.     

Kinetics and Molecular Weight Development of Dithiolactone‐Mediated Radical Polymerization of Styrene

Calculations of polymerization kinetics and molecular weight development in the dithiolactone‐mediated polymerization of styrene at 60 °C, using 2,2′‐azobisisobutyronitrile (AIBN) as initiator and γ‐phenyl‐γ‐butirodithiolactone (DTL1) as controller, are presented. The calculations were based on a polymerization mechanism based on the persistent radical effect, considering reverse addition only, implemented in the PREDICI® commercial software. Kinetic rate constants for the reverse addition step were estimated. The equilibrium constant (K = k_add/k_‐add) fell into the range of 10⁵–10⁶ L · mol^?1. Fairly good agreement between model calculations and experimental data was obtained.

     

Graphs of transportation polytopes

This paper discusses properties of the graphs of 2-way and 3-way transportation polytopes, in particular, their possible numbers of vertices and their diameters. Our main results include a quadratic bound on the diameter of axial 3-way transportation polytopes and a catalogue of non-degenerate transportation polytopes of small sizes. The catalogue disproves five conjectures about these polyhedra stated in the monograph by Yemelichev et al. (1984). It also allowed us to discover some new results. For example, we prove that the number of vertices of an m×n transportation polytope is a multiple of the greatest common divisor of m and n.     

Stable equivariant abelianization, its properties, and applications

Let G be a finite group. For a based G-space X and a Mackey functor M, a topological Mackey functor is constructed, which will be called the stable equivariant abelianization of X with coefficients in M. When X is a based G-CW complex, is shown to be an infinite loop space in the sense of G-spaces. This gives a version of the RO(G)-graded equivariant Dold-Thom theorem. Applying a variant of Elmendorf's construction, we get a model for the Eilenberg-Mac Lane spectrum HM. The proof uses a structure theorem for Mackey functors and our previous results.     

The number of faces of the tridiagonal Birkhoff polytope

Counting basic objects as the vertices of polyhedra is a demanding problem in general, even for the most basic structured polytope. In this paper, we determine the number of q-faces for some q ≥ 1 of the polytope of tridiagonal doubly stochastic matrices.     

GRASP with hybrid heuristic-subproblem optimization for the multi-level capacitated minimum spanning tree problem

We propose a GRASP using an hybrid heuristic-subproblem optimization approach for the Multi-Level Capacitated Minimum Spanning Tree (MLCMST) problem. The motivation behind such approach is that to evaluate moves rearranging the configuration of a subset of nodes may require to solve a smaller-sized MLCMST instance. We thus use heuristic rules to define, in both the construction and the local search phases, subproblems which are in turn solved exactly by employing an integer programming model. We report numerical results obtained on benchmark instances from the literature, showing the approach to be competitive in terms of solution quality. The proposed GRASP have in fact improved the best known upper bounds for almost all of the considered instances.     

How "sticky" are short-range square-well fluids?

The aim of this work is to investigate to what extent the structural properties of a short-range square-well (SW) fluid of range lambda at a given packing fraction eta and reduced temperature T* = kBT/epsilon can be represented by those of a sticky-hard-sphere (SHS) fluid at the same packing fraction and an effective stickiness parameter tau(T*,lambda). Such an equivalence cannot hold for the radial distribution function g(r) since this function has a delta singularity at contact (r = sigma) in the SHS case, while it has a jump discontinuity at r = lambda sigma in the SW case. Therefore, the equivalence is explored with the cavity function y(r), i.e., we assume that [formula: see text]. Optimization of the agreement between y(SW) and y(SHS) to first order in density suggests the choice tau(T*,lambda) = [12(e(1/T* - 1)(lambda - 1)](-1). We have performed Monte Carlo (MC) simulations of the SW fluid for lambda = 1.05, 1.02, and 1.01 at several densities and temperatures T* such that tau(T*,lambda) = 0.13, 0.2, and 0.5. The resulting cavity functions have been compared with MC data of SHS fluids obtained by Miller and Frenkel[J. Phys.: Condens. Matter 16, S4901 (2004)]. Although, at given values of eta and tau, some local discrepancies between y(SW) and y(SHS) exist (especially for lambda = 1.05), the SW data converge smoothly toward the SHS values as lambda-1 decreases. In fact, precursors of the singularities of y(SHS) at certain distances due to geometrical arrangements are clearly observed in y(SW). The approximate mapping y(SW)-->y(SHS) is exploited to estimate the internal energy and structure factor of the SW fluid from those of the SHS fluid. Taking for y(SHS) the solution of the Percus-Yevick equation as well as the rational-function approximation, the radial distribution function g(r) of the SW fluid is theoretically estimated and a good agreement with our MC simulations is found. Finally, a similar study is carried out for short-range SW fluid mixtures.     

Mimicking the atmospheric OH-radical-mediated photooxidation of isoprene: formation of cloud-condensation nuclei polyols monitored by electrospray ionization mass spectrometry

Recently, it has been proposed (M. Claeys et al., Science 2004; 303: 1173) that the atmospheric OH-radical-mediated photooxidation of isoprene is a source of two major secondary organic aerosol (SOA) components, that is, 2-methylthreitol and 2-methylerythritol. These diastereoisomeric tetrols, which were characterized for the first time in the fine size fraction (<2.5 microm aerodynamic diameter) of aerosols collected in the Amazon rain forest during the wet season, were proposed to enhance the capability of the aerosols to act as cloud-condensation nuclei. In the present study, we performed the oxidation of isoprene in aqueous solution under conditions that attempted to mimic atmospheric OH-radical-induced photooxidization, and monitored and characterized on-line the reaction products via electrospray ionization mass (and tandem mass) spectrometry in the negative ion mode. The results show that the reaction of isoprene with photo- or chemically generated hydroxyl radicals indeed yields 2-methyltetrols. Other polyols were also detected, and they may therefore be considered as plausible SOA components eventually formed in normal or more extreme OH-radical-mediated photooxidation of biogenic isoprene.