Monoesterification of styrene–maleic anhydride copolymers with alcohols in ethyl benzene: Catalysis and kinetics

A kinetic investigation on the monoesterification reaction of the maleic anhydride residue (MA) in styrene-maleic anhydride copolymers with aliphatic alcohols was carried out in ethyl benzene solution. By comparison to classic catalysts such as tributylamine (TBA) and pyridine, 4-dimethylaminopyridine (4DMAP) is by far the most effective catalyst for this reaction. While both general base and nucleophilic mechanisms contribute to the reaction catalyzed by TBA or pyridine, a nucleophilic mechanism prevails with 4DMAP. This reaction is reversible, and its chemical equilibrium constant decreases significantly with increasing temperature. Both kinetic and thermodynamic results showed that in the presence of 4DMAP, the forward and reverse reactions are second and first order, respectively. The existence of side reactions, reactivity of two styrene-maleic anhydride copolymers of different MA contents as well as two aliphatic alcohols of different lengths are also addressed. © 1993 John Wiley & Sons, Inc.     

The projective method for solving linear matrix inequalities

Numerous problems in control and systems theory can be formulated in terms of linear matrix inequalities (LMI). Since solving an LMI amounts to a convex optimization problem, such formulations are known to be numerically tractable. However, the interest in LMI-based design techniques has really surged with the introduction of efficient interior-point methods for solving LMIs with a polynomial-time complexity. This paper describes one particular method called the Projective Method. Simple geometrical arguments are used to clarify the strategy and convergence mechanism of the Projective algorithm. A complexity analysis is provided, and applications to two generic LMI problems (feasibility and linear objective minimization) are discussed.     

Parallel Algorithm for Unconstrained Optimization Based on Decomposition Techniques

We present a numerical implementation of the parallel gradient distribution (PGD) method for the solution of large-scale unconstrained optimization problems. The proposed parallel algorithm is characterized by a parallel phase which exploits the portions of the gradient of the objective function assigned to each processor; then, a coordination phase follows which, by a synchronous interaction scheme, optimizes over the partial results obtained by the parallel phase. The parallel and coordination phases are implemented using a quasi-Newton limited-memory BFGS approach. The computational experiments, carried out on a network of UNIX workstations by using the parallel software tool PVM, show that parallelization efficiency was problem dependent and ranged between 0.15 and 8.75. For the 150 problems solved by PGD on more than one processor, 85 cases had parallelization efficiency below 1, while 65 cases had a parallelization efficiency above 1.     

Differentiability of the Value Function of Nonclassical Optimal Growth Models

We consider an optimal growth (multi-sector) model with nonconvex technology. Using the Clarke results on generalized gradients, we prove that the value function has left and right derivatives with respect to the initial capital stock, without requiring supermodularity assumptions.     

POSITIVE SOLUTIONS FOR NONHOMOGENEOUS ELLIPTIC EQUATIONSWITH CRITICAL GROWTH ON R~(2)

1IntroductionIntillspaper,weare(follccrlledwitlltileexistellccofPositly(tsollltiollsoftilefollowillgnonhonlogelleousellipticProblclll:whereg(x)EL'(R'),g(:v)Z0alldg(x)t0,f(x,t)=h(x,t).hi=withb>0,h(x,t)EC(R=xR,R)alldtilefollowing(CI)-(C3)11old:(CI)sliphillM0.linljfl- x,h(T,t)(t--if-=011llif'orllllyforxeR2.hill}t:l-:,t)(axle(~ltJ')= lx,11lliforllllyl'Ora:6RZ.ltl~la(C3)ThereexistM>0,aE(0,1]sucllthatFOllowing[1,5],wesaythatf(x,t)=h(x,f…     

Noise-assisted mound coarsening in epitaxial growth

Two types of mechanisms are proposed for mound coarsening during unstable epitaxial growth: stochastic, due to deposition noise, and deterministic, due to mass currents driven by surface energy differences. Both yield the relation H=(RWL)² between the typical mound height W, mound size L, and the film thickness H. An analysis of simulations and experimental data shows that the parameter R saturates to a value which discriminates sharply between stochastic () and deterministic () coarsening. We derive a scaling relation between the coarsening exponent 1/z and the mound-height exponent which, for a saturated mound slope, yields . Received: 11 November 1997 / Revised in final form: 28 November 1997 / Accepted: 28 November 1997     

On Producing Multiple Solutions Using Repeated Trials

The number of trials that is required by an algorithm to produce a given fraction of the problem solutions with a specified level of confidence is analyzed. The analysis indicates that the number of trials required to find a large fraction of the solutions rapidly decreases as the number of solutions obtained on each trial by an algorithm increases. In applications where multiple solutions are sought, this decrease in the number of trials could potentially offset the additional computational cost of algorithms that produce multiple solutions on a single trial. The analysis framework presented is used to compare the efficiency of a homotopy algorithm to that of a Newton method by measuring both the number of trials and the number of calculations required to obtain a specified fraction of the solutions.     

Alkenylidenes in Organic Synthesis

Alkenylidenes R₂C?C: (= alkylidene carbenes) undergo regio- and stereoselective intramolecular C? H insertion reactions that are excellently suited for the synthesis of cyclopentenes. The 1, 2-shifts occurring with R?H and R?Ar are useful for the preparation of alkynes. Alkenylidenes are efficiently generated from carbonyl compounds by diazomethylation, from vinyl halides by α-elimination, from alkynyliodonium salts by addition of nucleophiles, and from alkynes by retro-1, 2-shifts. Specific applications of the various methods, particularly in the synthesis of natural products, are discussed.     

Extended convergence results for the method of multipliers for nonstrictly binding inequality constraints

In this paper, we extend the classical convergence and rate of convergence results for the method of multipliers for equality constrained problems to general inequality constrained problems, without assuming the strict complementarity hypothesis at the local optimal solution. Instead, we consider an alternative second-order sufficient condition for a strict local minimum, which coincides with the standard one in the case of strict complementary slackness. As a consequence, new stopping rules are derived in order to guarantee a local linear rate of convergence for the method, even if the current Lagrangian is only asymptotically minimized in this more general setting. These extended results allow us to broaden the scope of applicability of the method of multipliers, in order to cover all those problems admitting loosely binding constraints at some optimal solution. This fact is not meaningless, since in practice this kind of problem seems to be more the rule rather than the exception.In proving the different results, we follow the classical primaldual approach to the method of multipliers, considering the approximate minimizers for the original augmented Lagrangian as the exact solutions for some adequate approximate augmented Lagrangian. In particular, we prove a general uniform continuity property concerning both their primal and their dual optimal solution set maps, a property that could be useful beyond the scope of this paper. This approach leads to very simple proofs of the preliminary results and to a straight-forward proof of the main results.The author gratefully acknowledges the referees for their helpful comments and remarks. This research was supported by FONDECYT (Fondo Nacional de Desarrollo Científico y Technológico de Chile).