Methylol‐functional benzoxazines as precursors for high‐performance thermoset polymers: Unique simultaneous addition and condensation polymerization behavior

A new class of high‐performance resins of combined molecular structure of both traditional phenolics and benzoxazines has been developed. The monomers termed as methylol‐functional benzoxazines were synthesized through Mannich condensation reaction of methylol‐functional phenols and aromatic amines, including methylenedianiline (4,4′‐diaminodiphenylmethane) and oxydianiline (4,4′‐diaminodiphenyl ether), in the presence of paraformaldehyde. For comparison, other series of benzoxazine monomers were prepared from phenol, corresponding aromatic amines, and paraformaldehyde. The as‐synthesized monomers are characterized by their high purity as judged from ¹H NMR and Fourier transform infrared spectra. Differential scanning calorimetric thermograms of the novel monomers show two exothermic peaks associated with condensation reaction of methylol groups and ring‐opening polymerization of benzoxazines. The position of methylol group relative to benzoxazine structure plays a significant role in accelerating polymerization. Viscoelastic and thermogravimetric analyses of the crosslinked polymers reveal high T_g (274–343 °C) and excellent thermal stability when compared with the traditional polybenzoxazines. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

On safe tractable approximations of chance constraints

A natural way to handle optimization problem with data affected by stochastic uncertainty is to pass to a chance constrained version of the problem, where candidate solutions should satisfy the randomly perturbed constraints with probability at least 1 − ?. While being attractive from modeling viewpoint, chance constrained problems “as they are” are, in general, computationally intractable. In this survey paper, we overview several simulation-based and simulation-free computationally tractable approximations of chance constrained convex programs, primarily, those of chance constrained linear, conic quadratic and semidefinite programming.     

An abstract symmetric framework for duality in mathematical programming

The paper offers an abstract structure called environment (of mathematical programming) in which a pair of dual programs is settled symmetrically. Given an environment, the concepts of an optimization program, its dual and the associated Lagrangean are formalized and studied. The usual asymmetries in certain types of mathematical programming are due to selection of asymmetric environments. Common types of programming like: linear, nonlinear, convex, integer etc. are reviewed in the proposed framework.     

Weierstrass theorem for monotonically semicontinuous functions

The concept of monotone semicontinuity is introduced. It is shown that every monotonically semicontinuous function with values in a space equipped with arbitrary preference relation achieves its extremes on compacts     

The multi-attribute grey target decision method for attribute value within three-parameter interval grey number

Based on the grey system theory and methods, the grey-target decision-making problem is discussed, in which the attribute values are grey numbers and the maximum probability of the value of grey number is known. Firstly, the optimal effect vector is the positive bull’s-eye and positive bull’s-eye distance of each scheme is defined. Subjectively or objectively weighting method is integrated to determine the index weight and integrated optimization model of index weight is established. Finally, the critical effect vector is the negative bull’s-eye and negative bull’s-eye distance of each scheme is defined, then relative bull’s-eye distance and comprehensive the bull’s-eye distance of grey target decision-making are given. An example is also presented to illustrate the usefulness and effectiveness of the methods obtained in this paper and provides a new idea for grey target decision-making method research.     

An efficient metal catalyst free approach to synthesize 5-(4-(1,2,4,5 tetrazin-3-yl)benzylamino)-5-oxopentanoic acid

Despite the wide use of 1,2,4,5- tetrazines in biomaterials and materials science, currently there does not exist synthetic method(s) that can yield significant amount of 1,2,4,5- tetrazines without the use of potentially toxic metal catalysts. Here, we report a less energy intensive and more efficient metal catalyst free approach for the synthesis of an asymmetric tetrazine. A range of operating parameters such as extraction pH and temperature were regulated to achieve a practical yield nearly 1.5 times greater than the yields reported in the literature for similar synthetic procedures.     

Efficient monooleoyl glycerol synthesis employing hybrid ultrasonic-infrared-wave promoted reactor: Concurrent catalytic and noncatalytic esterification kinetics

For the first time, intensification of monooleoyl glycerol (MOG) synthesis has been investigated in an ultrasonic-infrared-wave (USIRW) promoted batch reactor. Esterification of octadecanoic acid (ODA) with glycerol (Gl) has been conducted [using Amberlyst 36 wet catalyst] in three different reactors, namely traditional batch reactor (TBR), infrared wave promoted batch reactor (IRWPBR), and USIRW-promoted batch reactor (USIRWPBR) to assess the relative efficacy. The energy-efficient USIRWPBR remarkably intensifies the ODA-Gl esterification as manifested through superior ODA conversion (92.5 ± 1.25%) compared to that achieved in IRWPBR (79.8 ± 1.2%) and TBR (36.39 ± 1.25%). The most favorable reaction condition for optimum ODA conversion and maximum MOG yield was identified through statistical optimization over a selected parametric range, namely 3-5 Gl/ODA mole ratio, 0.004-0.006 g/mL Amberlyst 36 catalyst concentration, 300-700 rpm impeller speed, and 333-353 K reaction temperature. The present study also reports the formulation and validation of an innovative reaction kinetics, that is, concurrent noncatalytic and heterogeneously catalyzed (CNCHC) reaction mechanism in addition to the conventional heterogeneous kinetic models (LH and Eley-Rideal mechanisms). Under combined USIRW, the CNCHC esterification mechanism could best describe ODA-Gl esterification (R² = 0.98) compared to LH (R² = 0.97) and Eley-Rideal (R² = 0.88) mechanisms. The optimal product (MOG) was characterized by differential scanning calorimetry and thermogravimetric analysis to assess its crystallization property and thermal stability for possible application as plasticizer/fuel additives.     

Combining 2D synchrosqueezed wave packet transform with optimization for crystal image analysis

We develop a variational optimization method for crystal analysis in atomic resolution images, which uses information from a 2D synchrosqueezed transform (SST) as input. The synchrosqueezed transform is applied to extract initial information from atomic crystal images: crystal defects, rotations and the gradient of elastic deformation. The deformation gradient estimate is then improved outside the identified defect region via a variational approach, to obtain more robust results agreeing better with the physical constraints. The variational model is optimized by a nonlinear projected conjugate gradient method. Both examples of images from computer simulations and imaging experiments are analyzed, with results demonstrating the effectiveness of the proposed method.     

Investigation of the equality constraint effect on the reduction of the rotational ambiguity in three-component system using a novel grid search method

The obtained results by soft modeling multivariate curve resolution methods often are not unique and are questionable because of rotational ambiguity. It means a range of feasible solutions equally fit experimental data and fulfill the constraints. Regarding to chemometric literature, a survey of useful constraints for the reduction of the rotational ambiguity is a big challenge for chemometrician. It is worth to study the effects of applying constraints on the reduction of rotational ambiguity, since it can help us to choose the useful constraints in order to impose in multivariate curve resolution methods for analyzing data sets. In this work, we have investigated the effect of equality constraint on decreasing of the rotational ambiguity. For calculation of all feasible solutions corresponding with known spectrum, a novel systematic grid search method based on Species-based Particle Swarm Optimization is proposed in a three-component system.