The effectiveness of some commercial emulsifiers in emulsion polymerization II. Anionic types

The initial polymerization rate of ethyl, butyl, and 2-ethylhexyl acrylate was studied in a thermally insulated polymerization reactor. The monomers were continuously added into the reactor and the effect of concentration of anionic emulsifiers on the temperature increase was investigated. Alkyl(aryl)polyethylenglykolethersulfate were found to be most effective in promoting the initial polymerization rate. An inhibition action of some emulsifiers was found.     

Optimal periodic control of a continuous “living” anionic polymerization. I. Theoretical study

Within certain limitations, this work shows that the production of polymers with any prespecified number average chain length and polydispersity is theoretically feasible when “living” anionic polymerizations are carried out in continuous stirred tank reactors (CSTRs) which are under optimal periodic forcing of the feed flows. The optimal periodic control problem was solved adopting a suboptimal objective function and a novel iterative numerical procedure. When the objective function is minimized in order to reduce the time average polydispersity, then the operation tends to become a sequential semibatch process. Conversely, if the objective is to maximize these variables, then the reagent concentrations inside the reactor tend to be 180° out of phase. Different periods of oscillation must be selected depending on whether the required average polydispersities are above or below the steady state value of 2. The greatest flexibility in the MWD control is obtained with fast kinetics, and, in this case, average polydispersities between 1.06 and 9.2 may be required.     

Molecular weight distribution control in a semibatch “living” anionic polymerization. I. Theoretical study

A method to produce homopolymers of preestablished molecular weight distribution (MWD), through “living” anionic polymerizations carried out in homogeneous semibatch reactors is proposed and theoretically justified. In the direct form of the technique, very fast reactions are assumed, and the monomer and “killing” agent feed flows are obtained from the knowledge of the desired MWD, the system spreading function, the total reaction time, the initial reaction volume, and the reagent concentrations. Alternatively, by controlling a reactor outlet flow instead of the “killing” agent feed, an external deactivation of the “living” ends can be implemented. The method can be extended to slow reactions, to more elaborated mechanisms, and to take into account the unwanted deactivation of “living” ends by impurities in the monomer solution feed.     

Modeling of “living” free‐radical polymerization processes. I. Batch,semibatch, and continuous tank reactors

A comprehensive mathematical model is developed for “living” free‐radical polymerization carried out in tank reactors and provides a tool for the study of process development and design issues. The model is validated using experimental data for nitroxide‐mediated styrene polymerization and atom transfer radical copolymerization of styrene and n‐butyl acrylate. Simulations show that the presence of reversible capping reactions between growing and dormant polymer chains should boost initiation efficiency when using free nitroxide in conjunction with conventional initiator and also increase the effectiveness of thermal initiation. A study shows the effects of the value of the capping equilibrium constant and capping reaction rate constants for both nitroxide‐mediated styrene polymerization (using alkoxyamine as polymer chain seeds) and atom transfer radical polymerization of n‐butyl acrylate (using methyl 2‐bromopropionate as chain extension seeds). Also the effect of introducing additional conventional initiator into atom transfer radical polymerization of n‐butyl acrylate is studied. It is found that the characteristics of long chain growth are determined by the fast exchange of radicals between growing and dormant polymer chains. Polymerization results in batch, semibatch, and a series of continuous tank reactors are analyzed. The simulations also show that a semibatch reactor is most flexible for the preparation of polymers with controlled architecture. For continuous tank reactors, the residence time distribution has a significant effect on the development of chain architecture. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1630–1662, 2002     

The “alexandrite effect” in gemstones

The term “alexandrite effect” is used in gemology to describe a distinct change of color appearance when a gemstone is switched from daylight to incandescent light. Gemstones that exhibit the alexandrite effect can actually be divided into four categories based upon the value of the calculated absolute hue-angle change of the material under different pairs of illuminants. the alexandrite effect is a non-color-constancy phenomenon. It can be explained by a combination of both chromaticity adaptations to the different light sources, and vision system responses to the spectral distribution of the light emitted by alexandrite effect gemstones when they are illuminated alternatively by the different light sources.     

Theory of “Cohesive” vs “Adhesive” Separation in an Adhering System

It is shown that there is limited validitity to the doctrine that true interfacial separation, in an adhering system, is highly improbable. An analysis employing the Griffith-Irwin crack theory yields these results: The important parameters are, difference in elastic moduli, ΔE; differences in g, the energy dissipation per unit crack extension; thickness, Δ₁ or δ₂, of the region where dissipation occurs; and the presence or absence of strong interfacial bonds. If the forces across the interface are appreciably weaker than the cohesive forces in either phase, there is a strong minimum in g at the interface. For flaws of equal size, an interfacial flaw will be the site of initiation of failure. If strong interfacial bonds are present, then if Δg and ΔE have the same sign, failure is most probable, deep within one phase. If Δg and ΔE have opposite signs, failure may be initiated, and may propagate, at a distance δ from the interface, in the phase with lower g. This may be mistaken for weak-boundary layer failure.     

Fatty acids characterization in “Alicante” and “Jijona” nougat bars,two Spanish sweets

In this work the fatty acids in two typical Spanish sweets have been characterized: Alicante and Jijona nougat bars, using gas chromatography with a flame-ionization detector. The majority of the fatty acids in these two sweets are unsaturated, and only a low proportion is saturated, which turns them into a type of food with low influence on cholesterol resulting in low atherogenic power, due to the low amount of saturated fatty acids, which is far from constituting 1/3 of the total sum of fatty acids granted by a diet, a limit that has been advised by a great number of International Scientific Committees.     

Thermal stability of “living” polymer–lithium systems

The thermal stabilities of polybutadienyllithium, polyisoprenyllithium, and polystyryllithium solutions have been determined in hydrocarbon solvents. Kinetic analysis indicated that a complex mechanism was involved in the thermolysis of polybutadienyllithium. The thermal stability was observed to increase with increasing lithium concentration, suggesting the presence of competitive reactions in addition to the expected elimination of lithium hydride. The thermal stability of the three systems studied was consistent with their reported degrees of association: dimeric polystyryllithium was less stable than tetrameric polyisoprenyllithium or hexameric polybutadienyllithium.     

Tetraphenylethane iniferters: Polyurethane-polystyrene multiblock copolymers through “living” radical polymerization

Toluene diisocyanate-based polyurethane iniferters containing tetraphenyl-ethane groups in between polyurethane blocks were prepared by the reaction of isocyanate-terminated prepolymers and 1,1,2,2-tetraphenyl-1,2-ethanediol. When these iniferters were decomposed in the presence of styrene, polyurethane-polystyrene multiblock copolymers were obtained through a “living” radical mechanism. The effect of changing polyol on the T_g, thermal stability, and molecular weight of polyurethane iniferters as well as block copolymers was studied. The molecular weight of the block copolymers increased with increasing both polymerization time and conversion. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1551–1560, 1997     

The role of pore structure in the catalytic behavior of “unaged” and “aged” silica-alumina catalysts

This is a review of research concerning the role played by the porous structure of silica-alumina catalysts on the evolution of organic catalytic processes. A strong effect of the geometrical shape of the pores on catalytic activity and selectivity has been evidenced. The experimental results have also been interpreted by means of a simplified mathematical model, able to relate selectivity for a reaction of the type A → B → C to the geometrical features of macro-microporous catalyst pellets, or granules. The theoretical results are in qualitatively satisfactory agreement with the experimental data.     

Classification of properties of elastomers using the “optimum property concept.” I. Introduction

An attempt is made to distinguish properties of elastomers by types. “Basic properties of materials” or “network properties” in elastomers are properties which either increase or decrease from the liquid to the solid state of materials or over the range of the “elastomeric plateau” of elastomers. From these are distinguished properties that exhibit characteristic maxima and are therefore “maximum properties” or bivalued properties. Mechanical failure properties show the characteristics of “maximum properties.” The maxima in “maximum properties” generally do not coincide. This noncoincidence of the maxima with a change in a “basic property of a material” has major theoretical and practical implications, for example, it is the cause of the crossovers in the relative performance rating of materials under different test conditions. The implications of this noncoincidence of the failure property maxima on the relevance of correlations between these properties are discussed. A change in the testing conditions is reflected in a shift of the optimum value in a “basic property of a material” with respect to a specific “maximum property.” Data and certain conclusions in the literature are interpreted on the basis of this concept. Examples of the limitations of the validity of mathematical relationships are presented. Also, a definition of the term “state of cure” is proposed and a suggestion for the rating of severities of test equipment and applications of elastomeric materials recommended. The effect of increased degrees of crosslinking for a series of polymers and crosslinking agents is assessed. It is suggested that the “mechanisms” of failure properties will remain elusive if their rationalization is attempted on the basis of other failure properties, e.g., the mechanism of abrasion on that of tear strength or cut growth. The main purpose of this proposal is to provide support for a drastic reduction in laboratory testing by identifying those properties which can lead to different relative ratings in routine evaluations and actual applications. A more empirical approach to materials evaluations is recommended based on the calibration of laboratory instrumentation with respect to specific applications. A de-emphasis of routine evaluations of materials on the basis of their “maximum properties” seems to be justified.     

High conversion study of “living” radical polymerization of styrene using DSC

The influence of temperature on nitroxide-controlled living radical polymerization of styrene was examined. It has been established that only in a temperature range of 110°C to 150°C nitroxides are able to control radical polymerization. At temperatures above 160°C the reaction was of rather a free radical character. The results were similar for all the various nitroxides used as capping agents: TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl), 4-hydroxy-TEMPO, 4-oxo-TEMPO and 4-acetamido-TEMPO. Differences were found only in the induction times of polymerization and were probably due to side reactions with the initiator (benzoyl peroxide). Living radical polymerization can be best controlled with these nitroxides at temperatures between 120°C and 140°C.     

The Electrolytic “Sintering” of Nickel Powder

Adherent and coherent deposits of nickel sponge similar to sintered nickel may be made from sulphate, chloride, fluoborate or sulphamate nickel plating solutions containing nickel powder in suspension, providing the concentration of free acid is maintained sufficiently high to inhibit co-depesition of Ni(OH) In nitrate solution, cathodic reduction of nitrate and deposition of Ni(OH)₂ predominates.