Kinetics and modeling of diethylene glycol bisallyl carbonate bulk polymerization

The free‐radical polymerization kinetics of diethylene glycol bisallyl carbonate in bulk were investigated with Fourier transform infrared and Fourier transform Raman techniques in a wide temperature range of 50–140°C with four different peroxide initiators. In addition, the ratios of the degradative kinetic rate constant to the propagation rate constant under different reaction conditions were obtained from molecular weight measurements under various reaction conditions. The ratio of the chemically controlled termination and propagation rate constants of the polymerization system were obtained with the initial rates of polymerization and the number‐average molecular weight data, which were between 8.22 × 10^?5 and 1.47 × 10^?3 L mol^?1 s^?1. The initiator efficiencies were evaluated with special experiments at low initiator concentrations with the theory of dead‐end polymerization. The computed conversions from the developed kinetic model were in good agreement with the conversion and molecular weight measured data. The values of the diffusion‐controlled propagation and termination rate constants, with clear and physical meaning, were the only two parameters obtained from the developed kinetic model fitting the measured conversion points. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 345–357, 2005     

Thermal Hydrolysis of Cyanides in Spent Pot Lining of Aluminium Electrolysis

The spent lining of electrolysis pots is the main source of solid wastes in the production of aluminium. Being contaminated by cyanides, they may cause serious environmental problems for ground and surface waters. They have to be disposed of as special waste, or decontaminated prior to final disposal. This paper described the removal of free and complex cyanides from the spent pot lining waste by thermal hydrolysis. In addition, fluorides in the hydrolysis filtrate were precipitated by Ca(OH)₂ and disposed of together with the hydrolysed spent pot lining material.     

Engineering analysis of crosslinking polymerization of diallyl lsophthalate

A kinetic model for crosslinking free radical polymerization of DAIM (monomer diallyl isophthalate) with initiator CHPC (dicyclohexyl peroxydicarbonate) is developed. An improved version of Batch and Macosko's model was used to describe the initiator efficiency (f) and the active radical fraction (F_act). The experimental data of allyl and carbonyl group consumption are used for the optimization of the model and calculating of f and F_act. From the developed kinetic model and experimental results, obtained by FT‐IR measurements of monomer conversion, the introduction of the F_act was proved. Application of this model may be of use in process modeling of DAIM and other crosslinking polymerizations with CHPC as initiator.     

Polyacryl–nanoclay composite for anticorrosion application

Polyacryl–nanoclay composites are new class of materials obtained by dispersing montmorillonite clay nanoplatelets (nanoclay) into the polymer matrix. In present work we investigate and confirmed that montmorillonite nanoclay significantly enhances barrier properties of acrylic composite. Two stage of dispersion process was used to prepare polyacry–nanoclay composites. Different percentages of montmorillonite clay nanolayers were added to polyacryl dispersion and applied on steel panel with 0% (w/w), 1% (w/w), 2% (w/w) and 4% (w/w) of nanoclay as composites. Performance of nanoclay intercalation in polyacryl composite was measured by X-ray diffraction (XRD) and the structure characteristics of samples were analyzed with transmission electron microscopy (TEM). The effectiveness of prepared nanocomposites was identified by the hardness measurements and mechanical properties. Further anticorrosion characteristics, especially barrier properties were indirectly detected by electrochemical impedance spectroscopy (EIS). This method was also used for the determination of montmorilonite nanoclay optimal concentration in acrylic composite where optimal barrier properties were achieved.     

Comparison of properties of acrylic–polyurethane hybrid emulsions prepared by batch and semibatch processes with monomer emulsion feed

Aqueous acrylic–polyurethane hybrid emulsions were prepared by batch and semibatch polymerization of acrylic monomer mixtures (butyl acrylate, methyl methacrylate and acrylic acid) in the presence of polyurethane dispersion. The acrylic component was introduced in the monomer emulsion feed. The weight ratio between acrylic and polyurethane components was varied to obtain different emulsion properties, microphase structure and mechanical film properties. Scanning electron microscopy, average particle size and molecular weight measurements were performed to characterize the latex systems. Mechanical properties were examined by measuring Koenig hardnesses of dried films. The average particle size increased with the acrylic/polyurethane ratio. Particles of larger than average size and, to some extent, higher than average molecular weights by batch process were formed. Koenig hardnesses decreased with increasing acrylic/polyurethane ratio. Properties of emulsions synthesized by semibatch processes were compared with the results reported for a different polyurethane dispersion. Copyright © 2003 Society of Chemical Industry     

Kinetics and modeling of the diffusion‐controlled diallyl terephthalate polymerization

Free radical polymerization kinetics of diallyl terephthalate in bulk was investigated in a wide temperature range from 50°C to 150°C with four different peroxide initiators. Conversion points were measured using Fourier Transform Infrared (FTIR) measurements. The initiator efficiencies and the initiator decomposition rate constants were evaluated from special experiments, applying the theory of dead end polymerization. In addition, the ratios between the degradative and the effective kinetic rate constants to propagation rate constants were obtained from molecular weight measurements at various initiator concentrations. The ratio of chemically controlled termination and propagation rate constant k/k_tc of the polymerization system was obtained using the initial rates of polymerization and the number average molecular weight data between 0.25 · 10^?3 and 15.7 · 10^?3 L mol^?1 s^?1. The glass transition temperature of the polymer, 191°C, was measured by the Alternating Differential Scanning Calorimetry (ADSC) technique. Computed conversions from the developed kinetic model were in good agreement with the conversion and molecular weight measured data. The values of diffusion controlled propagation and termination rate constants k_td0 and k_pd0 with clear and physical meaning were the only two parameters obtained from the developed kinetic model fitting. Polym. Eng. Sci. 44:2005–2018, 2004. © 2004 Society of Plastics Engineers.     

Kinetic investigations of acrylic–polyurethane composite latex

The effect of various reaction parameters on the rate of polymerization, R_p, and on the particle size and morphology of aqueous acrylic–polyurethane hybrid dispersions, prepared by semibatch emulsion polymerization, was investigated. The particles of polyurethane dispersion were used as seeds during the polymerization of acrylic component: methyl methacrylate (MMA), butyl acrylate (BA), and a mixture of MMA and BA with the ratio of 1:1. These emulsions were found to form structured polymer particles in aqueous media using scanning electron microscopy. The kinetics of the emulsion polymerization was studied on the basis of Wessling's model. The influence of emulsifier and initiator concentrations, including the monomer feed rates, R_m, on the rates of polymerization and on the properties of the resulting dispersions were studied. The number of particles and the particle size were also measured during the polymerization process. The final values were found to be independent of the concentration of the emulsifier, initiator and the monomer feed rate in monomer starved conditions. In the steady‐state conditions, during the seeded semibatch hybrid emulsion polymerization, the rate of polymerization and the monomer feed rate followed the Wessling relationship 1/R_p = 1/K + 1/R_m. The dispersions MMA/PU, BA/PU, and MMA/BA/PU have K values of 0.0441, 0.0419 and 0.0436 mol/min, respectively. The seeded BA/PU hybrid polymerization proceeded according to Smith‐Ewart Case I kinetics, while the MMA/PU hybrid emulsions demonstrate Case II of the Smith‐Ewart kinetic model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2639–2649, 2002     

The Influence of Modified Starch on the Process Water Quality in Papermaking and the Paper Properties

The influence of modified (cationic) starch on the process water quality in papermaking and paper properties has been investigated. The experiments were conducted on sulfate hardwood pulp by applying both tap and paper mill process water. When process water is used, the retained amount of starch on fibers decreases, which most probably results from a partial neutralization of the cationic charge on modified starch, thereby reducing its attraction to the anionic groups on a fiber. By adding the modified starch, the turbidity of process water is to some extent reduced, indicating that the suspended organic substances are removed from process water. Due to starch accumulation, the load of process water by organic substances (determined via the TOC analysis) is not reduced, but is rather increased when the modified starch is added. In most cases, the addition of modified starch improved the investigated paper properties. However, these properties varied in correlation with the quality of the used water, despite the fact that the dosage of modified starch remained constant. This demonstrates the influence of process water quality, not only on the paper properties, but also on the efficiency of process chemicals, such as the modified starch, in the papermaking process.     

Optimization of industrial‐scale deodorization of high‐oleic sunflower oil via response surface methodology

Optimization of industrial‐scale deodorization of high‐oleic sunflower oil (HOSO) via response surface methodology is presented in this study. The results of an experimental program conducted on an industrial‐scale deodorizer were analyzed statistically. Predictive models were derived for each of the oil quality indicators (QI) in dependence on the studied variable deodorization process parameters. The deodorization behavior of some minor components was analyzed on a pilot‐scale deodorizer. For comparison, a similar experimental program was also performed on the laboratory‐scale. The results of this study demonstrate that optimization of the deodorization process requires a suitable compromise between often mutually opposing demands dictated by different oil QI. The production of HOSO with top‐quality organoleptic and nutritional values (high tocopherol and phytosterol contents and low free and trans fatty acid contents) and high oxidative stability demands deodorization temperatures in the range between 220 and 235 °C and a total sparge steam above 2.0% (wt/wt in oil). The response surface methodology provides the tools needed to identify the optimum deodorization process conditions. However, the laboratory‐scale experiments, while showing similar response characteristics of QI in dependence on the process parameters and thus helpful as a guide, are of limited value in the optimization of an industrial‐scale operation.