Mechanochemical polymerization in mixtures of diallyl terephthalate and distilled water by ultrasonic irradiation

Summary Mechanochemical polymerization in systems of diallyl terephthalate-distilled water has been studied by ultrasonic irradiation at 90°C. An additional effect of distilled water on mechanochemical polymerization of diallyl terephthalate was investigated. When a 1.2 wt % distilled water solution, the conversion of poly(diallyl terephthalate) was the greatest and the initial rate of the polymerization R _p was 1.3x10^-5 mol/l sec. This polymerization proceeded by a radical mechanism and the primary radicals produced from water molecules by ultrasonic waves. In addition, changes in the iodine value and the weight-average molecular weight of the resulting polymers were proved.     

Kinetics of dispersion polymerization of dimethyl diallyl ammonium chloride and acrylamide

Dispersion copolymerization of dimethyl diallyl ammonium chloride with acrylamide has been investigated by the dilatometer technique using the mixture of poly(vinylpyrrolidone) and poly(dimethyl diallyl ammonium chloride) as the composite stabilizer and 2,2′-azobis(2-methylpropionconidine)dihydro chloride as the initiator. Monomer reactivity ratios of AM and DMDAAC were determined by the application of Fineman-Ross methods. The analysis of reactivity ratios revealed that DMDAAC is less reactive than AM, and copolymers formed are statistically in nature. The influences of the molar ratio of AM to DMDAAC, concentrations of monomers, stabilizer and initiator, etc. on polymerization rate and intrinsic viscosity of polymer have been examined. The rate of polymerization (R_p) can be represented by R_p μ [M]^1.44,R_p μ [S]^0.39,R_p μ [I]^0.60 {R_{\rm{p}}} \propto {[M]^{1.44}},{R_{\rm{p}}} \propto {[S]^{0.39}},{R_{\rm{p}}} \propto {[I]^{0.60}} . The overall activation energy for the rate of polymerization is 37.38 kJ/mol over the temperature range 35–55°C.Based on the experimental results, the polymerization mechanisms were discussed.     

Minimum time heating cycles for diffusion‐ versus permeability‐controlled binder removal from ceramic green bodies

A comparison of minimum time heating cycles (MTHCs) was conducted for binder removal from ceramic green bodies for two mass transfer mechanisms: diffusion and gas permeability. The MTHCs were determined by combining approximate analytic solutions to the governing reaction‐diffusion and reaction‐gas permeability equations with a variational calculus algorithm containing a constraint on pressure buildup within the green body. Both the temperature‐time profile and duration of the MTHCs were sensitive to the operative transport process as well as to a number of model parameters including the pressure constraint, the total furnace pressure, the reaction kinetics, the gas permeability, and the diffusivity as described by the free volume theory. Strategies were identified which are most effective for decreasing the cycle time for each mass transfer mechanism.     

Chemical‐looping combustion process: Kinetics and mathematical modeling

Chemical Looping Combustion technology involves circulating a metal oxide between a fuel zone where methane reacts under anaerobic conditions to produce a concentrated stream of CO₂ and water and an oxygen rich environment where the metal is reoxidized. Although the needs for electrical power generation drive the process to high temperatures, lower temperatures (600–800°C) are sufficient for industrial processes such as refineries. In this paper, we investigate the transient kinetics of NiO carriers in the temperature range of 600 to 900°C in both a fixed bed microreactor (WHSV = 2‐4 g CH₄/h/g oxygen carrier) and a fluid bed reactor (WHSV = 0.014‐0.14 g CH₄/h per g oxygen carrier). Complete methane conversion is achieved in the fluid bed for several minutes. In the microreactor, the methane conversion reaches a maximum after an initial induction period of less than 10 s. Both CO₂ and H₂O yields are highest during this induction period. As the oxygen is consumed, methane conversion drops and both CO and H₂ yields increase, whereas the CO₂ and H₂O concentrations decrease. The kinetics parameter of the gas–solids reactions (reduction of NiO with CH₄, H₂, and CO) together with catalytic reactions (methane reforming, methanation, shift, and gasification) were estimated using experimental data obtained on the fixed bed microreactor. Then, the kinetic expressions were combined with a detailed hydrodynamic model to successfully simulate the comportment of the fluidized bed reactor. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

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     

Kinetics and flow of diallyl phthalate resins

The analysis of molding operations for thermosetting polymers requires knowledge of the rheology and reaction rates of the materials. The purpose of this research was to measure kinetic and rheological data on diallyl phthalate resins and to integrate these results into models describing the flow behavior. The chemical kinetics of the curing reactions were derived from calorimetric measurements taken with a differential scanning calorimeter. The rheological data were measured with a mechanical spectrometer equipped with eccentric rotating discs. A model based on the theory of ideal rubber elasticity was used to correlate the elastic storage modulus with reaction time and temperature. For the region below the gel point, the dynamic viscosity exhibited a power law dependence on angular frequency and an Arrhenius dependence on temperature.     

Kinetics modeling of carbon‐fiber‐reinforced bismaleimide composites under microwave and thermal curing

This article focuses on the analysis of the curing kinetics of carbon‐fiber‐reinforced bismaleimide (BMI) composites during microwave (MW) curing. A nonisothermal differential scanning calorimetry (DSC) method was used to obtain an accurate kinetic model. The degree of curing, chemical characterization, and glass‐transition temperature of the resin and composites cured by thermal and MW heating were analyzed with DSC, Fourier transform infrared spectroscopy, and dynamic mechanical analysis. The experimental results indicate that MW accelerated the crosslinking reaction of the BMI resin and had different effects on the reaction processes, especially for the glass‐transition temperature and chemical bonds. However, the curing reaction rate of the BMI resin decreased when the carbon fibers were added to the BMI resin during thermal and MW curing. According to the experimental results, the curing kinetic model of the BMI composite was used to provide a theoretical foundation for MW curing analysis. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43770.     

Kinetics of drying polybutylene terephthalate and polyethylene terephthalate granulate

In studying the dynamics of drying of PBT and PET granulate, the parameters of the process that ensure sufficient process stability of their melts were determined. It was found that the rate of self-ordering of structural elements in the polymer substrate in drying is higher in PBT than in PET due to the greater flexibility of the macromolecules. __________ Translated from Khimicheskie Volokna, No. 1, pp. 7–10, January–February, 2006.     

Solid‐state polymerization and bulk crystallization behavior of poly(ethylene terephthalate) (PET)

The main variables involved in solid‐state polymerization of PET homopolymers, originally with molecular weight within the commercial range, were sequentially studied to determine their influence in polymerized products. These variables were precursor crystallinity, catalyst, and time and reaction temperature. An increasing molecular weight sequence was then used to study the bulk crystallization behavior with Avrami analyses. It was determined that thermal conditions at dissolution affect the prereaction morphology. This was important in the polymerization process because it was found that high crystallinity levels in precursors result in higher molecular weights. In agreement with other reports, typical catalysts used in melt polymerizations enhance postpolycondensation processes in the solid state. High reaction times and temperatures were also required to obtain high molecular weights. As the molecular weight increased, there was a decrease in nucleation density and Avrami analyses, applied to the isothermal bulk crystallization, indicating that the nucleation process changed from instantaneous to spontaneous with the increase in molecular weight. The consequences and relative importance of the observed results is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 78–86, 2000     

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.     

Kinetics of RAFT emulsion polymerization of styrene mediated by oligo(acrylic acid‐b‐styrene) trithiocarbonate

The kinetics of ab initio reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization of styrene using oligo(acrylic acid‐b‐styrene) trithiocarbonate as both polymerization mediator and surfactant were systematically investigated. The initiator concentration was set much lower than that in the conventional emulsion polymerization to significantly suppress the irreversible termination reaction. It was found that decreased rapidly but the nucleation efficiency of micelles increased with the decrease of the initiator concentrations due to the significant radical exit. The particle number ( ) did not follow the classic Smith–Eward equation but was proportional to [I]^?0.4[S]^0.7. It was suggested that RAFT emulsion polymerization could be fast enough for commercial use even at extremely low initiator concentrations and low macro‐RAFT agent concentrations due to the higher particle nucleation efficiency at lower initiator concentration. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2126–2134, 2016     

Kinetics of isothermal and non‐isothermal crystallization of poly(butylene terephthalate)/ liquid crystalline polymer blends

The melting behavior and isothermal and non‐isothermal crystallization kinetics of poly(butylene terephthalate) (PBT)/thermotropic liquid crystalline polymer (LCP), Vectra A950 (VA) blends were studied by using differential scanning calorimetry. Isothermal crystallization experiments were performed at crystallization temperatures (T_c), of 190, 195, 200 and 205°C from the melt (300°C) and analyzed based on the Avrami equation. The values of the Avrami exponent indicate that the PBT crystallization process in PBT/VA blends is governed by three‐dimensional morphology growth preceded by heterogeneous nucleation. The overall crystallization rate of PBT in the melt blends is enhanced by the presence of VA. However, the degree of PBT crystallinily remains almost the same. The analysis of the melting behavior of these blends indicates that the stability and the reorganization process of PBT crystals in blends are dependent on the blend compositions and the thermal history. The fold surface interfacial energy of PBT in blends is more modified than in pure PBT. Analysis of the crystallization data shows that crystallization occurs in Regime II across the temperature range 190°C‐205°C. A kinetic treatment based on the combination of Avrami and Ozawa equations, known as Liu's approach, describes the non‐isothermal crystallization. It is observed that at a given cooling rate the VA blending increases the overall crystallization rate of PBT.     

Gas‐phase polymerization of butadiene. Data acquisition using minireactor technology and particle modeling

Minireactor technology has been used for kinetic studies on polymerization kinetics, phase equilibrium, and mass transfer on a very small scale. There is a nonlinear influence of temperature and pressure on the polymerization rate. The phase equilibrium can be described by a Flory–Huggins approach, with a temperature‐dependent interaction parameter. The diffusion coefficient seems to be slightly pressure dependent, and the temperature dependence can be described with an Arrhenius equation. A simple formal kinetic scheme with formation of active sites, chain propagation, chain transfer to cocatalyst, and deactivation of active sites has been applied. This kinetic scheme was implemented in two different models; they are, a particle model taking into account mass transfer and a simple chemical model with no mass transfer. In principle, both models describe the experimental results for rate and molecular weight distribution equally well, with rate constants of the same magnitude. Molecular weight distributions calculated by the chemical model are narrower. However, the chemical model gives no explanation for the experimental observed rate dependence on catalyst particle size. With increasing catalyst activity, the differences between both models become more significant and the particle model becomes more and more important. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 270–279, 2003     

Melting behavior and crystallization kinetics of poly(butylene terephthalate‐co‐diethylene terephthalate) and poly(butylene terephthalate‐co‐triethylene terephthalate) copolyesters

The melting behavior of poly(butylene terephthalate‐co‐diethylene terephthalate) and poly(butylene terephthalate‐co‐triethylene terephthalate) copolymers was investigated by differential scanning calorimetry after isothermal crystallization from the melt. Multiple endotherms were found for all the samples, and attributed to the melting and recrystallization processes. By applying the Hoffman‐Weeks' method, the equilibrium melting temperatures of the copolymers under investigation were obtained. Two distinct peaks in the crystallization exothermic curve were observed for all the samples. Both of them appeared at higher times than that of PBT, indicating that the introduction of a comonomer decreased the crystallization rate. The observed dependence of this latter on composition was explained on the basis of the content of ether–oxygen atoms in diethylene and triethylene terephthalate units, and of the different sizes of these units. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3545–3551, 2001     

Mathematical modeling of molecular weight distribution in miniemulsion polymerization with oil‐soluble initiator

A mathematical model for the study of reaction kinetics and molecular weight distributions in miniemulsion polymerization systems with oil‐soluble initiators is presented. The mathematical model allows the computation of the evolution of the complete molecular weight distribution with chain lengths of up to 10⁵ mers in miniemulsion polymerization by direct integration in reasonable computational time. Also, no restriction in the kinetic regime is needed, as the model is able to represent both compartmentalized and pseud‐bulk systems. The model was validated with experimental results for methyl methacrylate and styrene homopolymerizations, with two different oil‐soluble initiators, and adequately represented both the kinetics and molecular weight distributions of these systems. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2128–2140, 2017     

Population balance modeling of particle size distribution in monomer‐starved semibatch emulsion polymerization

The evolution of particle size distribution (PSD) in the monomer‐starved semibatch emulsion polymerization of styrene with a neat monomer feed is investigated using a population balance model. The system under study ranges from conventional batch emulsion to semicontinuous (micro)emulsion polymerization depending on the rate of monomer addition. It is shown that, contrary to what is often believed, the broadness of PSD is not necessarily associated with the length of nucleation period. The PSDs at the end of nucleation are found to be independent of surfactant concentration. Simulation results indicate that at the completion of nucleation the particle size is reduced and the PSD narrows with decreasing rate of monomer addition despite nucleation time increasing. The broad distribution of particles frequently encountered in semibatch emulsion polymerizations is therefore attributed to stochastic broadening during the growth stage. The zero‐one‐two‐three model developed in this article allows perceiving that the dominant kinetic mechanism may be different for particles with different sizes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

A diffusion‐reaction model for α‐chymotrypsin carrying uniform thermosensitive gel beads

In this study, the kinetic behavior of α‐chymotrypsin‐immobilized, uniform poly(isopropylacrylamide) gel beads was investigated. The kinetic study was performed by using a continuous reactor operated at steady‐state conditions. In the experiments, substrate feed concentration, residence time, and reactor temperature were changed. The results were explained by a diffusion–reaction model developed for steady‐state conditions. The effectiveness factor and Thiele modulus values of the thermosensitive enzyme–gel system were estimated at different temperatures by using an iterative procedure based on fourth order Runge–Kutta algorithm. The results indicated that the overall hydrolysis rate was controlled by the substrate diffusion through the gel matrix. A bending point was detected for the Thiele modulus at the lower critical solution temperature (LCST) of the thermosensitive gel. The effective diffusion coefficient of substrate and effectiveness factor decreased suddenly at LCST. The mass transfer process within the thermosensitive carrier could be described in detail by the proposed model. The results of our numerical procedure were also compared with an analytical approximate solution available in the literature. The consistency between two different model was reasonably good. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1025–1034, 1999