Optimal estimation of reactivity ratios for acrylamide/acrylic acid copolymerization (original) (raw)
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Composition control through pH and ionic strength during acrylic acid/acrylamide copolymerization
Journal of Applied Polymer Science, 2013
The possibility of controlling the composition of acrylic acid/acrylamide copolymers by controlling the pH and the ionic strength of the reaction medium is investigated. The reactivity ratios of charged monomers depend on the pH of the medium, acrylic acid is the more reactive monomer below pH 3 and acrylamide above pH 4. The working pH was set at 3.6, a candidate for the crossover point, where no composition drift is expected. Copolymerization kinetics is investigated at this pH at various ionic strengths and a reaction without composition drift up to 80% conversion was achieved. All the chains produced in this reaction contain 30% 6 3% acrylic acid. Copolymer conversions, molecular weights, and composition distributions were measured through Automatic Continuous Online Monitoring of Polymerization (ACOMP) system. The copolymerization data were analyzed by a recent error in variables method (EVM) and reactivity ratios are calculated. The results show that in salt free conditions, the reactivity ratios depend on the ionic monomer concentration (ionic strength) in addition to the pH of the reaction medium. The effect of polyelectrolytic interactions on the reactivity ratios and the resulting composition drift during the reaction, sequence length distribution, and Stockmayer bivariate distribution are discussed in detail.
Industrial & Engineering Chemistry Research, 2014
An error-in-variables-model (EVM) framework is presented for the optimal estimation of reactivity ratios in copolymerization systems. This framework consists of several sequential steps and practical prescriptions that can yield reliable and statistically correct reactivity ratio values. These steps include: (a) screening experiments for estimating preliminary reactivity ratios, (b) optimal design of experiments, (c) full conversion range experiments and estimation of optimal reactivity ratios, and if necessary, (d) design of sequentially optimal experiments and re-estimation of reactivity ratios and diagnostic checks. This complete methodology should become common practice for determining reactivity ratios with the highest possible level of confidence. The performance of this framework is verified experimentally with data from the controlled nitroxide-mediated copolymerization of 9-(4-vinylbenzyl)-9Hcarbazole (VBK) and methyl methacrylate (MMA), a novel and largely unstudied copolymer system.
Macromolecular Reaction Engineering, 2016
A complete mathematical model of the free‐radical copolymerization of acrylic acid in an aqueous solution, taking place in a pilot‐scale tubular reactor equipped with static mixers, is presented. The developed kinetic/reactor model is numerically integrated in terms of a coupled deterministic–stochastic numerical approach that combines the advantages of speed, efficiency, and increased predictive capabilities. A series of experimental measurements on the monomer conversion and the molecular weight characteristics of the produced copolymer, under a wide range of process conditions, are used for the identification of the kinetic model parameters while a thorough analysis of the compositional characteristics of the produced copolymers is also carried out in terms of a series of bivariate distributed properties. image
Journal of Applied Polymer Science, 2014
The ionic strength (IS) of polyelectrolyte solutions plays an important role in influencing reaction kinetics. The largely unstudied effect of IS on monomer reactivity ratios and copolymerization rates of acrylamide (AAm) and acrylic acid (AAc), in the form of sodium acrylate (NaAc), is investigated. Salt addition affects the nature of overall charges of the polyelectrolyte solution and diminishes the electrostatic repulsions between reacting chains. Therefore, changing the IS of the solution by incorporating salts affect not only the point estimates of the monomer reactivity ratios but also the overall behavior of the copolymerization (with a transition to azeotropic behavior). Experimental results on copolymerization rates confirm the observed trends in reactivity ratio behavior. V C
Reactivity Ratio Estimation from Cumulative Copolymer Composition Data
Macromolecular Reaction Engineering, 2011
The goal is to present an alternative technique for reactivity ratio estimation in copolymerization. Typically, reactivity ratios are estimated using the instantaneous copolymer composition equation, based on low conversion copolymer composition data. However, using experimental data from the full copolymerization trajectory would, in principle, be more advantageous, and shy away from commonly used restrictive assumptions. Estimation using cumulative copolymerization data and models eliminates the difficulties associated with stopping reactions at low conversion, while one gains to study the full polymerization trajectory. The error-invariables-model (EVM) method is used for parameter estimation. Two cumulative model forms, the analytical integration of the differential composition equation and the one resulting from the direct numerical integration of this equation, are employed. Using these two types of models improves the reactivity ratio estimation and, in particular, the latter model form is a more reliable and direct method of estimating reactivity ratios.
Advanced manufacturing, 2015
The interest for models on a polymerization plant of acrylonitrile is (a) to predict the maximum capacity of an industrial reactor, (b) to increase the robustness of the process by defining stable operational conditions, and (c) to help the development of new copolymers. Using design of experiments (DOE), the copolymerization and terpolymerization of acrylonitrile with vinyl acetate and methyl-2 propene-1 sodium sulfonate were studied in aqueous suspension initiated by the redox system KClO 3 /NaHSO 3 /Fe 2þ. The molar fraction of the copolymers and terpolymers produced ranged from 93.0 to 98.2% for acrylonitrile, from 1.7 to 7.0% for vinyl acetate, and from 0.0 to 0.5% for sodium sulfonate. The mass molecular weight ranged from 76 000 to 419 000 g/gmol. Experiments were done in a pilot plant, consisting of 227 L of continuously stirred tank reactor, stripping and recycle systems, drum filter, and band dryer. The experiments were conducted according to a fractioned factorial 2 823 matrix with five central points. A statistic kinetic model was built, which explains well the copolymerization and terpolymerization of acrylonitrile. This model was applied with success on an industrial polymerization reactor, showing the potential of production increase, confirming the robustness of the process, and supporting the development of new copolymers of acrylonitrile. The focus of this paper is the development of a kinetic statistical polymerization model, the criteria to interrupt the regression analysis, and its application in the understanding of the polymerization phenomena.