Abstract This work evaluates the usage of the multimodal lognormal function to describe Particle Size Distributions (PSD) of emulsion and suspension polymerization processes, including continuous reactions with particle re-nucleation leading to complex multimodal PSDs. A global optimization algorithm, namely Particle Swarm Optimization (PSO), was used for parameter estimation of the proposed model, minimizing the objective function defined by the mean squared errors. Statistical evaluation of the results indicated that the multimodal lognormal function could describe distinctive features of different types of PSDs with accuracy and consistency.

In this work, the ability of on-line NIR spectroscopy for the prediction of the evolution of monomer concentration, conversion and average particle diameter in acrylamide inverse miniemulsion polymerization was evaluated. The spectral ranges were chosen as those representing the decrease in concentration of monomer. An increase in the baseline shift indicated that the NIR spectra were affected by particle size. Multivariate partial least squares calibration models were developed to relate NIR spectra collected by the immersion probe with off-line conversion and polymer particle size data. The results showed good agreement between off-line data and values predicted by the NIR calibration models and these latter were also able to detect different types of operational disturbances. These results indicate that it is possible to monitor variables of interest during acrylamide inverse miniemulsion polymerizations.

Miniemulsification and emulsion/solvent evaporation techniques were combined to produce poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanoparticles. Those nanoparticles were prepared with different PHBV molar masses and PHBV concentrations to verify their effect on the final particle size. Nanoparticles with an average diameter of 133 nm were obtained when a low molar mass (Mw = 44,350 g/mol) polymer was used. On the other hand, when high molar mass PHBV (Mw = 369,900 g/mol) was used under the same operational conditions, nanoparticles with a 300 nm average diameter and a broader particle size distribution were formed. Results also showed that increasing the PHBV concentration led to an increase of the particle size and, when the polymer/costabilizer (PHBV/hexadecane) weight ratio was close to 1, nanocapsules (hexadecane core surrounded by a PHBV shell) were formed.

The determination of conversion during suspension polymerization reactions is not an easy task due to the heterogeneity of the reaction medium and the tendency of particles to agglomerate rapidly when stirring is stopped. Usually, bulk polymerization in ampoules is employed to study the kinetics of suspension polymerization reactions. In this work, a comparison of different techniques for the determination of conversion during suspension polymerization reactions is presented. Results showed a good agreement between the conversion obtained by gravimetry during styrene suspension polymerization and on-line conversion monitoring data using fiber-optic based Raman Spectroscopy. Nevertheless, the polymerization rate of styrene bulk polymerization carried out in ampoules was higher than the real reaction rate of styrene suspension polymerization due to slightly higher reaction temperatures. Simulation results using the experimental temperature data in a mathematical model confirmed these results.

Time optimal monomer and reactor temperature set-point profiles were computed and implemented experimentally for the control of copolymer composition and minimization of reaction time in emulsion copolymerization systems. Iterative Dynamic Programming (IDP) was used for the off-line calculation of the optimal profiles. This approach can deal with constrained optimization of systems described by complex mathematical models, as those needed for the emulsion copolymerization. The optimization procedure was applied to vinyl acetate / butyl acrylate emulsion copolymerization under industrial-like conditions, which includes safety constraints normally found in the operation of large-scale reactors. The dynamics of the reactor heat exchange system were also taken into account in the mathematical model. The optimal trajectories obtained by the IDP procedure were implemented in a jacketed reactor with automated control of temperature and monomers feed flow rates. The real-time implementation of the optimal trajectories was successfully carried out resulting in a significant reduction in reaction time and the production of homogeneous copolymer composition.

The present work describes a methodology for estimation of monomer concentration during homopolymerization reactions by Raman spectroscopy. The estimation is done using linear models based on two different approaches: a univariate approach and a multivariate approach (with principal component regression, PCR, or partial least squares regression, PLS). The linear models are fitted with data from spectra collected from synthetic samples, i.e., samples prepared by dispersing a known concentration of monomer in polymer emulsions. Homopolymerizations of butyl acrylate and of vinyl acetate were monitored by collecting samples from the reactor, and results show that the methodology is efficient for the model fitting and that Raman spectroscopy is a promising technique for on-line monitoring of the emulsion polymerization process.

This work addressed the viability of using a pulsed sieve-plate column reactor to carry out continuous vinyl acetate/butyl acrylate emulsion copolymerization reactions. A rigorous mathematical model of emulsion copolymerization reactions in a tubular reactor with axial dispersion was used for this purpose. Operational conditions were defined to attain high monomer conversions at the reactor outlet in a relatively short residence time and, at the same time, produce a copolymer with a more homogeneous composition.

A new reactor, the pulsed sieve plate column (PSPC), was developed to perform continuous emulsion polymerization reactions. This reactor combines the enhanced flexibility of tubular reactors with the mixing behavior provided by sieved plates and by the introduction of pulses that is important to prevent emulsion destabilization. The main objective of this work is to study the kinetics of vinyl acetate (VA) emulsion polymerization reactions performed in this PSPC. Therefore, both experimental studies and reaction simulations were performed. Results showed that it is possible to obtain high conversions with rather low residence times in the PSPC.

Dynamic mathematical models are developed to simulate styrene emulsion polymerization reactions carried out in pulsed tubular reactors. Two different modeling approaches, the tanks-in-series model and the axial dispersion model, are compared. The models developed were validated with experimental data from the literature and used to study the dynamics during transient periods, e.g., the start-up of the reactor and the response to disturbances. The effect of the Peclet number on process variables such as conversion and particle concentration was also verified.