Particle formation under monomer-starved conditions in the semibatch emulsion polymerisation of styrene. Part II. Mathematical modelling

Models, together with a comparison with experimental data, are presented for the particle nucleation under monomer-starved conditions. In the first model, simplifications were made to obtain analytical solutions. The Smith and Ewart theory was extended to include particle formation under monomer-starved conditions. It was assumed that the rate of particle growth is controlled by the rate of monomer addition. An appropriate correlation for prediction of number of polymer particles in terms of surfactant and initiator concentrations and monomer addition rate was derived as N_p=k(a_s[S])^1.0R_I^2/3R_a^−2/3. The second model takes advantage of the new developments in understanding of the kinetics of the water phase and its effects on the radical capture efficiency of micelles. The model accounts for monomer solubilisation in the micelles. According to the model predictions, the size of micelles and their aggregation number are subject to variation during nucleation. The model could successfully predict some important features of particle formation under monomer-starved conditions.     

Effect of carboxylic acid monomer and butadiene on particle growth in the emulsifier-free emulsion copolymerization of styrene-butadiene-carboxylic acid monomer

Carboxylated styrene-butadiene rubber (XSBR) latexes were prepared by emulsifier-free batch emulsion copolymerization of styrene and butadiene with different types of carboxylic acid monomers (AA, MAA, IA). It was found that the particle growth is dependent on the hydrophilic nature of carboxylic acid monomers. SEM studies showed that N_p is almost constant in the particle growth stage (conversion above 10%). Through some calculations by data obtained from DLS technique, average diameter of monomer swollen polymer particles of all the XSBR latexes at the same conversion of 0.4 was obtained to be 368.91, 174.17 and 437.15 nm for AA, MAA and IA, respectively. Several kinetic parameters related to the particle growth stage such as the average number of growing chain per particle were calculated to be 0.474, 0.370 and 1.685 for AA, MAA and IA, respectively. It was observed that these kinetic parameters increase with increasing average diameter of monomer swollen polymer particles, which is consistent with the emulsion polymerization kinetics. Moreover, results indicated that the polymerization rate per particle or equivalently the average number of the growing chain per particle (particle growth stage) decreases by replacing a part of styrene with butadiene in the emulsion copolymerization recipe of styrene-carboxylic acid monomer.     

微波辐射无皂乳液聚合制备单分散热敏性微球

在微波辐射条件下苯乙烯(St)和N-异丙基丙烯酰胺进行无皂乳液聚合,结果表明所制备的微球粒径小于150nm且为单分散。利用透射电子显微镜(TEM)观察微球形态及粒径。通过动态激光光散射粒度仪(PCS)考察微球的热敏性,微球粒径随温度发生变化。     

纳米SiO_2/MMA无皂乳液聚合研究及其应用

以纳米 Si O2 为核 ,以 MMA为壳层单体 ,进行了无皂乳液聚合。研究了单体加入方式、引发剂用量、聚合反应温度等对无皂乳液聚合的影响。核壳产物对 PVC材料的力学性能有明显的提高。     

Population balance model versus lumped model for emulsion polymerisation: Semi-batch and continuous operation

In this article, a systematic comparison is made of a detailed population balance model of the emulsion polymerisation process that accounts for the dynamic evolution of the entire particle size distribution with a simple model of the process that accounts only for the dynamic evolution of the average particle size and the total particles. Both models account for the underlying mechanisms of the process to the level admissible within their respective frameworks. The predictions of the two models are compared under both batch and continuous operation. The aim is to elucidate the degree of disparity of model predictions for batch operation, and to elucidate the ability of the simple lumped models to predict oscillatory dynamics for continuous operation. The focus is on the comparison of the predictions of important control variables such as solids content (conversion), total particles and average particle size, but also those of important particle phenomena of nucleation, growth and coagulation. It is found that with respect to these lumped control variables, the simple model performs well in matching the detailed model, and hence will be a very valuable tool for the purpose of on-line feedback control. However, the detailed models will be important for distributed control variables such as the entire particle size distribution.     

Operation of semi-batch emulsion polymerisation reactors: Modelling, validation and effect of operating conditions

A detailed dynamic model was developed for a styrene emulsion polymerisation semi-batch reactor to predict the evolution of the product particle size distribution (PSD) and molecular weight distribution (MWD) over the entire range of monomer conversion. A system exhibiting zero-one kinetics was employed, with the model comprising a set of rigorously developed population balance equations to predict monomer conversion, PSD and MWD. The modelling equations included diffusion-controlled kinetics at high monomer conversion where the transition from the zero-one regime to a pseudo-bulk regime occurs. The model predictions were found to be in good agreement with experimental results. Both particle growth and the PSD were found to be strongly affected by the monomer feedrate. Reactor temperature had a major influence on the MWD which was, however, insensitive to changes in the monomer feedrate. These findings were confirmed experimentally. As a result, it seems reasonable to propose that the use of the monomer feedrate to control the PSD and the reactor temperature to control the MWD are appropriate in practical situations. Consequently, an optimal monomer feed trajectory was developed off-line (using the validated reactor simulation) and verified experimentally by producing a polymer with specific PSD characteristics.     

Ultrasonically initiated emulsifier-free emulsion copolymerization of n-butyl acrylate and acrylamide. Part I: Polymerization mechanism

The polymerization mechanism of ultrasonically initiated emulsifier-free emulsion copolymerization of n-butyl acrylate (BA) and acrylamide (AM) was investigated. A four-step polymerization mechanism of the ultrasonically initiated emulsifier-free emulsion was put forward based on the monomer conversion and the main reaction locus. Improving the power output would increase the monomer conversion and the rate of polymerization. However, when the reaction temperature was 30 °C and the concentration of Na₂SO₄ was 0.1%, the monomer conversion and the rate of polymerization achieved maximum. The FTIR spectra showed that the sample obtained by this way was the copolymer of BA and AM, but not the blend of poly(butyl acrylate) and polyacrylamide.     

Effects of inorganic electrolytes upon emulsion polymerisation reactions. I. Effects upon kinetics of styrene emulsion homopolymerisation and of styrene-acrylic acid emulsion copolymerisation

Results are given for the effects of two added inorganic electrolytes, potassium chloride and calcium chloride, upon the kinetics of the emulsion homopolymerisation of styrene and of the emulsion copolymerisation of styrene with a minor amount of acrylic acid, using sodium dodecylbenzenesulphonate as surfactant and potassium persulphate as initiator. Three reaction systems were investigated. Two were for the emulsion homopolymerisation of styrene, one reaction system using a relatively high level of surfactant and the other a relatively low level of surfactant. The third reaction system was for the emulsion copolymerisation of styrene and acrylic acid using an intermediate level of surfactant. The results show that the effects of added electrolytes can be varied and complex: they depend upon several factors such as the nature and amount of the added electrolyte, the level of surfactant, and the presence or absence of the acidic comonomer.     

Shell growth mechanism in emulsifier-free emulsion polymerization: Morphological and kinetic studies

For systems of emulsifier-free emulsion polymerization having particle diameter (D_p) greater than 0.15–0.2μm, a shell-growth mechanism for particle growth was proposed. According to the mechanism, the polymeric radicals can propagate only within the shell region having a thickness about equal to the most probable end-to-end distance of the terminated polymer. This mechanism was considered to result from anchoring of hydrophilic ends of the growing radicals on the particle surface and from a high average number of radicals per particle. The occurrence of limiting conversion for such large particles was attributed to the consequence of shell-region polymerization characteristic of large emulsion particles and a monomer-diffusion-controlled polymerization mechanism within the particles during the high conversion period.     

Surfactant-free emulsion polymerisation of methyl methacrylate and methyl acrylate using intensified processing methods

The feasibility of enhancing the latex yield and colloid characteristics in the surfactant-free emulsion polymerisation (SFEP) of methyl methacrylate (MMA) and methyl acrylate (MA) through the use of intensified processing technologies is reported in this paper. The effects of high power ultrasonic energy as a well-established technique for mixing and mass transfer enhancements were compared with thermal initiation in a conventional mechanically agitated reactor. Although increases in ultrasonic power input resulted in higher rates of reaction and larger particles in the MMA polymerisation, reaction yields were nevertheless found to be low compared with the thermally initiated stirred tank reactor experiments. This was attributed to the low frequency ultrasound used (24 kHz) that was observed to provide excellent emulsification but was ineffective in terms of radical generation. The results for a thermally initiated SFEP of MA in a narrow channel reactor as an example of a continuous flow reactor technology showed that reaction rates were comparable with those achieved in the stirred tank reactor but at only a fraction of the specific power input whilst smaller particles with a tighter distribution are generated. These effects highlight the process intensification characteristics of the narrow channel reactor for the SFEP of MA.     

Particle features and morphology of poly(vinyl chloride) prepared by living radical polymerisation in aqueous media. Insight about particle formation mechanism

The aim of this work is to evaluate PVC resins prepared by Single Electron Transfer Degenerative Chain Transfer Living Radical Polymerisation (SET-DTLRP) in a 150 L reactor under industrial conditions. The product features were analysed considering the standard resin features of PVC prepared by the conventional free radical polymerisation (FRP) method. It was proved that the FRP and SET-DTLRP have different particle growing mechanism and led to grains with completely different features (particle size, particle size distribution and morphology). It is critical for the PVC producers the preparation of PVC with a predetermined grain shape, particle size distribution and porosity which have an indubitable in?uence on polymer processing. It is presented a detailed study on the particle formation of the PVC synthesised by SET-DTLRP providing ?rst insights into PVC features associated with a new polymerisation technique taking into account the normal requirements of the PVC industry. A possible mechanism of the SET-DTLRP particle formation is proposed.     

Crystal structure and ab initio calculations of CaZrO3

Calcium zirconate (CaZrO₃), because of its high melting point, low thermal expansion coefficient, high strength and excellent corrosion resistance against alkali oxides, is a good candidate for a novel refractory material. CaZrO₃ is mostly synthesized by the reaction in the solid state but the material obtained in such a way often suffers low bulk density, high porosity and other defects which lower its potential application value. To overcome these obstacles a novel synthesis method by an electric arc melting technique was proposed. The crystal structure of melted CaZrO₃ was compared with a conventionally synthesized material. According to X-ray measurements the obtained material has an orthorhombic perovskite-like structure. Its stoichiometry was confirmed by the scanning electron microscope and EDS analysis. The material is almost poreless with its density close to theoretical. The estimated crystal structure parameters were used to calculate the electronic structure of CaZrO₃ using the full potential linear augmented plane wave (FLAPW) method. It has been found that CaZrO₃ is an insulator with the energy band gap of 4.1 eV. The Ca-O bond is typically ionic while Zr-O bond is of a significant covalent character.     

Excited-state nature in benzodifuranone dyes: Insights from ab initio simulations

Using ab initio theoretical tools simultaneously accounting for electron correlation and environmental effects, we have simulated the optical spectra of benzodifuranone dyes. In a first step, a valuable computational protocol has been defined and it turned out that a PCM-TD-M06-2X/6-311+G(2d,p)//PCM-PBE0/6-311G(d,p) approach provides an adequate balance between computational requirements and accuracy (deviations of ca. 10 nm with respect to experiment). In a second stage, we have calculated the spectrum of a large series of push-pull structures, and it turned out that the benzodifuranone core is a strong electron capturing group at the excited-state. Indeed, strong auxochroms like the nitro and cyano groups fall short to significantly perturb the LUMO of this series of chromogens. Eventually, in a last phase, the implications of these results are discussed for a series of organic dyes of potential interest for solar cells (DSSC).     

Solvation of hydrocarbon radicals in sub-CW and SCW: An ab initio MD study

Solvation of methyl radicals in subcritical and supercritical water was investigated with the ab initio MD simulation to increase the understanding of the thermal cracking of hydrocarbons under the severe hydrothermal environments. The calculation results show that water clusters around the radical could be formed with the following prerequisites: the bulk density of water is close to liquid phase, and the state point of water on its phase diagram is far away from the critical point and from the vapor-liquid equilibrium boundary. The occurrence of water clusters superimposes a negative influence on the originally depressed diffusivity of the radical under the dense hydrothermal environments, and the interference from the immediately adjacent water molecules with the frontier orbitals of the radical results in randomly reduced activity of the radical. Regardless of whether there are water clusters around the radical or not, in subcritical and supercritical water the bimolecular reactions participating via hydrocarbon radicals should be partially suppressed by the reduced diffusivity and lower activity of the radical.     

Modelling particle size distributions and secondary particle formation in emulsion polymerisation

An extensive model is given for the particle size distribution (PSD), particle number, particle size and amount of secondary nucleation in emulsion polymerisations. This incorporates what are thought to be all of the complex competing processes: aqueous phase kinetics for all radical species arising from both initiator and from exit (desorption), radical balance inside the particles, particle formation by both micellar and homogeneous nucleation mechanisms, and coagulation (the rate of which is obtained using the Healy–Hogg extension of DLVO theory). The predictions of the model are compared to extensive experimental results on rates, time evolution of the particle size distribution, and relative amounts of secondary nucleation, for styrene initiated by persulfate with sodium dodecyl sulfate and with sodium dihexyl sulfosuccinate as surfactants. For this system values of almost all of the many parameters needed for the model are available from independent measurements, and thus no significant parameter adjustment is plausible. Accord with experiment is imperfect but quite acceptable, supporting the validity of the various mechanisms in the model. Effects such as the experimental variation of particle number with ionic strength, as well as calculated coagulation rate coefficients as functions of particle size, suggest that coagulation of precursor (i.e., newly-formed) particles is a significant effect, even above the cmc. The modelling also suggests why secondary nucleation occurs readily in systems stabilised with polymeric surfactant.     

Feedback controllability assessment and control of particle size distribution in emulsion polymerisation

In this article, the importance of particle size distribution (PSD) control as a means for the inferential control of the rheology of emulsion polymers is illustrated. A controllability assessment is presented to illustrate the attainability or otherwise of bimodal PSD using feedback control through a consideration of the process mechanisms—measurement limitations and process constraints that prevent the implementation of feedback corrections. The suitability of a batch-to-batch iterative feedback PSD control is demonstrated, which could act in addition to any in-batch feedback control, the latter being less feasible in certain cases, as argued in this article. A detailed population balance model is used for the batch-to-batch control, which simplifies model update and feedback correction.     

无皂乳液聚合理论及动力学模型

介绍了无皂乳液聚合理论和相关的动力学模型，并进行了简要评述和展望。