Emulsion polymerization reactor operation

The derivation and development of a mathematical model which is as general as possible and incorporates detailed knowledge from phenomena operative in emulsion polymerization reactors, its testing phase and its application to latex reactor design, simulation, optimization and control are the objectives of this paper and will be described in what follows. 

The development of a very general computer program for simulating any emulsion polymerization reactor is underway at present. This progreim will have the ability to provide reactor simulations at several information levels so that by specifying a few modelling assumptions and reactor operating conditions, model predictions can be obtained. 

The commercially used emulsion polymerization reactors (stirred-tank and continuous-loop) are designed to achieve perfect mixing. As will be discussed in Section 6.4.5, perfect mixing is not always achieved. Nevertheless, this flow model allows a good prediction of the emulsion polymerization reactor performance with a moderate mathematical effort, and it will be used here. Macroscopic balances (i.e., considering the reactor as a whole) are used. For the sake of generality, inlet and outlet streams are included in the balances. Both terms should be removed for batch operation, the outlet term should be eliminated in semibatch and both maintained in continuous processes. 

Achieving optimal control and operation of emulsion polymerization reactors requires the integration of mechanistic... 

FIGURE 18.1 Mechanisms occurring in emnlsion polymerization. From Zeaiter J. A framework for advanced/inteUigent operation of emulsion polymerization reactors [PhD Thesis]. Sydney University of Sydney 2002. 

FIGURE 18.4 Evolution of the PSD at 72°C in styrene polymerization—samples taken at half-hourly intervals (semibatch, monomer federate at 1.6 X 10 mol s" ). (a) Experimental data (b) model simulations. From Zeaiter J. A framework for advanced/intelUgent operation of emulsion polymerization reactors [PhD Thesis]. Sydney University of Sydney 2002. (See insert for color representation of the figure.)... 

One unique but normally undesirable feature of continuous emulsion polymerization carried out in a stirred tank reactor is reactor dynamics. For example, sustained oscillations (limit cycles) in the number of latex particles per unit volume of water, monomer conversion, and concentration of free surfactant have been observed in continuous emulsion polymerization systems operated at isothermal conditions [52-55], as illustrated in Figure 7.4a. Particle nucleation phenomena and gel effect are primarily responsible for the observed reactor instabilities. Several mathematical models that quantitatively predict the reaction kinetics (including the reactor dynamics) involved in continuous emulsion polymerization can be found in references 56-58. Tauer and Muller [59] developed a kinetic model for the emulsion polymerization of vinyl chloride in a continuous stirred tank reactor. The results show that the sustained oscillations depend on the rates of particle growth and coalescence. Furthermore, multiple steady states have been experienced in continuous emulsion polymerization carried out in a stirred tank reactor, and this phenomenon is attributed to the gel effect [60,61]. All these factors inevitably result in severe problems of process control and product quality. 

Consider for example a continuous stirred tank dispersion polymerization reactor operating with a low viscosity emulsion ... 

PVDE is manufactured using radical initiated batch polymerization processes in aqueous emulsion or suspension operating pressures may range from 1 to 20 MPa (10—200 atm) and temperatures from 10 to 130°C. Polymerization method, temperature, pressure, recipe ingredients, the manner in which they are added to the reactor, the reactor design, and post-reactor processing are variables that influence product characteristics and quaUty. 

Processes that are essentially modifications of laboratory methods and that allow operation on a larger scale are used for commercial preparation of vinyhdene chloride polymers. The intended use dictates the polymer characteristics and, to some extent, the method of manufacture. Emulsion polymerization and suspension polymerization are the preferred industrial processes. Either process is carried out in a closed, stirred reactor, which should be glass-lined and jacketed for heating and cooling. The reactor must be purged of oxygen, and the water and monomer must be free of metallic impurities to prevent an adverse effect on the thermal stabiUty of the polymer. 

A semi-batch reactor has the same disadvantages as the batch reactor. However, it has the advantages of good temperature control and the capability of minimizing unwanted side reactions by maintaining a low concentration of one of the reactants. Semi-batch reactors are also of value when parallel reactions of different orders occur, where it may be more profitable to use semi-batch rather than batch operations. In many applications semi-batch reactors involve a substantial increase in the volume of reaction mixture during a processing cycle (i.e., emulsion polymerization). 

The physical picture of emulsion polymerization is complex due to the presence of multiple phases, multiple monomers, radical species, and other ingredients, an extensive reaction and particle formation mechanism, and the possibility of many modes of reactor operation. 

Step 3—In a separate step, styrene-acrylonitrile (SAN) resin is prepared by emulsion, suspension, or mass polymerization by free-radical techniques. The operation is carried out in stainless-steel reactors operated at about 75°C (167°F) and moderate pressure for about 7 hours. Tlie final chemical operation is the blending of the ABS graft phase with the SAN resin, plus adding various antioxidants, lubricants, stabilizers, and pigments. Final operations involve preparation of a slurry of fine resin particles (via chemical flocculation), filtering, and drying in a standard fluid-bed dryer at 121-132°C (250-270°F) inlet air temperature. 

On the Optimal Reactor Type and Operation for Continuous Emulsion Polymerization... 

The present review paper, therefore, refers firstly to the particle formation mechanism in emulsion polymerization, the complete understanding of which is indispensable for establishing a correct kinetic model, and then, deals with the present subject, that is, what type of reactor and operating conditions are the most suitable for a continuous emulsion polymerization process from the standpoint of increasing the volume efficiency and the stability of the reactors. 

Although the early literature described the application of a tubular reactor for the production of SBR latexes(1), the standard continuous emulsion polymerization processes for SBR polymerization still consist of continuous stirred tank reactors(CSTR s) and all of the recipe ingredients are normally fed into the first reactor and a latex is removed from the last one, as shown in Figure 1. However, it is doubtful whether this conventional reactor combination and operation method is the most efficient in continuous emulsion polymerization. As is well known, the kinetic behavior of continuous emulsion polymerization differs very much according to the kind of monomers. In this paper, therefore, the discussion about the present subject will be advanced using the... 

Our final goal in the present paper is to devise an optimal type of the first stage reactor and its operation method which will maximize the number of polymer particles produced in continuous emulsion polymerization. For this purpose, we need a mathematical reaction model which explains particle formation and other kinetic behavior of continuous emulsion polymerization of styrene. 

Optimal reactor type and its operation method for the first stage in continuous emulsion polymerization was discussed in this paper. It was clarified theoretically and experimentally uaing a... 

---