Vinyl acetate polymerization CSTR

Teymour and Ray reported both laboratory-scale CSTR experiments (52) and modeling studies (55) on vinyl acetate polymerization. The period of oscillation was long, about 200 minutes, which is typical for polymerization in a CSTR. Papavasiliou and Teymour review nonlinear dynamics in CSTR polymerizations in chapter 22. 

Fig. 1.1. Branching diagram for the vinyl acetate polymerization in a CSTR. [B = 5.458371e3 s, c, / = 16.3, all other constants are as in Teymour, Ray (1991).)...

Figure 11.1 (a) Time series for conversion and temperature for vinyl acetate polymerization in a CSTR. Vertical arrow indicates change in residence time from 60 to 90 min. (b) Experimental phase plot for data in part a. (Adapted from Teymour and Ray, 1992a.)... 

Figure 2.8 Oscillatory behavior of vinyl acetate polymerization in a CSTR. Adapted from Teymour and Ray [64],...

A recent paper by Kiparissides, et al. (8) details a mathematical model for the continuous polymerization of vinyl acetate in a single CSTR. Operating conditions were shown to exist in which either steady-state operation or sustained conversion oscillations would occur for vinyl acetate. Experimental results for both cases were successfully simulated by their model. In addition, regulatory conversion control policies were considered in which both initiator feed rate and emulsifier feed rate were used as manipulated variables (Kiparissides (9)). The problem of conversion control in the operating region in which sustained conversion oscillations occur is one of significant commercial importance. Most commonly, however, a uniform concentration of emulsifier is required in the emulsion recipe and, hence, emulsifier flow rate cannot be used as a manipulated variable. 

The objective of this paper is to illustrate, by simulation of the vinyl acetate system, the utility of the analytical predictor algorithm for dead-time compensation to regulatory control of continuous emulsion polymerization in a series of CSTR s utilizing initiator flow rate as the manipulated variable. 

Aizpurua et al. [96] have studied the kinetics of vinyl acetate miniemulsions stabilized with PS or PVAc. Guyot and coworkers [97] used PS as the costabilizer for the mini emulsion encapsulation of pigment. Samer [67] has used PMMA to stabilize MMA miniemulsions for continuous polymerization in a CSTR. 

The major purpose of this paper is to present experimental results for the emulsion polymerization of vinyl acetate (VA) and methyl methacrylate (MMA) in a single CSTR. Both steady state and transient results will be presented and discussed. Possible causes for prolonged unsteady behavior will be outlined and several techniques for achieving steady operation with a CSTR will be described. 

Although theoretical models seem to be quite adequate for styrene emulsion polymerization in either batch reactors or CSTR s, such is not the case with other monomers like vinyl acetate, methyl acrylate, methyl methacrylate, vinyl chloride, etc. One of the early papers to discuss scane of the important mechanisms involved with these other moncaners was written by Priest ( ). He studied the emulsion polymerization of vinyl acetate and identified most of the key mechanisms involved. Priest s paper has been largely overlooked, however, perhaps because of the success of the Smith-Ewart approach to styrene. 

Vinyl Acetate CSTR. Figure 1 shows the effect of initiator concentration on the conversion in a CSTR at three different values of mean residence time. Conversion is directly related to rate of polymerization (Rp) by the following equation. 

For the calculation of molecular weights in CSTR emulsion reactors, a vsefnl classification comes to mind. This includes those monomer systems whose molecular weight and branching development depends on particle size and those that do not. Styrene falls into the former class and vinyl chloride and vinyl acetate into the latter class. Thus, in vinyl chloride emulsion polymerization where LCB is neglected, the instantaneous molecular weight distribution is given by... 

To illustrate this approach we consider the emulsion polymerization of vinyl acetate in a sin e CSTR. The dynamic model given by Eqs. (56-60), and Eqs. (69) and (70) can he represented more concisely by the set of nonlinear differential equations... 

In a simulation study, Leffew and Deshpande [62] have evaluated the use of a dead-time compensation algorithm in the control of a train of CSTRs for flie emulsion polymerization of vinyl acetate. In this study, monomer conv ion was controlled by manipulating the initiator flow rate. Experiments indicate that there is a period of no response (dead-time) between the time of increase in the flow of initiator and the response of monomer conversion. Dead-time compensation attempts to correct for this dead-time by using a mathematical model of the polymerization system. Reported results indicate that if the reactor is operated at low surfoctant concentration (where oscillations are observed), the control algorithm is incapable of controlling monomer conversion by the manipulation of either initiator flow rate or reactor temperature. The inability of the controller to eliminate oscillations is most probably due to the choice of manipulated variable (initiator flow rate) rather than to the perfotmance of the control algorithm (deadtime conq)ensation). 

Kipaiissides et al. [36] have applied suboptimal control to the CSTR emulsion polymerization of vinyl acetate. A mathonatical model was used to develop a simulation of the polymerization process. Verification of the model was done by open-loop bench-scale polymerization. Closed-loop control of monomer conversion via manipulation of both monoma and initiator flow rates was... 

Jaisinghani and Ray (40) also predicted the existence of three steady states for the free-radical polymerization of methyl methacrylate under autothermal operation. As their analysis could only locate unstable limit cycles, they concluded that stable oscillations for this system were unlikely. However, they speculated that other monomer-initiator combinations could exhibit more interesting dynamic phenomena. Since at that time there had been no evidence of experimental work for this class of problems, their theoretical analysis provided the foundation for future experimental work aimed at validating the predicted phenomena. Later studies include the investigations of Balaraman et al. (43) for the continuous bulk copolymerization of styrene and acrylonitrile, and Kuchanov et al. (44) who demonstrated the existence of sustained oscillations for bulk copolymerization under non-isothermal conditions. Hamer, Akramov and Ray (45) were first to predict stable limit cycles for non-isothermal solution homopolymerization and copolymerization in a CSTR. Parameter space plots and dynamic simulations were presented for methyl methacrylate and vinyl acetate homopolymerization, as well as for their copolymerization. The copolymerization system exhibited a new bifurcation diagram observed for the first time where three Hopf bifurcations were located, leading to stable and unstable periodic branches over a small parameter range. Schmidt, Clinch and Ray (46) provided the first experimental evidence of multiple steady states for non-isothermal solution polymerization. Their... 

Continuous stirred-tank reactors (CSTRs) are used for large productions of a reduced number of polymer grades. Coordination catalysts are used in the production of LLDPE by solution polymerization (Dowlex, DSM Compact process [29]), of HDPE in slurry (Mitsui CX-process [30]) and of polypropylene in stirred bed gas phase reactors (BP process [22], Novolen process [31]). LDPE and ethylene-vinyl acetate copolymers (EVA) are produced by free-radical polymerization in bulk in a continuous autoclave reactor [30]. A substantial fraction of the SBR used for tires is produced by coagulating the SBR latex produced by emulsion polymerization in a battery of about 10 CSTRs in series [32]. The CSTRs are characterized by a broad residence time distribution, which affects to product properties. For example, latexes with narrow particle size distribution cannot be produced in CSTRs. 

Fig. 9.6. Radical polymerization of vinyl acetate in a CSTR sensitivity of chain length distribution to rate of TDB propagation. Reactor and kinetic data initiator feed ...

---