Vinyl acetate polymerization continuous stirred tank reactor

While vinyl acetate is normally polymerized in batch or continuous stirred tank reactors, continuous reactors offer the possibility of better heat transfer and more uniform quality. Tubular reactors have been used to produce polystyrene by a mass process (1, 2), and to produce emulsion polymers from styrene and styrene-butadiene (3 -6). The use of mixed emulsifiers to produce mono-disperse latexes has been applied to polyvinyl toluene (5). Dunn and Taylor have proposed that nucleation in seeded vinyl acetate emulsion is prevented by entrapment of oligomeric radicals by the seed particles (6j. Because of the solubility of vinyl acetate in water, Smith -Ewart kinetics (case 2) does not seem to apply, but the kinetic models developed by Ugelstad (7J and Friis (8 ) seem to be more appropriate. 

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. 

With their combination of complex kinetics and thermal, convective, and viscosity effects, polymerizing systems would seem to be fertile ground for generating oscillatory behavior. Teymour and Ray reported both laboratory-scale Continuous Stirred-Tank Reactor (CSTR) experiments and modeling studies on vinyl acetate polymerization [63-66]. The period of oscillation was long, about 200min, which is typical for polymerization in a CSTR (Figure 2.8). Papavasiliou and Teymour [67] reviewed nonlinear dynamics in CSTR polymerizations. 

Tobita H. A simulation-model for long-chain branching in vinyl-acetate polymerization. 2. Continuous polymerization in a stirred-tank reactor. J Polym Sci Part B Polym Phys 1994 32 911-919. 

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