Tubular reactor seeded emulsion polymerization

The objective of this study was to investigate the feasibility of using a tubular reactor for the seeded emulsion polymerization of vinyl acetate, and to study the effect of process variables on conversion rate and latex properties. 

There are many variations on this theme. Fed-batch and continuous emulsion polymerizations are common. Continuous polymerization in a CSTR is dynamically unstable when free emulsifier is present. Oscillations with periods of several hours will result, but these can be avoided by feeding the CSTR with seed particles made in a batch or tubular 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. 

The data on particle size distributions for both PVA and PMMA emulsions suggest that small particles could be quite important in the kinetic scheme, and that the larger particles probably grow by internal polymerization and by flocculation with smaller particles. The experiments with the tubular reactor installed upstream of the CSTR demonstrate a practical way to eliminate uncontrolled transients with continuous systems. We believe that the particles generated in the tube prevent CSTR oscillations by avoiding the unstable particle formation reactions in the CSTR. Berrens (8 ) accomplished the same results by using a particle seed in the feed stream to a CSTR with PVC emulsion polymerizations. 

Polystyrene can be easily prepared by emulsion or suspension techniques. Harkins (1 ), Smith and Ewart(2) and Garden ( ) have described the mechanisms of emulsTon polymerization in batch reactors, and the results have been extended to a series of continuous stirred tank reactors (CSTR)( o Much information on continuous emulsion reactors Ts documented in the patent literature, with such innovations as use of a seed latex (5), use of pulsatile flow to reduce plugging of the tube ( ), and turbulent flow to reduce plugging (7 ). Feldon (8) discusses the tubular polymerization of SBR rubber wTth laminar flow (at Reynolds numbers of 660). There have been recent studies on continuous stirred tank reactors utilizing Smith-Ewart kinetics in a single CSTR ( ) as well as predictions of particle size distribution (10). Continuous tubular reactors have been examined for non-polymeric reactions (1 1 ) and polymeric reactions (12.1 31 The objective of this study was to develop a model for the continuous emulsion polymerization of styrene in a tubular reactor, and to verify the model with experimental data. 

Process models are also important components of reactor control schemes. Kiparissides et al. [17] and Penlidis et al. [16] have used reactor models for control simulation studies. Particle number and size characteristics are the most difficult latex properties to control. Particle nucleation can be very rapid and a strong function of the concentration of free emulsifier, electrolytes and various possible reagent impurities. Hence the control of particle number and the related particle surface areas can be a difficult problem. Even with on-line light scattering, chromatographic [18], surface tension and/or conversion measurements [19], control of nucleation in a CSTR system can be difficult. The use of a pre-made seed or an upstream tubular reactor can be utilized to avoid nucleation in the CSTR and thereby imjHOve particle number control as well as increase the number of particles formed [20-22]. Figures 8.6 and 8.7 illustrate open-loop CTSR systems for the emulsion polymerization of methyl methacrylate with and... 

To resolve this instability problem, adopting a feed stream of seed latex particles [62] or installing a continuous tubular reactor, which generates seed particles, upstream of the continuous stirred tank reactor [53] have been proved quite effective (Figure 7.4b). For the latter approach, small latex particles form as a seed latex before the reacting stream enters the continuous stirred tank reactor when the monomer conversion at the exit of the tubular reactor is maintained at an adequate level. As a result, the continuous emulsion polymerization system can be operated at a stable steady state. The work of Nomura and Harada [54] also suggests that a tube-stirred tank reactor series... 

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