Polymer devolatilization

S. T. Lee and J. A. Biesenberger, Fundamental Study of Polymer Melt Devolatilization. IV Some Theories and Models for Foam-enhanced Devolatilization, Polym. Eng. Sci., 29, 782-790 (1989). 

The thermal stability of die neutralized and devolatilized polymers under nitrogen was significantly improved compared with polymers using traditional anionic and cationic polymerization catalysts (Table 3). Decomposition onset temperatures were greater than 500 °C as measured by TGA. This is attributed to the very low levels of catalyst used in the polymerization and also the stability of the neutralized complex that is formed. The qipearance of the polymers at these catalyst concentrations and 15 ppm of neutralizing agent was clear without filtration. 

One other experimental observation demonstrates the difference between old and new technologies. When a composition such as treated fumed silica In polymer B Is heated, haze develops. This haze Is due to the fact that the refractive Index of the polymer changes with temperature quite drastically while that for the solid filler does not. To demonstrate the change In refractive Index with temperature, the refractive Index, of j catalyst free devolatilized polymer A sample gave the following data ... 

If a linear mbber is used as a feedstock for the mass process (85), the mbber becomes insoluble in the mixture of monomers and SAN polymer which is formed in the reactors, and discrete mbber particles are formed. This is referred to as phase inversion since the continuous phase shifts from mbber to SAN. Grafting of some of the SAN onto the mbber particles occurs as in the emulsion process. Typically, the mass-produced mbber particles are larger (0.5 to 5 llm) than those of emulsion-based ABS (0.1 to 1 llm) and contain much larger internal occlusions of SAN polymer. The reaction recipe can include polymerization initiators, chain-transfer agents, and other additives. Diluents are sometimes used to reduce the viscosity of the monomer and polymer mixture to faciUtate processing at high conversion. The product from the reactor system is devolatilized to remove the unreacted monomers and is then pelletized. Equipment used for devolatilization includes single- and twin-screw extmders, and flash and thin film evaporators. Unreacted monomers are recovered for recycle to the reactors to improve the process yield. 

Commercial polystyrenes are normally rather pure polymers. The amount of styrene, ethylbenzene, styrene dimers and trimers, and other hydrocarbons is minimized by effective devolatilization or by the use of chemical initiators (33). Polystyrenes with low overall volatiles content have relatively high heat-deformation temperatures. The very low content of monomer and other solvents, eg, ethylbenzene, in PS is desirable in the packaging of food. The negligible level of extraction of organic materials from PS is of cmcial importance in this appHcation. 

Since the total pressure (p = p,) of the devolatilization process is usually known, computation of weight fraction (w,) of solvent remaining in the polymer at the limit of phase equilib-... 

We have seen above in two instances, those of liquid-liquid phase separation and polymer devolatilization that computation of the phase equilibria involved is essentially a problem of mathematical formulation of the chemical potential (or activity) of each component in the solution. 

It is often of industrial interest to be able to predict the equilibrium sorption of a gas in a molten polymer (e.g., for devolatilization of polyolefins). Unfortunately, the Prigogine-Flory corresponding-states theory is limited to applications involving relatively dense fluids 3,8). An empirical rule of thumb for the range of applicability is that the solvent should be at a temperature less than 0.85 Tp, where Tp is the absolute temperature reduced by the pure solvent critical temperature. 

There are relatively few phase equilibrium data relating to concentrated polymer solutions containing several solvents. Nevertheless, In polymer devolatilization, such cases are often of prime Interest. One of the complicating features of such cases Is that. In many Instances, one of the solvents preferentially solvates the polymer molecules, partially excluding the other solvents from Interaction directly with the polymer molecules. This phenomenon Is known as "gathering". 

Equilibrium between Monomer and Polymer. A monomer-with-polymer equilibrium is quite different from the polymer-with-condensation-product equilibrium discussed in Section 13.1.1. If the condensation product is removed from the reaction mixture, a condensation polymer increases in molecular weight. If the monomer is removed when it is in equilibrium with the polymer, the polymer depolymerizes to re-form the monomer. At temperatures suitable for long-term use, the equihbrium will be shifted toward stable polymer. However, at fabrication temperatures and at the high temperatures common in devolatilization, the production of monomer and low-molecular-weight ohgomers can be significant. 

Most condensation polymers have negligible heats of reaction. See Table 13.2. Heat must be supplied to evaporate by-products such as water or ethylene glycol. An external heat exchanger is the best method for heating large reactors. Flashing the recycle stream as it enters the vessel also aids in devolatilization. 

Polymer Devolatilization, Eractionation, and Plasticization Supercritical fluids may be used to extract solvent, monomers, and oligomers from polymers, including biomaterials. After extraction the pressure is reduced to atmospheric, leaving little residue in the... 

Single-screw and double-screw extruders are normally used for polymer melts to accomplish the deaeration or devolatilization of residual volatiles. Devolatilization in an extruder is effected through formation of the venting zone inside the chamber by carefully designed upstream and downstream screw sections. 

Nauman, E.B., Flash devolatilization, in Encyclopedia of Polymer Science and Engineering, Supplement Volume,... 

Biesenberger, J.A., Devolatilization of Polymers Fundamentals, Equipment, Applications. Hanser Publishers, Munich, Vienna, New York, 1983. 

In addition to the development of new products with previously unavailable property combinations, the task of making the process more efficient is important, particularly in this day and age. The cost factor energy can still be reduced if, for example, the heat of polymerization can be better utilized. It has been suggested that heat pumps be used for this purpose and the energy recovered be employed for the devolatilization step (38). In the same paper the author also suggests the integration in one factory of the monomer/polymer and end product fabrication, the latter since the polymer is already available in the molten state. 

The engineering analysis and design of these operations addresses questions which are different than those addressed in connection with the shaping operations. This is illustrated in Fig. 1 which is a flow sheet, cited by Nichols and Kheradi (1982), for the continuous conversion of latex in the manufacture of acrylonitrile-butadiene-styrene (ABS). In this process three of the nonshaping operations are shown (1) a chemical reaction (coagulation) (2) a liquid-liquid extraction operation which involves a molten polymer and water and (3) a vapor-liquid stripping operation which involves the removal of a volatile component from the molten polymer. The analysis and design around the devolatilization section, for example, would deal with such questions as how the exit concentration of... 

Fig. 1. Process flow sheet for the continuous conversion of latex in a counterrotating, tangential twin-screw extruder as it might be arranged for the production of acrylonitrile-butadiene-styrene polymer (Nichols and Kheradi, 1982). Polystyrene (or styrene-acrylonitrile) melt is fed upstream of the reactor zone where the coagulation reaction takes place. Washing (countercurrent liquid-liquid extraction) and solids separation are conducted in zones immediately downstream of the reactor zone. The remainii zones are reserved for devolatilization and pumping.

Collins et al. (1 3) have suggested that this same concept can be applied to polymer devolatilization processes, except that the HTU might be more appropriately termed the LTU when screw extruders are used since these need not be vertical. By analogy, the following expressions can be written ... 

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