Polymerization screw extruders

Several commercial products of PVC/TPU blends are available. The BF Goodrich Chemical Group has a PVC/ TPU blend based on their Estane series TPUs. For example, their Estane 54620, a polyester-based TPU with a °ShA 85 hardness, shows excellent compatibility with flexible PVC. The blends are produced by mixing PVC, TPU, plasticizer, stabilizer, and lubricant in a twin-screw extruder. These polymeric blends show intermediate mechanical properties between PVC and TPU. 

Elucidation of degradation kinetics for the reactive extrusion of polypropylene is constrained by the lack of kinetic data at times less than the minimum residence time in the extruder. The objectives of this work were to develop an experimental technique which could provide samples for short reaction times and to further develop a previously published kinetic model. Two experimental methods were examined the classical "ampoule technique" used for polymerization kinetics and a new method based upon reaction in a static mixer attached to a single screw extruder. The "ampoule technique was found to have too many practical limitations. The "static mixer method" also has some difficult aspects but did provide samples at a reaction time of 18.6 s and is potentially capable of supplying samples at lower times with high reproducibility. Kinetic model improvements were implemented to remove an artificial high molecular weight tail which appeared at high initiator concentrations and to reduce step size sensitivity. 

It was observed that brominated phosphate blends easily into various resins in a single or twin screw extruder. Compounding rates also are increased. It has been assumed that this is partly due to its high degree of solubility in aromatic solvent. This is in contrast with the polymeric flame retardants which are more difficult to incorporate or compound into various resins. 

In commercial practice, when a volatfle component must be extracted from a polymeric solution of high viscosity, say 500 P or greater, the extraction operation is almost always conducted in geometries which mechanically generate a wiped film. And here, screw extruders have played a major role. 

When devolatilization processes are conducted in screw extruders, the screw channels are only partially filled with the polymeric solution to be stripped of the volatile component (see Fig. 5) while the unoccupied portion of the screw channel serves to carry away the evaporated liquid. Because the barrel has a component of motion Vbz in the down channel direction, the solution is caused to flow from the extruder inlet to the outlet, which, in this case, is out of the plane of the paper. The crosschannel component of the barrel motion, Vtx, has two effects. First, it causes a circulation of the fluid in the nip and because of the continual... 

One of the earliest published studies on extraction in twin-screw extruders was conducted by Todd (1974). In this work devolatilization was conducted under vacuum using two different polymeric systems, polystyrene in one and polyethylene in the other. In the case of polystyrene, styrene was not used as the volatUe component so as to avoid problems associated with further polymerization or depolymerization instead, use was made of mixtures of thiophene and toluene or ethylbenzene. Todd found good agreement between the measured exit concentrations of the volatile component and the predicted values using Pe = 40 in the solution to Eq. (38) (see Fig. 15). The value of 5 in Eq. (39) was not reported and it is not known whether a value was chosen to provide a fit with the data or whether it was known a priori. In any event, what is clear is that the exit concentration varies with IVwhich suggests that mass transfer is occur-... 

Werner (1980) has studied devolatilization in corotating twin-screw extruders when the volatile component was stripped from the polymeric solution by applying a vacuum to the system. Rough estimates of the equilibrium partial pressure of the volatile component in the feedstream for each of the systems studied by Werner indicate that this pressure was less than the applied pressure, which means that bubbles could have been formed. Figure 17 shows the influence of the externally applied pressure on the exit concentration for a methyl methacrylate-poly(methyl methacrylate) system of fixed concentration. Note that the exit concentration decreases as the pressure is decreased, but seems to approach an asymptotic value at the lowest pressures studied. Werner also reported that at a fixed flow rate and feed concentration the exit concentration did not vary with screw speed (over the range 150-300 min" ), which also suggests that ky alay, is independent of screw speed. Figure 18 is a plot of data obtained by Werner on an ethylene-low-density poly(ethylene) system and also shows that decreases in the applied pressure result in decreases in the exit concentration, but here a lower asymptote is not observed. 

Fig. 17. Experimentally measured values of the exit concentration as a function of pressure for a polymeric solution consisting of methyl methacrylate-polyfmethyl methacrylate). Data were obtained by Werner using a twin-screw extruder. (Reproduced with permission from Werner, 1980.)...

Fig. 20. Photographs taken through a transparent barrel section in a twin-screw extruder showing the presence of bubbles at an extraction pressure of 8 Torr (MacKenzie, 1979). The polymeric solution is heptane-poly(dimethyl siloxane). (a) Screw rotational speed is 15 min . Note how bubbles are dispersed on pushing side of flight. Flow is from right to left, (b) Stationary screw. Note how the bubbles shown in (a) coalesce when the screw is stopped. 

Highly viscous polymeric reactions (e.g., the hydrolytic polyamide reaction) are often carried out in a gear-pump reactor (Tadmore and Klein, 1970). This type of reactor is often difficult to operate because the clearance of the gear teeth is increased by wear caused by flow and the reaction process. For smaller viscosity of the melt, a screw reactor or a twin-screw extruder is often used. Sterbecek et al. (1987) used a twin-screw extruder (i.e., Wemer-Pfleiderer extruder ZSK 83) for studying fast ion-catalyzed polymerization (6-caprolactam) in a melt. They indicated that power input and quality of product in such a reactor depends on the slot width between reactor wall and impeller in a twin screw extruder. They provided an optimum design of a twin-screw reactor for a fast ion-catalyzed polymerization in a melt. 

If a linear rubber is used as a feedstock for the mass process (85), the rubber becomes insoluble in the mixture of monomers and SAN polymer which is formed in the reactors, and discrete rubber particles are formed. This is referred to as phase inversion since the continuous phase shifts from rubber to SAN. Grafting of some of the SAN onto the rubber particles occurs as in the emulsion process. Typically, the mass-produced rubber particles are larger (0.5 to 5 JJ.ni) than those of emulsion-based ABS (0.1 to 1 Jim) 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 facilitate 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 extruders, and flash and thin film evaporators. Unreacted monomers are recovered for recycle to the reactors to improve the process yield. 

The F curve is another function that has been defined as the normalized response to a particular input. Alternatively, Equation (13-12) has been used as a definition of F(t), and it has been stated that as a result it can be obtained as the response to a positive-step tracer test. Sometimes the F curve is used in the same manner as the RTD in the modeling of chemical reactors. An excellent example is the study of Wolf and White, who investigated the behavior of screw extruders in polymerization processes. 

Reactive processing is limited to polymerization or chemical reactions of polymers in conventional singlescrew or twin-screw extruders, excluding processes in oscillatory kneaders, Banbury-type continuous mixers, or Diskpack equipment. Emphasis is placed on continuous processes that have been implemented commercially or that can serve as models for commercial purposes. 

Plastification of polymeric material requires energy to be transferred from an outside source into the material. In the twin-screw extruder, this energy transfer occurs through both mechanical and thermal mechanisms. However, as the extruder gets larger, the surface to volume ratio decreases significantly. Therefore, mechanical energy transfer is the dominant mechanism for plastification. 

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