Reactive processing of LLDPEs in corotating intermeshing twin-screw extruder. I. Effect of peroxide treatment on polymer molecular structure

Commercial ethylene-octene linear low-density polyethylene (LLDPE) polymers were reactively extruded with low levels of 2,5-dimethyl-2,5 di(t-butylperoxy)hexane to modify their molecular structure and processing properties. Peroxide levels were kept low to avoid crosslinking. This article examines the effects of reactive extrusion in a corotating intermeshing extruder. Gel content analyses and examination of extruded thin tapes indicated that the products were gel-free, but line-broadening in high-resolution ¹³C-NMR spectra suggested that some crosslinking did occur. Molecular weight distributions were broadened toward higher molecular weights, as expected. SEC estimates of long-chain branching in reacted polyethylenes were consistent with the results of ¹³C-NMR analyses. Under our extrusion conditions, the products contained about one long branch per number-average molecule. This result and data on changes in carbon-carbon unsaturation indicate that the major chain extension mechanism is an end-linking reaction between terminal vinyls or allylic radicals formed at chain ends and secondary radicals. Both types are produced by hydrogen abstraction on the LLDPE. All long branches originated at tertiary branch points. Changes in thermal behavior, as measured by DSC analyses, paralleled those observed by temperature-rising elution fractionation (TREF). SEC molecular weight measurements and long-branch determinations by SEC and ¹³C-NMR can be used to quantify the effects of peroxide treatment on the molecular structure of polyethylenes. DSC and TREF techniques, however, appear to be more sensitive than are SEC or NMR. Relatively minor variations in the degree of mixing and temperature control during reactive extrusion have noticeable effects on the molecular structures of the peroxide-treated LLDPEs. © 1995 John Wiley & Sons, Inc.     

Reactive processing of LLDPEs in counterrotating nonintermeshing twin-screw extruder. III. Methods of peroxide addition

An ethylene–octene linear low-density polyethylene (LLDPE) was treated with peroxide in a reactive extrusion system. A counterrotating nonintermeshing twin-screw extruder (System 2) was contrasted with a corotating intermeshing twin-screw machine (System 1). In System 2, the peroxide solution was pumped into the melted polymer, while it entered with the polymer pellets in the feed section of System 1. Molecular structure changes and the rheological behavior of peroxide-modified resins are similar in both operations but System 2 is much more effective. Much lower peroxide levels were needed in System 2. However, reactions in this setup were also more difficult to control. The presence of microgel was clearly evident in System 2 products but not in those made in System 1. The results of such reactive extrusion processes depend critically on the method of the peroxide feed and mixing conditions. Reaction conditions that favor optimum economy and peroxide efficiency are those which may compromise product homogeneity. © 1996 John Wiley & Sons, Inc.     

Three-dimensional flow modeling of a self-wiping corotating twin-screw extruder. Part II: The kneading section

Three-dimensional flow simulations of kneading elements in an intermeshing corotating twin-screw extruder are performed by solving the Navier Stokes equations with a finite element package, Sepran. Instead of using the whole geometry of the 8-shaped barrel a simplified geometry is used, representing a large part of the geometry during the rotating action of the kneading paddle. The goal of these calculations is to study the dependence of several factors that influence mixing, such as shear rate, elongation rate, pressure, and the flow profile in the extruder on various extruder parameters, such as fluid viscosity, rotation speed, and throughput. The shear and elongation rate and the pressure drop are calculated for varying viscosities. The various stagger angles possible for disc configurations in the corotating twin-screw extruder are modeled. The axial backflow volume is calculated for varying values of rotation speed and throughput.     

The modeling of continuous mixers. Part I: The corotating twin-screw extruder

In many operations in polymer processing, such as polymer blending, devolatilization, or incorporation of fillers in a polymeric matrix, continuous mixers are used; e.g., corotating twin-screw extruders (ZSK), Buss Cokneaders and Farrel Continuous Mixers. Theoretical analysis of these machines tends to emphasize the flow in complex geometries rather than generate results that can be directly used (1–5). In this paper, a simple model is developed for the hot melt closely intermeshing corotating twin-screw extruder, analogous to the analysis of the single-screw extruder carried out in 1922 and 1928 (6, 7). With this model, and more specifically with its extension to the complete nonisothermal, non-Newtonian situation, it is possible to understand the extrusion process and to calculate the energy, specific energy, and temperature rise during the process with respect not only to the viscosity of the melt, but also to the screw geometry (location and number of transport elements, kneading sections and blisters, pitch, positive or negative, screw clearance, and flight width) and screw speed. To support the theoretical analysis, model experiments with a Plexiglas-walled twin-screw extruder were performed, in addition to practical experiments with melts on small- and large-scale extruders, with very reasonable results, In Part 2, the Buss Cokneader will be analyzed analogously.     

Simulation of flow in compounding machinery: Internal mixers and modular corotating intermeshing twin-screw extruders

Hydrodynamic lubrication theory has been applied to analyze flow in internal mixers and twin-screw extruders. Fluid motions in mixing regions are interpreted as being due to coupling of drag flow and pressure gradients. Pressure fields and mean flow patterns have been computed. Distributive and dispersive mixing are interpreted in terms of computed fluid fluxes in the processing machinery.     

A study of degradation of high density polyethylene in a corotating intermeshing twin screw extruder

A study of the effect of extrusion conditions on the degradation of high density polyethylene was carried out. The extent of degradation was quantified by dynamic viscometry. The effect of barrel temperature profile, screw speed, and feed rate on the degradation of high density polyethylene was determined. The viscosity response of high density polyethylene is complex with respect to extrusion conditions. Residence time studies were carried out to correlate the viscosity data. Simulations of simple theoretical models give an insight into the flow behavior of the polymer in a twin screw extruder.     

Three-dimensional flow modeling of a self-wiping corotating twin-screw extruder. Part I: The transporting section

A three-dimensional modeling of the transporting elements in a self-wiping corotating twin-screw extruder has been carried out by using the finite element package Sepran (1). This simulation uses the 3D geometry of the channel rolled over the twin-screw, which consists of the intermeshing and normal areas. The flow profile, the backflow volume, the pressure buildup, the shear and elongation rates, and the adiabatic axial temperature gradient have been calculated by solving the Navier-Stokes equations and the continuity equation for a Newtonian fluid. These results are given for different extruder parameters such as the throughput of the extruder, the rotation speed of the screws and the helix angle of the screws to better understand the influence of different extruder configurations. This study belongs to a program of research on the self-wiping corotating twin-screw extruder that also includes the modeling of the kneading elements (Part II) and, in the future, the study of scale-up and heat transfer.     

Reactive processing of LLDPEs with peroxides in counter-rotating nonintermeshing twin-screw extruder. IV. Effects of molecular structure of LLDPEs

The effects of reactive extrusion with peroxide have been compared for two linear lowdensity polyethylenes (LLDPEs). Resin C is a butene copolymer, while Resin B is an octene–ethylene copolymer. Both have similar molecular weight distributions, but Resin B is significantly richer in terminal vinyl groups. Under the same reactive extrusion conditions, Resin B is much more reactive. Resin C is easier to process in this system, producing products clean of microgel. Concurrently, however, a given peroxide level produces less molecular weight enhancement and long-branch formation in Resin C. Reactive extrusion with peroxide is suitable to effect improvements in the processability of LLDPEs for film applications, provided that the choice of peroxide and the process details are tailored to the characteristics of the particular LLDPE. © 1996 John Wiley & Sons, Inc.     

Transport in a twin-screw extruder for the processing of polymers

The fluid flow and heat transfer in polymer extrusion in a twin-screw extruder was studied numerically by using the finite volume method. In the mathematical model, the coordinate system is fixed to the screw so that it is held stationary and the barrel is moved to simplify the complicated geometry. The screw channel of a twin-screw extruder is approximated as two regions: translation and intermeshing. The flow in the translation region is similar to that in a shallow single screw extruder and is treated by the numerical methods given in the literature. In the nip or intermeshing region, strong mixing effects are expected, along with the diffusion of energy and momentum. The full governing equations are solved in this region to determine the velocity components in all the three coordinate directions. The energy equation is coupled with the equations of motion through viscosity, since the viscosity of the polymeric, non-Newtonian, fluids considered here is dependent upon the shear rate and temperature. There is no clear physical demarcation between the nip region and the translation region. Therefore, a domain matching was employed at an arbitrary location that was varied numerically to ensure that the results were independent of this location. The variation of pressure and bulk temperature along the helical channel of the twin-screw extruder is obtained, along with the shear rate. An experimental investigation of the velocity profiles in the translation region of a self-wiping twin-screw extruder, which is often used in practical applications, was carried out using a Laser Doppler Anemometer. The numerically predicted velocity profiles are compared with those from the experiments, yielding fairly close agreement.     

Functionalization of polypropylene with oxazoline and reactive blending of PP with PBT in a corotating twin-screw extruder

The aim of this study was to prepare a compatibilized PP/PBT blend in a twin-screw extruder, using oxazoline-functionalized PP. First we prepared the functionalized PP (PP-g-OXA), and then we used it as a compatibilizer in the subsequent reactive blending stage. Polypropylene was successfully functionalized by ricinoloxazoline maleinate in a corotating twin-screw extruder using a melt free radical grafting technique. Grafting yields up to 2.1 phr were achieved. This functionalized PP used as a compatibilizer markedly improved the mechanical properties of the uncompatibilized PP/PBT (PBT content 30 wt %) blend. Significant improvements were observed, especially in impact strength (Charpy) and elongation at break of the compatibilized blends. The increased interactions between the phases were characterized by SEM analysis, DMTA, and DSC experiments. The properties of the blend greatly depended on the degradation of the PP during grafting. An optimal content of compatibilizer exists, which is dependent on the degradation of PP, grafting yield of oxazoline monomer, and on the amount of free, ungrafted monomer present in the compatibilizer. These factors can be adjusted by properly choosing the processing conditions and chemical parameters. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 883–894, 1997     

Reactive processing of polyethylenes on a single screw extruder

The modification of low density polyethylene, linear low density polyethylene, and their blend by dicumyl peroxide at the time of the extrusion on a single screw extruder is reported. The study shows that the optimum conditions of modification can be determined on a torque rheometer and these can then be applied for actual extrusion. A low level of crosslinking can be introduced by reactive extrusion for improving the heat stability without adversely affecting the processing behavior. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2545–2549, 2001     

Continuous polymerization of ω‐lauryl lactam in an intermeshing corotating twin‐screw extruder

This article describes the synthesis of poly(ω‐lauryl lactam) by a reactive extrusion process. Anionic ring‐opening polymerization was performed in an intermeshing corotating twin‐screw extruder. We investigated the evolution of conversion of ω‐lauryl lactam as a function of reaction time, screw speeds, different feed rates, and different screw configurations along the screw axis in a twin‐screw extruder. For comparison with continuous polymerization in a twin‐screw extruder, we studied polymerization in an internal mixer, which was considered a batch reactor. We found the final conversion of ω‐lauryl lactam made in a twin‐screw extruder was higher than in an internal mixer. Higher molecular weights are found at lower screw speeds and feed rates. Melt viscosities and mechanical properties of the polymers were measured. Residence time, molecular weights, and shear mixing have the main effect on the mechanical properties of products. The twin‐screw extruder performance was interpreted in terms of commercial software. It was found that twin‐screw extruder reaction rate was higher than those in the batch reactor and increased locally with screw speed and feed rate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1605–1620, 2005     

A twin-screw extruder for oil extraction: II. Alcohol extraction of oleic sunflower seeds

Our work is about the extraction of sunflower seed oil in a twin-screw extruder with or without the injection of 2-ethylhexanol and acidified 2-ethylhexanol. 2-Ethylhexanol is mixed with phosphoric acid. The oil recovery is increased to 90% by the co-injection of acidified alcohol. Mixing phosphoric acid with the alcohol enhances the lability of the oily spherosomes. Its addition increases the destruction of the membranes enveloping the lipid-containing organelles to release the oil more easily. Phosphoric acid exhibits an extracting and a degumming role. The best oil quality was obtained at a low extraction temperature (80°C), when 88% of the oil was removed. After alcoholic distillation, the oil exhibited a total acid value (mineral acidity plus organic acidity) of 4 mg KOH/g of oil and an organic phosphorus content below 30 ppm. This work was presented as an oral communication at the 2nd American Oil Chemists’ Society Europe Symposium, October 1–4, 1998, at Cagliari, Italy.     

Solid transportation in the feeding zone of intermeshing co-rotating twin-screw extruders

A mathematical model was proposed for the characteristics of solid transportation in the feeding zone of an intermeshing co-rotating twin screw extruder. The model was based on the observations made from a “transparent” extruder. The analysis considered optimal solid conveyed with maximum throughput rate, i.e., when the upper and lower intermeshing zones, and the two sides of the screws were all partially filled with solid resin to an extent that a slight increase in the solid filling would immediately cause blocking of the solid transportation. Because of these starve-fed characteristics, the conventional approach for analysing solid feeding used in single-screw extruders was inadequate for twin-screw extruders. This paper also suggests a solution for the mathematical expressions describing the stress and velocity fields in the solid feeding zone of a twin-screw extruder. Finally, the predicted values are compared with our experimental findings.     

Development of polymer blend morphology during compounding in a twin-screw extruder. Part II: Theoretical derivations

In Part II of the work, the intermeshing twin-screw extruder is briefly described and the theoretical procedures used to model its operation are summarized. Based on the microrheological considerations discussed in Part I, a predictive procedure of the morphology evolution during compounding of two immiscible polymers is proposed. In this first generation model, only the shear flow effects are considered. Furthermore, to avoid complications due to coalescence a low concentration of the dispersed phase was assumed. In the procedure, two drop breakup mechanisms are discussed. The first assumes that the drops do not break under flow while the second postulates that breakup occurs under flow. Two dispersion mechanisms are considered, the first postulating continuously increasing polydispersity of drop size and the second postulating that drop polydispersity is inversely proportional to deformation strain. The influence of the screw configuration and operating conditions on blend morphology evolution is studied. It is expected that the computed drop size distribution provides limiting values for the experimental data. Dependency of predicted morphology on operating conditions is also investigated. Increasing screw rotating speed (resulting in increasing energy consumption) and decreasing throughput (resulting in decreasing productivity) lead to prediction of finer drop size. In practice, therefore, a compromise would be required. The proposed procedure is limited to melt flow (excluding the die region) within the region of large capillary parameter values, k > 4k_crit.     

双螺杆挤出机螺杆组合及喂料工艺对增韧ABS力学性能的影响

介绍双螺杆挤出机各种规格的螺杆元件及三种螺杆组合方式，分析了不同螺杆组合方式及喂料工艺对增韧ABS挤出工艺和材料力学性能的影响，并设计了一种适合于增韧ABS加工的螺杆组合方式。结果表明：通过适当的螺杆组合和喂料工艺可改善增韧ABS的挤出工艺，提高材料的力学性能。     

The copolymerization of methacrylates in a counter-rotating twin-screw extruder

The copolymerization of n-butylmethacrylate with 2-hydroxypropylmethacrylate was studied in a closely intermeshing counterrotating twin-screw extruder. The average molecular weight of the product can be increased by increasing the screw rotation rate or the die resistance or by decreasing the throughput or the barrel temperature. The conversion can be improved by decreasing the throughput, increasing the die resistance, and (within limits) increasing the barrel temperature, as well as through post-initiation. Compared with various classical polymerization processes, this situation requires that particular attention be paid to the occurrence of a gel effect, the existence of a thermodynamic ceiling temperature, and the reactivity ratio of the monomers used.     

PP-R双螺杆挤出熔体输送和降解行为的研究

对无规共聚聚丙烯(PP-R)在ZSK-300型双螺杆挤出机中熔体输送特性和热降解行为进行了研究,计算了ZSK-300的最大挤出量．分析了熔体输送流场;并对加料量、熔体流动指数、助剂量、熔体温度等工艺操作条件对熔体输送和降解行为的影响进行了讨论。结果表明,加料量的改变需要适当调整加热温度：粉料熔体流动指数的微小波动,对挤出物的质量和挤出过程的稳定性没有影响;降低熔体挤出温度,可明显降低PP-R的热氧降解。     

Dynamical modelling of a reactive extrusion process: Focus on residence time distribution in a fully intermeshing co-rotating twin-screw extruder and application to an alginate extraction process

The context of this study is the modelling of reactive extrusion process based on an alginate extraction protocol. Residence Time Distribution (RTD) is one important part to predict the kinetics of reactive compounds. A simple model is proposed to predict RTD in fully intermeshing co-rotating twin-screw extruders without reaction. This model, which can be easily extended to reactive case in a future work, is based on the extension of an axial dispersion model, including control parameters (screw speed and flow rate) and geometrical parameters (screw profile and die design). Simulations were performed for various operating and geometrical conditions so as to illustrate possibilities offered by the proposed model. Validation was conducted for two different extrusion applications, seaweed extrusion and polymer extrusion. This highlighted the model ability to predict RTD for various kinds of materials after adjusting only one parameter thanks to a unique experimental RTD curve.     

Experimental investigation of the morphology development and mechanical properties of waste ethylene propylene diene monomer/polypropylene blend in modular intermeshing corotating twin‐screw extruder

Nowadays, with the increase in the number of automobiles, waste EPDM (ethylene propylene diene monomer) is causing a significant environmental problem. From environmental and economical perspectives, recycling is one of the popular methods to solve environmental problems. This study, which involved waste EPDM/PP (polypropylene) blends with the ratio range of 70/30 and 75/25, set out to ascertain the relevance of the mass percentage of the dispersed phase, the influence of the screw geometry, the screw rpm, and the melting temperature of PP materials on the morphology and mechanical properties of the waste rubber blend. The purpose of this study is to develop a high‐value thermoplastic elastomer from waste EPDM. This investigation concentrated on determining the optimum conditions for producing a blend by extrusion, relative to screw geometry, screw rational speed, and operating temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2276–2282, 2002