The source of degradation during extrusion of polystyrene

The nature and magnitude of mechanical reactions of polystyrene in capillary flow has been examined in a model extrusion process. Studies on polystyrene quantify the sensitive increase in shear degradation tendency with increasing polymer molecular weight. A molecular weight spectrum caused by the shear stress profile was measured across the extrudate radius by the new technique of solvent coring. It was further determined that an appreciable fraction of the mechanical reaction is shear induced in the capillary reservoir. This is confirmed by precision determinations of molecular weights and distributions by gel permeation chromatography on samples taken from concentric layers in the capillary reservoir after 50% sample extrusion. These results, involving traces of oxygen as a chemical probe, describe the stress profile in the reservoir and in the capillary during the pressure extrusion of high molecular weight polystyrene. Thus, changes in molecular weight and distribution may be attributable to changes in different portions of the shear geometry rather than the uniform changes generally considered. Clear evidence is also presented showing the dramatic effects of oxygen on these shear-induced changes in molecular weight and distribution.     

The particle flow of polystyrene during capillary extrusion

The melt flow of emulsion polymerized polystyrene has been investigated in accordance with the particle flow concepts developed by Berens and Folt. Particles were found to be present in the extrudate up to 210°C and resins with larger particles were found to have lower viscosities. The molecular weight appears to have no significant effect on the melt viscosity above a certain molecular weight. The energy of activation for viscous flow at 190°C and at shear stress of 5 × 10⁵ dynes/cm² was found to be 29–33 kcal/mol depending on type of resin.     

Polypropylene degradation control during reactive extrusion

In this work, a proportional‐integral‐derivative (PID) control scheme with two different tuning methods to control the degree of degradation of polypropylene (PP) during reactive extrusion is proposed. The concentration of dicumyl peroxide is taken as the manipulated variable. The molten viscosity of PP under processing is taken as the controlled variable. The degree of degradation is determined by a viscosity function derived by an off‐line identification. A first‐order‐plus‐time‐delay empirical model is identified to simulate the system plant. Both Ziegler–Nichols tuned PID and internal model control (IMC)‐based PID controllers are implemented on the system. Better performances in settling time and precision can be achieved using the IMC‐based PID controller. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 280–289, 2005     

In situ compatibilization of polypropylene/polystyrene blend by controlled degradation and reactive extrusion

In situ compatibilization of polypropylene (PP) and polystyrene (PS) was achieved by combinative application of tetraethyl thiuram disulfide (TETD) as degradation inhibitor and di‐tert‐butyl peroxide as degradation initiator in the process of reactive extrusion. The PP/PS blends obtained were systematically investigated by rheological measurement, scanning electron microscopy, and differential scanning calorimetry. The results indicate that peroxide‐induced degradation of PP can be effectively depressed by adding TETD, which may favor the formation of PP‐g‐PS copolymer during melt processing. The PP‐g‐PS copolymer formed may act as an in situ compatibilizer for PP/PS blends, and subsequently decreases the size of dispersed PS phase and changes both rheological and thermal properties of the blends. Based on the present experimental results, the mechanisms for the controlled degradation of PP and in situ formation of PP‐g‐PS copolymer in the PP/PS blends have been proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal and mechanical degradation during polymer extrusion processing

Polymer processing often activates material degradation, which affects to some extent the performance or the life cycle of the obtained products. Polymer degradation is usually evidenced by molecular weight variations as consequence of exposure to high processing temperature and to relevant mechanical stresses. The degrading effects of melt extrusion under different thermo‐mechanical conditions on polymethyl‐methacrylate and polystyrene are investigated. Materials were processed at different temperatures and rates in a single screw extruder and in a capillary rheometer. Processed and as‐received materials were analysed by Gel permeation chromatography, solution viscosity, and melt rheology. Evaluations of molecular weight and rheological behavior changes after processing, as compared with as‐received materials, evidenced the extent of degradation in the different conditions. Experimental analysis was accompanied by finite elements simulation of the polymer flow and heat transmission within the extruder. This allowed an estimation of the expected shear stresses and temperatures distributions, thus indicating potentially critical situations. It was found that the materials processed at the highest rates in extruder presented lowest molecular weight reductions. This was attributed to the shorter residence time in the extruder and to the possibility of wall slip phenomena, which likely reduce the actual shear stress and viscous dissipation in the fast processing conditions. POLYM. ENG. SCI., 47:1813–1819, 2007. © 2007 Society of Plastics Engineers     

The thermal degradation of polystyrene nanocomposite

Nanocomposite formation brings about an enhancement of many properties for a polymer, including enhanced fire retardancy. This study was carried out to determine if the presence of clay causes changes in the degradation pathway of polystyrene. In the case of virgin PS, the degradation pathway is chain scission followed by β-scission (depolymerization), producing styrene monomer, dimer and trimer, through an intra-chain reaction. As the clay loading is increased, the evolved products produced through inter-chain reactions become significant. Due to the barrier effect of the clay layers, the radicals have more opportunity to undergo radical transfer, producing tertiary radicals, and then radical recombination reactions, producing head-to-head structures, and hydrogen abstraction from the condensed phase also occurs. In the presence of clay, the color of solid residues darkens as the clay content increases. It is thought that this color change is caused by the formation of conjugated double bonds in the presence of clay.     

Process control for polypropylene degradation during reactive extrusion

This paper describes the development of process control schemes for the free radical initiated (reactive) degradation of polypropylene in an extruder (reactive extrusion). The objective of the work was to control the amount of degradation in order to produce polypropylene with a specified molecular weight. The die pressure drop was used as a measure of the amount of degradation (the measured variable) and the initiator concentration was used to control the amount of degradation (the manipulated variable). The reactive degradation process was modeled empirically to determine the dynamic relationship between the input degradation initiator concentration and the output die pressure drop. Several control schemes were evaluated for controlling the die pressure drop (amount of degradation) with emphasis placed on schemes designed to overcome the non-linear process gain and dead time.     

Effects of ultrahigh speed twin screw extrusion on the thermal and mechanical degradation of polystyrene

This article characterizes a novel twin screw extrusion (TSE) process with the capability of rotating at speeds up to 4500 rpm. The resulting extreme high shear rate is expected to result in molecular weight changes due to thermomechanical degradation of the polymeric materials being extruded, polystyrene (PS) in this case. In order to differentiate between mechanical and thermal factors affecting degradation of PS running at ultrahigh speeds and also to evaluate the relative importance of the two mechanisms, PS has been extruded at different screw speeds and different barrel temperatures with corresponding melt temperatures. Viscosity measurements and size exclusion chromatography measurements show the extent of degradation due to mechanical stress as a result of high screw rotational speeds. Furthermore, through analyzing the kinetics of PS depolymerization, the reaction rate and hypothetical apparent temperatures at each screw speed have been calculated. All results support the idea that the mechanical shear stress can be considered as the controlling factor of polymer degradation in ultrahigh speed TSE. POLYM. ENG. SCI., 56:743–751, 2016. © 2016 Society of Plastics Engineers     

Thermal degradation of polystyrene

The importance of the study of thermal degradation of polymeric fuels arises from their role in the combustion of solid propellants. Estimation of the condensed-phase heat release during combustion can be facilitated by the knowledge of the enthalpy change associated with the polymer degradation process. Differential scanning calorimetry has been used to obtain enthalpy data. Kinetic studies on the polymeric degradation process have been carried out with the following objectives. The literature values of activation energies are quite diverse and differ from author to author. The present study has tried to locate possible reasons for the divergence in the reported activation energy values. A value of 30 kcal has been obtained and found to be independent of the technique employed. The present data on the kinetics support to chain-end initiation and unzipping process. The activation energies are further found to be independent of the atmosphere in which the degradation of polymer fuel is carried out. The degradation in air, N₂, and O₂ all yield a value of 30 kcal/mole for the activation energies.     

Controlled degradation of polystyrene

For the purpose of efficient utilization of waste polystyrene, the recovery method of a styrene oligomer having a molecular weight of 1000–3000 was studied. Thermal and catalytic degradations were carried out. It was impossible to obtain a styrene oligomer with a molecular weight less than 5000 by thermal degradation in the temperature range of 300–500°C. Catalytic degradation in the presence of silica–alumina catalyst in the temperature range of 190–230°C made it possible to control the decrease in molecular weight and to obtain a styrene oligomer having a molecular weight of 500–3000. Simultaneously, the molecular structures of the reaction products from thermal and catalytic degradations were determined by NMR analysis.     

Reactive extrusion of polystyrene/polyethylene blends

The feasibility of inducing beneficial changes to polystyrene/polyethylene (PS/PE) blends via reactive extrusion processes is considered. Experiments have been conducted on 50:50 wt.% PS/PE blends that were treated with different levels of dicumyl peroxide and triallyl isocyanurate coupling agent. Both a low molecular weight and a high molecular weight blend series have been investigated. A “more reactive” polystyrene was synthesized by incorporation of a minor amount of ortho-vinylbenzaldehyde. Blends containing this modified polystyrene were subjected to identical processing' conditions on a counter-rotating twin screw extruder. Examination of the tensile properties of the extrusion products suggested that a judicious level of peroxide and coupling agent additives would be beneficial to the ultimate physical properties. The quantity of styrenic phase becoming chemically grafted to the polyethylene matrix was influenced most strongly by the level of the chosen coupling agent. As determined by scanning electron microscopy, the phase morphologies of the tensile test fracture surfaces were strongly dependent upon the reaction extrusion process; those extruded blends that had been exposed to the additive pre-treatment displayed substantially finer microstructure. The enthalpy of fusion of the polyethylene melting endotherm was likewise influenced by both the presence or absence of the additives as well as the molecular weight nature of the blend series.     

Online monitoring of the thermal degradation of POM during melt extrusion

Because of its high stiffness, chemical resistance, and low viscosity, Poly (oxymethylene) (POM) is of high relevance for technical applications. The thermal degradation of POM during processing affects its final properties and decreases the long‐term stability. The degradation is indicated by the emission of formaldehyde (FA) gas. The aim of this study is to monitor the thermal degradation of POM online, during the melt extrusion in a co‐rotating twin screw extruder (TSE). The effect of the processing conditions on the thermal stabilisation of the POM is observed by FA emission and online viscosity measurements. The effect of processing conditions on the compounding of POM with two different FA scavengers is also studied. Fourier transform infrared (FTIR) spectroscopy is used for the online measurement of FA gas and acetyl acetone colour measurement for the offline characterisation. The online viscosity is measured by passing the melt through a slit die at constant volume flow rate. An enhanced thermal degradation is found with decreasing throughput and increasing screw speed. A good correlation between the online viscosity and offline FA measurement is observed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Production of controlled-rheology polypropylene resins by peroxide promoted degradation during extrusion

Results of experimental and modeling studies of the peroxide promoted degradation of polypropylene (PP) are presented. Experiments were carried out, in glass ampoules and in a plasticating extruder. The initiator, 2.5-dimethyl-2,5-bis(tert-butylperoxy)hexane was used as a radical generator. The extruder used had a 38 mm diameter and 24:1 L/D single-screw. In these experiments, the effect of peroxide concentration and screw speed on the molecular weight distribution (MWD) of the polypropylene resin was studied. Samples collected from the experimental runs were analyzed for melt flow index (MFI), flow curve, extrudate swell, and MWD. The measured data are presented and correlations among various parameters are considered. Generally, it can be concluded that controlled-rheology (CR) resins with lower molecular weight, narrower MWD, and reduced viscosity and elasticity, can be produced, A kinetic model for the peroxide Initiated degradation of PP is proposed. Simulations based on this model are compared with experimental data for the production of CR resins. The experimental data were obtained from three sources: (i) industry, (ii) literature, and (iii) present experimental work. The comparison was done in terms of average molecular weights of the resin. Agreement between model predictions and experimental results is quite satisfactory suggesting that this model should find use in commercial practice.     

Kinetic study on the first stage during thermal degradation of polystyrene

The kinetic parameters of the first stage of polystyrene degradation have been investigated to elucidate the reaction mechanisms using the flow reactor system. The decrease in molecular weight of polystyrene was recorded at minute intervals over the temperature range 310°–390°C. Generally, the first and second stages were observed by thermogravimetric analysis (t.g.a.), however in the early stage of the degradation volatile yields of at least 5% occurred. Therefore, using t.g.a. analysis it is difficult to detect this earlier stage. It became evident that the first stage in the earlier part of the reaction could be detected by g.p.c. analysis. We have observed the hidden kinetic parameters of the nature of the first stage of the polystyrene degradation. The results indicate that the main chains were degraded randomly with the small quantitative volatile groups in the first stage and the rates of decrease in molecular weight in the first stage against reaction temperatures were evaluated as log k_s = 12.0 ? 41300/RT.     

Effect of supercritical carbon dioxide on polystyrene extrusion

A study on the extrusion of polystyrene was carried out using supercritical carbon dioxide (scCO₂) as foaming agent. scCO₂ modifies the rheological properties of the material in the barrel of the extruder and acts as a blowing agent during the relaxation at the passage through the die. For experiments, a single-screw extruder was modified to be able to inject scCO₂ within the extruded material. The effect of operating parameters on material porosity was studied. Samples were characterized by using water-pycnometry, mercury-porosimetry and scanning electron microscopy. Polystyrene with expansion rate about 15–25% was manufactured. A rapid cooling just downstream the die is important to solidify the structure. The die temperature allows the control of the porosity structure. CO₂ concentration shows no significant influence.     

Orientation development in tubular film extrusion of polystyrene

The tubular film extrusion of atactic polystyrene is described. The in-plane and out-of-plane birefringence of the polystyrene film was determined and compared with both the kinematics (drawdown, blow-up ratio) and applied tensions and bubble pressures. The data can be correlated by comparing the birefringences with the stresses acting in the film at the position of vitrification. The data compare quantitatively with Oda, White, and Clark's correlation developed for the birefringence of samples vitrified during shear and uniaxial extensional flow. The experimental results are interpreted in terms of White and Spruiell's biaxial orientation factors.     

Modeling of polypropylene degradation during reactive extrusion with implications for process control

This paper presents the development of a model for free radical initiated polypropylene degradation during reactive extrusion that combines a kinetic model of the polypropylene degradation reaction with a simplified model of the melting mechanism in the extruder. The free radical initiated degradation of polypropylene is characterized by a narrowing of the molecular weight distribution (MWD) and a decrease in the molecular weight averages. A high temperature SEC is used to determine MWD's for three different commercially available polypropylenes degraded at various initiator concentrations in a 1.5 inch single screw extruder (L/D = 24:1). The predictions of the kinetic model alone and the combined kinetic-melting model are compared with the experimentally determined MWD's and molecular weight averages for the degraded polypropylenes. The predictions of a modified kinetic model that includes the possibility of termination by combination are also examined. The kinetic-melting model is found to provide significantly improved predictions of the experimentally determined MWD's and molecular weight averages in comparison to the original kinetic model. A viscosity-molecular weight relationship is also developed, which is then used to determine the gain of the degradation process as a function of the initiator concentration from the molecular weight averages predicted by the kinetic-melting model. Earlier work has shown such prior knowledge of the process gain can be used to significantly improve the performance of process control schemes for the degradation process.     

单甘脂对聚苯乙烯挤出发泡性能的影响

利用超临界二氧化碳挤出发泡法,研究了单硬脂酸甘油脂（GMS）母粒的添加量对聚苯乙烯（PS）发泡性能的影响。采用毛细管流变仪研究了GMS添加量对PS/GMS体系的流变特性的影响,观察并测试了发泡材料的微观泡孔结构。研究结果表明,GMS的添加会降低树脂的黏度。母粒中含有的多组分GMS和少组分乙烯-醋酸乙烯（EVA）共同影响制品的表观密度、平均泡孔直径和泡孔密度等参数。在GMS添加量为1.05%,EVA添加量为0.45%时,制品的平均泡孔直径最小,泡孔密度最大。