Morphology of High Impact Polypropylene Particles† (original) (raw)
Related papers
Probing into the pristine basic morphology of high impact polypropylene particles
Polymer, 2009
In this paper, the pristine basic morphology of high impact polypropylene (hiPP) particles prepared with an industrial MgCl 2 /TiCl 4 Ziegler-Natta catalyst undergoing sequentially occurred propylene (P) homopolymerization and ethylene (E)/propylene copolymerization has been probed mainly using transmission electron microscopy (TEM) techniques including plain TEM and the advanced transmission electron microtomography (TEMT). It is revealed that the basic structure units comprising a whole hiPP particle are the submicron PP (polypropylene) globule and nano-sized EP (ethylene-co-propylene) droplet. EP rubber (EPR) domain is formed by the agglomeration of EP droplets. Continually formed EP droplets turn to fill, from inside out, the micro-and macro-pores inside the preformed PP skeleton, affording different-sized EPR domains. Taking the two basic structure units into account, new quaternary structure model describing the manifold structures of hiPP particles has been proposed. From these findings, it is suggested that, to gain hiPP polymers with excellent stiffness/toughness-balanced properties, it is crucial to control the first-staged propylene homopolymerization alongside a rational design of the catalyst architecture to accomplish desired EPR dispersion morphologies that dictate hiPP properties.
Polymer International, 2010
A commercial high-impact polypropylene (hiPP) was fractionated by temperature-gradient elution fractionation into nine fractions. All fractions were studied using Fourier transform infrared spectroscopy and differential scanning calorimetry. The amount of ethylene in the fractions was also determined. The results demonstrate that the ethylene-propylene statistical copolymer (or ethylene-propylene rubber, EPR) content in this hiPP is rather low and the amounts of ethylene-propylene segmented copolymer and ethylene-propylene block copolymer (that act as adhesive and compatibilizer between elastomeric phase and matrix, respectively) are negligible. Furthermore, the morphology of the resin was studied using scanning electron microscopy observations of microtome-cut original and etched samples, which reveals that EPR particles are too large and their distribution inside the matrix is not uniform.
Morphological analysis of high-impact polypropylene using X-ray microCT and AFM
European Polymer Journal, 2013
Detailed visualization and understanding of high-impact polypropylene (hiPP) particle morphology and its evolution on the scale of entire particles is important for obtaining the required mechanical and optical properties of this material and for the quantitative description of mass transport in hiPP particles. Shape and size of hiPP particles as well as the spatial distribution of pores, PP homopolymer and ethylene-propylene rubber (EPR) phases in individual particles is visualized by micro-computed tomography (microCT) and atomic force microscopy (AFM) techniques. The morphology of each hiPP particle depends on many factors including catalyst system, the initial pore structure of porous catalyst and homopolymer particles, reactor conditions and particle history. These factors affect the required content, the constitution and the spatial distribtuion of EPR phase. To understand particle morphology and its evolution in a quantitative way we need a highquality morphology data. The presented results include the AFM visualization of rubber layer on the surface of hiPP particles, the microCT visualization of not only porous homopolymer PP particles but also of large rubber domains in hiPP particles and the AFM mapping of the fine networked structure of EPR rubber and pores in hiPP particles.
Impact polypropylene copolymers: fractionation and structural characterization
Polymer, 1993
Impact polypropylene copolymers may be produced in a two-reactor system to yield a blend of homopolymer with an ethylene-propylene rubber (EPR). The polypropylene homopolymer, which is itself brittle and has low impact strength, is markedly toughened by the presence of the EPR. The rubber-like EPR exists as a phase-segregated discrete particle in a continuous matrix of the hard phase. The molecular structure analysis of the resulting complex mixture is a formidable task. The purpose of this paper is to describe a preparative and an analytical temperature-rising elution fractionation (t.r.e.f.) technique as the primary tools to separate and characterize a commercial impact copolymer. These techniques permit the isolation and subsequent characterization of the components of the impact copolymer by ancillary techniques, primarily 13C nuclear magnetic resonance and differential scanning calorimetry. These techniques were applied to the structural analysis of a commercial impact-grade polypropylene with a melt flow rate of 6. It was found that this impact copolymer was composed of about 75wt% of isotactic polypropylene, about 17wt% of a highly non-crystalline EPR and about 8 wt% of semicrystalline ethylene-propylene copolymers. A major component of the semicrystalline ethylene-propylene copolymers was an ethylene-rich copolymer containing between 0 and 8 wt% of propylene comonomer. The separate characterization of the components of the impact copolymer gives insight into the chemical synthesis process used to produce these copolymers. Further, it permits one to gain a better understanding of the location and function of each of the components in the complex mixture.
Degradation of polypropylene impact-copolymer during processing
Polymer Degradation and Stability, 2008
The effect of processing on molecular structure and properties of polypropylene impact-copolymer (ICPP) was investigated. It was confirmed that multiple extrusions induced changes in molecular weight resulting in increased MFI and decreased long-term thermooxidation stability. In terms of mechanical properties only impact strength well reflected the processing history. Tensile and flexural properties remained almost unchanged. The sizes of rubbery domains observed by SEM exhibited only minimum changes. The results of SSA and TREF techniques provided further data helping to elucidate the phenomena in rubbery phase. Based on indirect indications one could conclude that while typical polypropylene degradation resulting in chain backbone cleavage took place in the PP homopolymer phase, the rubbery phase containing EPR and PE homopolymer underwent a certain extent of crosslinking.
Journal of Applied Polymer Science, 2012
Four different grades of commercial, highimpact polypropylene (hiPP) were fractionated by temperature-gradient extraction fractionation, and the chain structure and melting behavior of the fractions were studied by Fourier transform infrared spectroscopy and differential scanning calorimetry. Furthermore, the morphology of the disperse phase in the resins was characterized by scanning electron microscopy of the microtome-cut etched and original samples. The results show that there was a strong relation between the chain structure, content, and distribution of the dispersed phase and the mechanical properties of hiPP. These parameters of the elastomeric phase are really critical in reaching the best rigidity-impact balance in hiPP. V
Origins of Product Heterogeneity in the Spheripol High Impact Polypropylene Process
Industrial & Engineering Chemistry Research, 2006
In the Spheripol process (Basell), high impact polypropylene (hiPP) is produced in two stages in series. First, isotactic polypropylene (i-PP) particles are produced in liquid propylene. These particles are transferred to a gas phase fluidized bed reactor where the elastomeric phase is produced within the isotactic polypropylene. The particulate product obtained in the commercial process is heterogeneous. This heterogeneity may be deleterious for the product performance. In this work, the origins of product heterogeneity were studied combining a detailed characterization of the product sampled from the exit lines of the homopolymerization stage (i-PP particles) and the fluidized bed reactor (hiPP particles) of a commercial unit with a mathematical model of the process. It was found that the experimental results were consistent with equally accessible active sites of uniform activity, the residence time distribution of the catalyst in the different reactors playing the major role in product heterogeneity.
Journal of Applied Polymer Science, 2012
In this article, the equilibrium morphology of a typical polypropylene (PP) impact copolymer (ICP) system is investigated by numerical self-consistent field simulations. The ICP was fractionated using temperature rising elution fractionation (TREF) to obtain the data necessary to define the simulation parameters. The results demonstrated the formation of a stratified droplet structure, in which ethylene content decreases from the center of the droplet toward the PP interface. This structure is shown to be in accordance with observations from transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. The components are confined to a narrow layer whose position is primarily determined by its ethylene content. Leakage into a neigh-boring layer occurs to a degree that is determined by the component molecular weight and the difference in ethylene content between the layers. Simulations for a range of droplet sizes enable calculation of the interfacial tension. A typical drawback of TREF involves the inability to fractionate the amorphous part, leading to a large difference in ethylene content between the matrix and its neighboring layers. Although this effect is shown not to have a significant influence on the stratified structure, it is shown to have a significant influence on the derived interfacial tension.
Phase separation and the kinetics of phase coarsening in commercial impact polypropylene copolymers
Journal of Polymer Science Part B: Polymer Physics, 1994
The phase segregation and subsequent minor phase coarsening of a commercial impact polypropylene copolymer was studied. The major components of the impact polypropylene copolymer studied were 82.4 wt % polypropylene homopolymer and 17.6 wt % ethylenepropylene rubber (EPR) . The system was artificially manipulated to ensure homogeneity by precipitation from solution with a nonsolvent. This ensured that the initial system did not exhibit large-scale phase segregation. The homogeneous initial system was subjected to storage in the melt at 193°C for a series of times. The two-phase morphology of commercial impact polypropylenes was generated in the melt state by storage in the melt for various periods of time from 5 s to 1 h. Small nuclei of particles appeared at short time and increased in volume with increasing time in the melt state. The coarsening of the minor phase EPR component was shown to follow the theoretically predicted d -t1I3 and Nt-' (where d = diameter, N = number of particles, and t = time in the melt) relationships to a close approximation in accord with Ostwald ripening theory. At short times these relationships were not obeyed. The indication was that the long-time coarsening regime was not entered until several minutes elapsed in the melt state. The particle size distribution was initially quite narrow and exhibited a trend of broadening at longer times of coarsening. This may be due to a shift from the short-time regime to the long-time coarsening regime. The initial polymer, which was precipitated from solution, was shown not to have undergone largescale phase segregation in that it exhibited a one-phase morphology (i.e., no particles with > 0.1 pm diameter) as determined by ' "Xe NMR spectroscopy. The precipitated blend produced incipient particle nuclei (> 0.1 pm diameter) after a very short time ( 5 s ) in the melt state.
Mechanical and morphological characterization of polypropylene toughened with olefinic elastomer
Materials Research-ibero-american Journal of Materials, 2000
The effect of incorporating (C2-C8) ethylene-octene elastomer on the mechanical properties and morphology of polypropylene copolymers has been investigated employing two types of PP copolymer, with and without nucleating agent. The results were compared to the ones presented by a commercial PP heterophase (reactor impact modified PP/EPR). The addition of the elastomer increases the toughness of the blends but reduces their stiffness. PP blends in the low elastomer content region (< 20%) show low values of the Izod impact strength and both, elastomer content and impact strength, are directly proportional to the area under the β damping peak or its maximum intensity of the elastomer. The morphology is a continuous pattern of segregate elastomeric particles with average particle size in the range of 0.27 µm to 0.39 µm. The average particle size and particle size distribution plotted in log-normal distribution curves, increases slightly with the increase in the elastomer content. The reactor modified PP heterophase has a broader particle size distribution and an average particle size of 0.56 µm, at the lower limit but inside the range for good impact performance, as observed.