Three procatalysts of the MgCl 2 /TiCl 4 type, differing mainly in their morphological characteristics, were investigated in ethylene polymerization and ethylene-1-butene copolymerization. Apparently, hydrogen has an intrinsic and general deactivating effect but it can also play an activating effect in homopolymerization. This peculiarity was found to be related to a catastrophic breakage of the polymer/catalyst particles during growth and thus to the exposure of new active centers. In this case the kinetic profiles are irregular and characterized by one or more secondary peaks which reflect the moment when this morphology-driven rate-enhancement effect takes place. In general, the prepolymerization of the procatalysts with propylene tends to slightly enhance homopolymerization rate, to slow down copolymerization rate and to stabilize the morphology of the growing polymer particles, thus preventing the occurrence of the irregular kinetic profiles observed during homopolymerization in the presence of hydrogen. The behavior of the procatalysts investigated was found to depend on the distribution of their pore size rather than the absolute values of their porosity. Likely this is due to an easier diffusion of the monomer and a more regular and homogeneous growth of the polymer within larger as opposed to smaller pores.
Biobased nanocomposites were manufactured through the melt intercalation of nanoclays and starch esters synthesized at the Fraunhofer Institute for Applied Polymer Research (TAP) from high amylose starch. Starch acetates (SAs) and starch propionates (SPs) were tested in combination with glycerol triacetate (triacetin) as a plasticizer for concentrations up to 30 and 20 wt %, respectively, with different types of organomodified and unmodified montmorillonites (MMTs). The mechanical properties of injection-molded test bars were determined by a tensile experiment giving the strength, modulus, and elongation of the composites. X-ray diffraction (XRD) analysis and transmission electron microscopy (TEM) were used to study clay dispersion and intercalation/exfoliation. Dynamic mechanical analysis was used to track the temperature dependence of the storage modulus and tan delta behavior of the starch/clay hybrid. Because they were the best performing compositions, SP with 5 wt % plasticizer and SA with 20 wt % plasticizer were filled with 5 wt % nanoclay. For SP, a certain increase in modulus was observed for all clays. However, the strength was practically unchanged, and the elongation decreased in most cases. One exception was found for the 2.5 wt % organomodified clay composition, where the elongation increased. For SA, the addition of 5 wt % nanoclay always increased the strength and modulus, in one case up to 60 and 75%, respectively. In the particular case with 5 wt % unmodified clay, the strength, modulus, and elongation increased by 30, 40, and 1000%, respectively. This was a dramatic improvement in the ductility of the material without losses in the strength and stiffness. XRD and TEM revealed the existence of exfoliated modified clay throughout the starch matrix, whereas for the unmodified case (with the exceptional increase in the elongation), no intercalation was observed
Activity, selectivity, and deactivation behavior of catalyst materials
determine their efficiency in hydrocarbon conversion processes. For
hydrocarbon cracking, the industrial catalyst is an important parameter
in reaction technology to produce valuable compounds,
e.g.
, light olefins (C
3
–C
5
) and gasoline
from crude oil fractions with high molecular weight (C
16+
). One strategy to enhance the catalytic activity for precracking
is increasing the matrix activity, which depends on the used binder
and additives. In this work, three binders (water glass, aluminum
chloride, and a mixture of colloidal silica with aluminum dihydrogen
phosphate) were used in combination with active zeolite Y, kaolin
as filler, and ZSM-5 as additive to produce composite materials. Specific
surface area and surface acidity measurements were combined with catalytic
testing of the formulated samples in order to find the relation between
the catalyst morphology and its activity. In addition, constraint
index was used as a control parameter for the determination of the
shape-selective properties and their correlation with the catalytic
activity. The results show that the binders determine the porosity
of the matrix and so the accessibility to zeolite pores and active
sites. Matrixes with low porosity and activity enhance coke production
and deactivate faster than matrixes with mesopores. Furthermore, ZSM-5
modifies the individual morphological and catalytic effects of the
binders. Everything considered, the small crystals of ZSM-5 together
with mesopores increase the olefins yield, reduce coking, and therefore
enhance the performance of the final grain.
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