Olefin polymerization and copolymerization
Mohsen Javaheri; Mehdi Nekoomanesh; Yousef Jahani
Abstract
The concentration of ethylene and 1-butene in n-hexane as polymerization media was calculated at five different pressure levels (4, 6, 8, 10, and 12 bar) and four different 1-butene concentrations (0.13, 0.26, 0.39, and 0.52 mol/L) in n-hexane at T= 80°C using the Peng-Robinson thermodynamic equation ...
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The concentration of ethylene and 1-butene in n-hexane as polymerization media was calculated at five different pressure levels (4, 6, 8, 10, and 12 bar) and four different 1-butene concentrations (0.13, 0.26, 0.39, and 0.52 mol/L) in n-hexane at T= 80°C using the Peng-Robinson thermodynamic equation of state. Some combinations of conditions were selected to perform the copolymerization reaction in the presence of an industrial TiCl4/MgCl2 Ziegler-Natta catalyst. The forms of the synthesized products were visually and qualitatively classified as either powder or sticky. The percentage of incorporated 1-butene comonomer into the polyethylene chains was analyzed using calibrated FTIR tests. It was shown that for ethylene/1-butene concentration ratios (β) in n-hexane above approximately 1.80, the product forms as a powder. For values below 1.30 threshold, the product was sticky. Thus, this ratio could be used as a criterion for selecting the proper combination of copolymerization pressure and 1-butene concentration when aiming to achieve a powdered form of the product. It was shown that β has a strong correlation with the weight percentage of 1-butene in the final LLDPE polymer. Therefore it can be used as an accurate prediction for wt.% of incorporated 1-butene into the LLDPE chain within the studied concentration ranges with the specific catalyst system utilized.
Polyolefins Functionalization
Mohammad Shahbazi; Yousef Jahani
Abstract
In this work, the grafting of maleic anhydride onto two types of linear low density polyethylene with hexene-1 comonomer (LLDPE-H1) and butene-1 comonomer (LLDPE-B1), in the presence of styrene monomer (St) and dicumyl peroxide initiator (DCP) has been studied. The combined influences of MAH, St and ...
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In this work, the grafting of maleic anhydride onto two types of linear low density polyethylene with hexene-1 comonomer (LLDPE-H1) and butene-1 comonomer (LLDPE-B1), in the presence of styrene monomer (St) and dicumyl peroxide initiator (DCP) has been studied. The combined influences of MAH, St and DCP on the grafting efficiency via a melt reactive mixing process have been investigated using response surface methodology and the central cubic design has been employed for experimental design and data analysis. IR spectroscopy, contact angle measurements and adhesion test have been used to evaluate the extent of grafting reaction. The results showed that LLDPE-H1 with a 2.2% maximum grafting content showed more grafting content than the LLDPE-B1 (1.86%). This effect could be attributed to the type of comonomer in LLDPE-H1 which made it more prone to chain scission than LLDPE-B1, and a higher level of grafting was achieved. The gel content measurement showed that lower cross-linked structure was formed during the grafting process in the LLDP-H1 than that in the LLDPE-B1. The optimum conditions of maximum grafting and minimum gel content were statically investigated. The optimum percentage of grafting for LLDPE-H1 was 1.82% and it was 1.74% for LLDPE-B1, with the minimum gel content of 6.5% and 9%, respectively. It was found that the amount of grafted percentage was sensitive to the concentrations of the MAH, DCP, and St, while the extent of the gel content was more sensitive to the percentage of DCP.
Characterization
Reza Poorghasemi; Yousef Jahani
Abstract
In this work, the compatibility and crystallinity of low density polyethylene (LDPE) and polybutene-1 (PB-1) blends were studied. Various blends of LDPE/PB-1 containing 5, 10 and 20 wt.% PB-1 were prepared in a corotating twin-screw extruder and characterized by scanning electron microscopy (SEM), shear ...
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In this work, the compatibility and crystallinity of low density polyethylene (LDPE) and polybutene-1 (PB-1) blends were studied. Various blends of LDPE/PB-1 containing 5, 10 and 20 wt.% PB-1 were prepared in a corotating twin-screw extruder and characterized by scanning electron microscopy (SEM), shear oscillation rheology and wide-angle X-ray diffractometry (WAXD). A matrix-droplet morphology was observed in SEM images, indicating incompatibility of the two polymers in the solid state. Compared to neat LDPE, the relaxation spectra of the blends were broadened, and a slight increase in their relaxation times was observed. The relaxation time of the blends was enhanced by increasing PB-1 content, which was further proved by fitting rheological data in the Carreau-Yasuda model. Deviation of Cole-Cole diagrams from circular shape means that the blend samples were not miscible and the positive-deviation behavior of the complex viscosity and storage modulus from the mixing rule revealed the formation of strong interfacial interactions. The crystallinity of both LLDPE and PB-1 was decreased as a result of blending. The peaks attributed to the form II of PB-1 crystals were eliminated and the peaks related to LDPE were obviously weakened, suggesting to prevent crystallinity of polymers which is associated with a reduction in the total crystallinity percentage for the blend. The reduction of crystallinity was more pronounced in PB-1 phase.
Polymer processing
Ali Foroozan; Tahereh Behboodi; Yousef Jahani
Abstract
In this study, the compatibility of the blends of polypropylene (PP) and polybutene-1(PB-1) homopolymer before and after long chain branching process were studied. The blends were prepared and long-chain branched directly via reactive extrusion process in presence of free radical initiator and trimethylolpropane ...
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In this study, the compatibility of the blends of polypropylene (PP) and polybutene-1(PB-1) homopolymer before and after long chain branching process were studied. The blends were prepared and long-chain branched directly via reactive extrusion process in presence of free radical initiator and trimethylolpropane tri methacrylate (TMPTMA) poly functional monomer. The optimum percentage of TMPTMA and PB-1 resin have determined by measuring the grafting efficiency and by studying the rheological behavior in shear steady state and transient extensional mode and the morphology of samples were investigated by scanning electron microscopy (SEM). Referring to the blends’ morphologies observed in SEM images which were approved by rheological data, it was found an enhanced compatibility in the blend by branching with 1.5wt% for TMPTMA and 10wt% for PB-1 resin. In this composition, the highest grafting efficiency of 37% and branch index of 5.2 achieved. The zero shear viscosity (η0) of PP is increased from 4500 Pa.s to 6800 Pa.s after branching process and enhanced more to 2400 Pa.s by using 10 wt% PB-1 resin. The Long-chain branched structure showed prominent higher zero-shear viscosity, longer relaxation time and pronounced strain-hardening behaviors. The branching behavior of samples were quantified by using extensional viscosity data and the branch index of samples were determined.
Structure and property relationship
Jalil Morshedian; Yousef Jahani; Farshad Sharbafian; Foroogh Sadat Zarei
Abstract
HDPE monofilaments were obtained using different extruders and drawn by post-extruder equipments. After solidification, drawn and undrawn monofilaments (draw ratio 7:1) were irradiated with 10 MeV electron beams in air at room temperature at 25, 50, 75, 100 and 125 kGy dose ranges to induce a network ...
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HDPE monofilaments were obtained using different extruders and drawn by post-extruder equipments. After solidification, drawn and undrawn monofilaments (draw ratio 7:1) were irradiated with 10 MeV electron beams in air at room temperature at 25, 50, 75, 100 and 125 kGy dose ranges to induce a network structure. HDPE crosslinking was studied on the basis of gel content measurements. The fibers were examined by differential scanning calorimetry (DSC) and measurements of mechanical properties.It was noted that gel fraction increased with irradiation dose up to 75 kGy and showed a significant increase with draw ratio, but at higher doses remained without considerable change. Melting temperature of drawn fiber increased with raising irradiation dose but decreased in undrawn sample. Also a bimodal endotherm peak was observed for drawn polyethylene irradiated in air.The changes in melting temperature and appearance of bimodal endotherm were related to the radiation chemistry of polyethylene in the presence of oxygen and interlamellar interactions. Heat of fusion and degree of crystallinity slightly increased for undrawn and drawn samples but, heat of crystallization was reduced by increasing irradiation dose due to increase the degree of crosslinking. Results of mechanical properties reveal that no significant changes seen in Young’s modulus by increasing irradiation dose. As a result of oxidative degradation happened by presence the oxygen molecules during the irradiation process, tensile properties of irradiated fibers decreased but elongation at yield for undrawn and elongation at break for drawn fibers boosted by increasing irradiation dose up to 125 kGy.
