Polyolefin blends
Mahsa Mobini-Dehkordi; Gholam-Reza Nejabat; Mohammad-Mahdi Mortazavi
Abstract
Varying amounts of a high molecular weight poly(1-hexene) (PH, Mv=1.7×106 Da) are substituted for EPDM in an iPP/iPP-g-MA/EPDM blend (weight ratio: 76:4:20) and mechanical properties as well as phase morphology of the blends are studied and compared. The results show that by substituting the entire ...
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Varying amounts of a high molecular weight poly(1-hexene) (PH, Mv=1.7×106 Da) are substituted for EPDM in an iPP/iPP-g-MA/EPDM blend (weight ratio: 76:4:20) and mechanical properties as well as phase morphology of the blends are studied and compared. The results show that by substituting the entire EPDM with PH, the tensile strength-at-break increases from 18.7 to 21.1 MPa, elongation-at-break increases from 15.5% to 370.8%, and impact strength increases from 6.4 to 50.1 kJ.m-2. Dynamic mechanical thermal analysis (DMTA) of the blends proved their immiscibility and SEM analysis confirmed these findings by showing droplet-matrix morphologies. Studying the creep behavior of the samples shows that the blends containing PH have more creep so that by substituting all EPDM in the blends with PH, the permanent deformation increases from 0.425% to 0.505%. According to the results, PH is introduced as a candidate for improving the impact properties of iPP/iPP-g-MA/EPDM blend.
Polyolefin degradation
Sara Zarei; Gholam-Reza Nejabat; Mohammad-Mahdi Mortazavi; Soheyl KhajehPour-Tadavani
Abstract
Varying amounts of an amorphous poly(1-hexene) (PH, Mv 1.7×106 Da) were added to an LLDPE matrix containing 3% w/w Addiflex oxo-biodegradable additive (HES-W) and extruded and converted into films. Then the effect of presence of PH was investigated on microstructure, thermal and tensile behavior ...
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Varying amounts of an amorphous poly(1-hexene) (PH, Mv 1.7×106 Da) were added to an LLDPE matrix containing 3% w/w Addiflex oxo-biodegradable additive (HES-W) and extruded and converted into films. Then the effect of presence of PH was investigated on microstructure, thermal and tensile behavior of polymer films before and after 6 weeks of ultra violet irradiation (UVR). Due to UVR, viscosity average molecular weight (Mv) of the sample without PH decreased from 9.6×104 to 4.6×103 Da and for the sample containing 3% w/w PH from 11.3×104 to 3.0×104 Da, also carbonyl index (CI) of the sample without PH increased from 0 to 28.7 while for the sample containing 3% w/w PH increased from 1.8 to 30.4. Moreover, differential scanning calorimetry (DSC) showed that crystallinity of the sample without PH increased from 34.4% to 36.9% and from 28.7% to 32.1% for the sample containing 3% w/w PH. Thermal gravimetric analysis (TGA) showed lower decomposition temperature for the samples containing PH. The elongation-at-break decreased from 723.0% to 88% for the sample without PH and from 410% to 10% for the sample containing PH. Atomic force microscopy (AFM) indicated smoother surfaces for samples containing 3% w/w PH before and after UVR. Although, the aforementioned results showed that the presence of limited amounts of PH in the LLDPE matrix deteriorated thermal and mechanical properties of the matrix, it hindered the oxo-biodegradablity of the matrix by opposing assimilation process perhaps due to high Mv and/or gelation.
Reaction engineering
Ali Ebrahimi; Saeid Ahmadjo; Mohsen Mohammadi; Mohammad-Mahdi Mortazavi; Mostafa Ahmadi
Abstract
Coordinative chain transfer polymerization (CCTP) has opened a new path for the development of novel products like olefin block copolymers and chain-end functional polyolefins. However, conflicting results are frequently reported on the catalyst performance including activity and comonomer selectivity ...
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Coordinative chain transfer polymerization (CCTP) has opened a new path for the development of novel products like olefin block copolymers and chain-end functional polyolefins. However, conflicting results are frequently reported on the catalyst performance including activity and comonomer selectivity under CCTP conditions. Here we have selected two catalysts including rac-ethylenebis(1-η5-indenyl)zirconocene and bis(imino) pyridine iron, with drastically different comonomer affinities. The effect of diethyl zinc as the chain transfer agent (CTA) on their individual performances is evaluated at different 1–hexene concentrations, in copolymerization with ethylene. Combined thermal fractionation and GPC results confirm that not all chains experience the reversible transfer reaction. Nevertheless, the metallocene catalyst shows twice activity and about 30% lower comonomer incorporation in the presence of CTA. Conversely, the late transition metal catalyst demonstrates lower activity and remains comonomer irresponsive. It could be concluded that, in addition to establishing a reversible transfer reaction, CTA affects the nature of active centers. This finding can help designing olefin copolymers with a more defined chemical composition based on CCTP reaction.
Polyolefin degradation
Soheyl Khajehpour-Tadavani; Gholam-Reza Nejabat; Mohammad-Mahdi Mortazavi
Abstract
Crystallinities of high-density polyethylene (HDPE) films containing various amounts of an oxo-biodegradable additive (HES-W) were investigated immediately after preparation and 6 weeks after ultraviolet (UV) irradiation (λ=254 nm). HDPE granules were mixed with oxo-biodegradable masterbatch in ...
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Crystallinities of high-density polyethylene (HDPE) films containing various amounts of an oxo-biodegradable additive (HES-W) were investigated immediately after preparation and 6 weeks after ultraviolet (UV) irradiation (λ=254 nm). HDPE granules were mixed with oxo-biodegradable masterbatch in a twin-screw extruder and the extrudates were converted into films with thicknesses of 35±5 micrometers. The films were exposed to UV light for 6 weeks. Crystallinities of the films are investigated by X-ray diffraction spectroscopy (XRD) and differential scanning calorimetry (DSC). The XRD results show that upon UV exposure, the crystallinities of the films enhance. The DSC thermograms have confirmed the XRD results and also show a decrease in melting points of the samples after UV exposure. Further investigations on viscosity average molecular weights (Mv) of the samples show that their Mv decrease sharply after UV exposure. Scanning electron microscopy (SEM) shows clear cracks on the samples surfaces after 6 weeks exposure to UV irradiation. Investigating the functionalities of the polymers through Fourier transform infrared spectroscopy (FTIR) show the emergence of carbonyl peaks after UV irradiation so that the carbonyl index of the samples increases. It is concluded that maximum oxo-biodegradation enhancement of the HDPE film samples can be achieved by using a specific amount of the oxo-compound (3 wt%); furthermore the crystallinities of the samples show considerable enhancement after UV exposure which can be due to better packing ability of low molecular weight chains along with probable dipole-dipole attractions between the carbonyl groups on different newly formed short polar chains.
Characterization
Mostafa Ahmadi; Seyed Mohammad Mehdi Mortazavi; Saeid Ahmadjo; Majid Zahmati; Khosrow Valieghbal; Davoud Jafarifar; Reza Rashedi
Abstract
Ethylene / 1-butene copolymers at different comonomer levels were synthesized using Ziegler-Natta catalyst to evaluate the applicability of thermal fractionation methods in predicting chemical composition distribution (CCD). The continuous melting endotherms by DSC were converted to continuous CCD, and ...
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Ethylene / 1-butene copolymers at different comonomer levels were synthesized using Ziegler-Natta catalyst to evaluate the applicability of thermal fractionation methods in predicting chemical composition distribution (CCD). The continuous melting endotherms by DSC were converted to continuous CCD, and the average comonomer contents were compared with NMR results. DSC underestimated comonomer content specifically at higher levels and was more sensitive to the drawn baseline. The thermally fractionated melting endotherms by SSA method were deconvoluted and transformed into discrete CCDs. SSA method underestimated average comonomer content even more, however results were more reproducible. The main shortcoming of the thermal methods was the inability of short ethylene sequences in forming discernible lamella thicknesses at high comonomer levels. Calibration curves were created for converting the predicted comonomer contents into absolute values and used for studying industrial LLDPEs with different comonomer levels. It was shown that SSA provides more reliable results and correlates more reasonably to the measured densities.
Catalysis
Gholam-Reza Nejabat; Mehdi Nekoomanesh; Hassan Arabi; Hamid Salehi-Mobarakeh; Gholam-Hossein Zohuri; Mohammad-Mahdi Mortazavi; Saeid Ahmadjo; Stephen A. Miller
Abstract
Several types of hybrid catalysts are made through mixing of 4th generation Ziegler-Natta (ZN) and (2-PhInd)2ZrCl2 metallocene catalysts using triethylaluminum (TEA) as coupling agent. Response surface methodology (RSM) is used to evaluate the interactive effects of different parameters including ...
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Several types of hybrid catalysts are made through mixing of 4th generation Ziegler-Natta (ZN) and (2-PhInd)2ZrCl2 metallocene catalysts using triethylaluminum (TEA) as coupling agent. Response surface methodology (RSM) is used to evaluate the interactive effects of different parameters including amounts of metallocene and TEA and temperature on metallocene loading. Analyzing the amounts of Al and Zr elements in the hybrid catalysts through ICP-OES and EDXA reveals that temperature plays a crucial role on anchoring of the metallocene catalyst on ZN while TEA has the least determining effect. The ICP analysis shows that as the concentration of Al goes up in the hybrid catalyst the concentration of Zr passes a maximum, while EDXA shows a direct relationship between the Al and Zr contents. Using triisobutylaluminum (TIBA) and methylaluminoxane (MAO) as the coupling agents, almost similar metallocene loadings are observed. Finally, the performance of hybrid catalysts is investigated in propylene polymerization and the obtained polymers are characterized using DSC and DMTA through which the presence of two types of polymers in the final product are confirmed.
