Olefin polymerization and copolymerization
Majedeh Mroofi; Gholamhossein Zohuri; Saeid Ahmadjo; Navid Ramezanian
Abstract
Bicenter (BCn) cobalt-bis(imine) catalysts were synthesized, used to polymerize methyl methacrylate (MMA), and 1-hexene. The effect of catalyst structure, bridging ligand, and polymerization reaction conditions were investigated. Synthesis of primary ligand of (2,6-dibenzhydryl-4-ethoxyphenyl)-N=(CH3)-C(CH3)=O ...
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Bicenter (BCn) cobalt-bis(imine) catalysts were synthesized, used to polymerize methyl methacrylate (MMA), and 1-hexene. The effect of catalyst structure, bridging ligand, and polymerization reaction conditions were investigated. Synthesis of primary ligand of (2,6-dibenzhydryl-4-ethoxyphenyl)-N=(CH3)-C(CH3)=O is prepared. Following to that, the final ligands of BC1 and BC2 bicenter catalysts were prepared via reacting the primary ligand with 2,3,5,6-tetramethylbenzene-1,4-diamine and 4,4-methylenedianiline bridges, respectively. The BC1 catalyst demonstrated higher activity than the BC2 catalyst. The highest activity for the BC1 catalyst was obtained when the co-catalyst to catalyst molar ratio was [Al]/[Co]=1500:1, and the polymerization temperature was 40 °C. In comparison the BC2 catalyst demonstrated the highest activity in [Al]/[Co]=500:1 ratio, polymerization temperature of 70 °Cand showed higher thermal stability. 1HNMR analysis revealed that the highest branching density for poly(methyl methacrylates) (PMMA) produced by BC1 and BC2 catalysts was 222 and 249 branches per 1000 carbon atoms, respectively. PMMA synthesized with BC2 catalysts had the highest syndiotacticity (59%). The polymer produced with bicenter catalyst (BC1) had a relatively broad molecular weight distribution (2.9), according to GPC analysis. The synthesized catalysts demonstrated appropriate activity for the polymerization of MMA, but only moderate activity for 1-hexene monomer
Characterization
Mehri Dana; Gholam Hossein Zohuri; Navid Ramezanian; Saeid Asadi Shahidi; Sohail Yazdanbakhsh
Abstract
Silane cross-linking of metallocene-based polyethylene-octene elastomer (POE)/linear low density polyethylene (LLDPE) blend was carried out using two-step Sioplas process in an industrial scale twin-screw extruder. In the study, grafting and cross-linking reactions of vinyl trimethoxy silane (VTMS) were ...
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Silane cross-linking of metallocene-based polyethylene-octene elastomer (POE)/linear low density polyethylene (LLDPE) blend was carried out using two-step Sioplas process in an industrial scale twin-screw extruder. In the study, grafting and cross-linking reactions of vinyl trimethoxy silane (VTMS) were analyzed using FTIR technique. It was found that the cured compound showed absorption peaks at 1078 cm-1 and 955 cm-1 related to Si-O-Si bonds. A peak was also observed at 3405 cm-1 of hydroxyl group produced from hydrolysis of methoxyethylene group during of curing process, reflecting that curing reaction was not completed. The samples were cured at different time intervals (15 min-16 hours). The gel content values determined by solvent extraction and FTIR were in good agreement at curing times more than 4 hours. The efficiency of the silane grafting reaction was determined using the ratio of the absorption peak at 1092 cm-1 characteristic of methoxy to the transmittance peak at 1378 cm-1 characteristic of methyl group, which is considered as the internal standard. The results showed the highest efficiency of silane grafting reaction at 5 w% of VTMS with the least amount of internal standard ratio (0.029), at which the lowest MFI value, and the highest values for gel content, tear strength, compression set and hot set 200 °C were obtained.
Polymeric foams
Mohammad Nourmohammadi; Reza Jahanmardi; Hamid Moeenfard; Gholamhossein Zohuri; Saeed Bazgir
Abstract
Novel EPDM-based polymer foams were prepared using a combination of nanomaterials, namely nano silica, nano clay, and graphene nanoplatelets. In order to achieve optimal acoustic performance, the Taguchi design (TD) technique was applied to reduce the number of experiments and optimize the formulation. ...
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Novel EPDM-based polymer foams were prepared using a combination of nanomaterials, namely nano silica, nano clay, and graphene nanoplatelets. In order to achieve optimal acoustic performance, the Taguchi design (TD) technique was applied to reduce the number of experiments and optimize the formulation. By employing an orthogonal array of L9(34), four controlled factors, including content of the three nanomaterials and the blowing agent (Unicell D200A), were chosen. In practice, the acoustic properties of the nine suggested experiments with TD were examined with an impedance tube, and the signal-to-noise ratio analysis revealed two more optimal formulations for foam composites. Further experiments for the last two formulations compared to the nine Taguchi tests, showed an improvement of 13.04 and 19.68%, respectively, for noise reduction coefficient (NRC) and average transmission loss (ATL). It seemed that the idea of using multiple nanomaterials simultaneously is to be an effective way. Besides, the SEM images of nine samples proved that the smaller cell size of the foam were achieved using the higher concentration of nanoparticles. These findings are in accordance with the acoustic results, as the sample with larger cell size and more open cells (C3) showed higher NRC and the sample with larger cell size and closed cells (B2) showed higher ATL values. To complete the study, some blank samples with zero level or only one type of the nanomaterial were also investigated. Interestingly, the obtained results indicated that the formula should contain more than one type of nanoparticle to achieve a better acoustic performance. Comparing the result obtained in this study for EPDM foam with the same EVA foam in our previous work, it can be seen that EPDM showed an increase of 15.56% in NRC and a slight decrease of 2.5% in ATL. This behavior could be due to the difference in their morphology, in which the EPDM has probably more open cells and thinner cell walls.
Catalysis
Majedeh Maroofi; Gholam Hossein Zohuri; Saeid Ahmadjo; Navid Ramezanian
Abstract
A mono-nuclear catalyst of bis-imine cobalt (MC) was synthesized with using 2,6-dibenzhydryl-4-ethoxy phenyl as a ligand. The so huge ligand was prepared via the reaction of 2,6-dibenzhydryl-4-ethoxy phenyl)-N=(CH3)-C(CH3)=O with diacetyl with equal mole stoichiometry in presence of formic acid catalysis. ...
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A mono-nuclear catalyst of bis-imine cobalt (MC) was synthesized with using 2,6-dibenzhydryl-4-ethoxy phenyl as a ligand. The so huge ligand was prepared via the reaction of 2,6-dibenzhydryl-4-ethoxy phenyl)-N=(CH3)-C(CH3)=O with diacetyl with equal mole stoichiometry in presence of formic acid catalysis. The catalyst was synthesized via a reaction between the ligands and cobalt salt (CoCl2). The catalyst was used for polymerization of methyl methacrylate (MMA), (a polar monomer) in the presence of modified methylaluminoxane (MMAO). The highest polymerization activity (8.6 g PMMA/mmol cat. h) was obtained at [cocatalyst]/[catalyst]=1000:1 molar ratio and at room temperature reaction. For the prepared PMMA, Polymer with branching density of 263/1000C was obtained using 1H NMR technique calculation. The microstructure of one of the produced PMMA was as follow: 48% syndiotactic, 29% isotactic and 23% atactic. GPC analysis of the polymer showed a number average molecular weight of about 5.7 × 105 g/mol and a narrow molecular weight distribution of 1.57.
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.
Catalysis
G. Hossein Zohuri; Saman Damavandi; Saeid Ahmadjo; Reza sandaroos; Mohammad A. Shamekhi
Abstract
A FI Zr-based catalyst of bis[N-(3,5-dicumylsalicylidene)-2′,6′diisopropylanilinato]zirconium(IV) dichloride was prepared and used for polymerization of ethylene. The effects of reaction conditions on the polymerization were examined in detail. The increase in ethylene pressure and rise ...
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A FI Zr-based catalyst of bis[N-(3,5-dicumylsalicylidene)-2′,6′diisopropylanilinato]zirconium(IV) dichloride was prepared and used for polymerization of ethylene. The effects of reaction conditions on the polymerization were examined in detail. The increase in ethylene pressure and rise in polymerization temperature up to 35 oC were favorable for catalyst/MAO to raise the catalytic activity as well as the viscosity-average molecular weight (Mv) of polyethylene. The activity of the catalyst was linearly increased with increasing MAO concentration and no optimum activity was observed in the range studied. Although introduction of the bulky cumyl and 2′,6′-diisopropyl alkyl substitution groups on ortho positions to the phenoxy-oxygen and on phenyl ring on the N, respectively enhanced the viscosity average molecular weight (Mv) of the obtained polymer strongly, diminished the activity of the catalyst. Neither the activity of the catalyst nor the (Mv) of the obtained polymer were sensitive to hydrogen concentration. However, higher amount of hydrogen could slightly increase the activity of the catalyst. The (Mv) of polyethylene ranged from 2.14×106 to 2.77×106 at the monomer pressure of 3 and 5 bar respectively which are much higher than that of the reported FI Zr-based catalysts.
