Structure and property relationship
Alireza Nikfarjam; Roham Rafiee; Mostafa Taheri
Abstract
Isolated carbon nanotubes (CNTs), CNT films and CNT-polymer nanocomposites are a new generation of materials with outstanding mechanical, thermal, electrical and electromagnetic properties. The main objective of this article is to provide a comprehensive review on the investigations performed in the ...
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Isolated carbon nanotubes (CNTs), CNT films and CNT-polymer nanocomposites are a new generation of materials with outstanding mechanical, thermal, electrical and electromagnetic properties. The main objective of this article is to provide a comprehensive review on the investigations performed in the field of characterizing electrical and electromagnetic properties of isolated CNTs and CNT-reinforced polymers either theoretically or experimentally. The results reported in literature are reviewed and evaluated based on employed and/or developed methods by focusing on the electrical conductivity, permittivity and permeability properties. Available analytical and numerical simulations for predicting electrical properties of CNT-based composites are also reviewed. Besides, equivalent circuit modeling of nanocomposites containing CNTs is presented. The influence of effective parameters on overall electrical and electromagnetic characteristics of CNT-reinforced polymers is discussed based on published data. Therefore, highlighting the recent trends and challenges engaged in new investigations, those aspects which are required to be more deeply explored are introduced.
Polyolefin degradation
Zaher Tamri; Ali Vaziri Yazdi; Mehdi Nekoomanesh Haghighi; Mehrdad Seifali Abbas-Abadi; Amir Heidarinasab
Abstract
Pyrolysis of high impact polystyrene (HIPS) waste has been investigated under different process parameters, such as temperature, heating rate and types of zeolitic catalysts to produce valuable liquid products. Liquid, gas and coke as products of pyrolysis and aromatic, naphthene, olefin and paraffin ...
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Pyrolysis of high impact polystyrene (HIPS) waste has been investigated under different process parameters, such as temperature, heating rate and types of zeolitic catalysts to produce valuable liquid products. Liquid, gas and coke as products of pyrolysis and aromatic, naphthene, olefin and paraffin as liquid components were obtained and their molecular weight distributions were studied with changing the process parameters in a stirred reactor. Aromatic-rich hydrocarbons within the gasoline range were the main pyrolysis products. Type of zeolitic catalysts, temperature and heating rate had significant effects on the products quality and quantity. Non-isothermal mass losses of high impact polystyrene were measured using a thermo-gravimetric analyzer (TGA) at heating rates of 5, 15, 30, 45 and 90°C min-1 until the furnace wall temperature reached 600°C. The DTG (differential thermal gravimetric) curves showed that heating rate had no obvious effect on the degradation trends in the studied range, and by increasing heating rate, the activation energies were decreased obviously from 222.5 to183.6 kJ mol-1.
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.
Reaction engineering
Nickolay Ostrovskii; Ladislav Fekete
Abstract
The olefins polymerization process in a slurry reactor is discussed. The reaction rate dynamics was analyzed and the contributions of feed flow, gas-liquid mass transfer, polymerization reaction, and catalyst deactivation were estimated. The propylene solubility in a solvent mixture “heptane” ...
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The olefins polymerization process in a slurry reactor is discussed. The reaction rate dynamics was analyzed and the contributions of feed flow, gas-liquid mass transfer, polymerization reaction, and catalyst deactivation were estimated. The propylene solubility in a solvent mixture “heptane” was calculated using Soave-Redlich-Kwong equation of state. These data were then approximated by Henry-like equation and the results were verified in experiments. The influence of propylene dissolving in ”heptane which was examined in special experiments without catalyst has provided the independent estimation of gas-liquid mass transfer coefficient. It has been shown that the reaction rate during the first 20-30 min of test is much lower (or higher) than total monomer consumption, depending on reactant addition sequence. The method of kinetic experiments interpretation and corresponding mathematical model are proposed. The method enables to estimate the kinetic parameter of monomer dissolution, the reaction rate constant of polymerization, as well as the parameters of active centers transformation – activation, deactivation and self-regeneration. An adequacy of model was proved by the description of experiments at two different pressures but with the same parameters values.
Polyolefin degradation
Larissa Stieven Montagna; Ana Paula Testa Pezzin; Maria Madalena Forte; Ruth Marlene Santana
Abstract
In abiotic degradation the action of light radiation is one of the most important parameters, because polymers undergo degradation due to the action of light (natural or artificial). The aim of this study was to investigate the degradation rate for samples of polypropylene (PP) modified with an organic ...
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In abiotic degradation the action of light radiation is one of the most important parameters, because polymers undergo degradation due to the action of light (natural or artificial). The aim of this study was to investigate the degradation rate for samples of polypropylene (PP) modified with an organic pro-degradant submitted to ageing in a natural environment and to accelerated ageing test. The degradation behavior of the samples exposed to the ageing processes was evaluated through changes in the degree of crystallinity (Xc ), surface morphology (Scanning Electron Microscopy) and molecular weight. The results indicated that for the modified polypropylene samples natural ageing led to a 42.3% reduction in the molecular weight and the surface morphology showed evidence of erosion. In the accelerated ageing process the UV radiation was stronger, which led to a 94.3% increase in the degree of crystallinity and micro-voids were present on the surface of the modified polypropylene.
Olefin synthesis
Salman Beyraghi; Mohammad Rostamizadeh; Reza Alizadeh
Abstract
Methanol dehydration is a high potential route for the production of light olefins (C2-C4). In this study, hierarchical Si-rich [B]-ZSM-5 catalysts (Si/Al= 200) were prepared through one-pot hydrothermal synthesis, including boron as a promoter and ethanol as a low-cost secondary template. N2 adsorptiondesorption, ...
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Methanol dehydration is a high potential route for the production of light olefins (C2-C4). In this study, hierarchical Si-rich [B]-ZSM-5 catalysts (Si/Al= 200) were prepared through one-pot hydrothermal synthesis, including boron as a promoter and ethanol as a low-cost secondary template. N2 adsorptiondesorption, XRD, FE-SEM, and FT-IR techniques were applied to characterize the catalysts. The effect of different amounts of ethanol and different operating conditions was studied on the ZSM-5 catalyst preparation and performance in methanol-to-olefins (MTO) reaction. The results showed that the optimum amount of ethanol (ethanol/TPABr=5) led to the highest crystallinity (91.2%), the highest specific surface area (>400 m2g-1), and total pore volume (0.19 cm3g-1). The best catalytic performance was obtained at temperature of 480°C and methanol hourly space velocity (WHSV) of 7.2 h-1. The optimum catalyst had the highest propylene selectivity (58%) and light olefin selectivity (85%). The results proved the high capability of the new strategy for the efficient and fast development of the MTO catalyst.
Polymer processing
Moammadreza Nakhaei; Ali Ahmadi; Ghasem Naderi
Abstract
Polyamide 6 / nitrile butadiene rubber / nanoclay (PA6/NBR/clay) nanocomposite has gathered wide acceptance in industry. Laser welding, as a fabrication method, is applied to welding of polymer nanocomposites. In this study, the input parameters (clay (Closite 30B) content, laser power, scan velocity ...
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Polyamide 6 / nitrile butadiene rubber / nanoclay (PA6/NBR/clay) nanocomposite has gathered wide acceptance in industry. Laser welding, as a fabrication method, is applied to welding of polymer nanocomposites. In this study, the input parameters (clay (Closite 30B) content, laser power, scan velocity and stand-off-distance) are varied to achieve the best responses (tensile strength of welds). Response surface methodology (RSM) is utilized to investigate the effect of input parameters on mechanical properties. Morphology and tensile properties of nanocomposites were observed with scan electron microscopy (SEM), transmission electron microscopy (TEM) and tensile test. The results demonstrated that increasing the clay content from 1 to 5%wt and stand-off-distance from 4 to 8 mm decreased tensile strength of welds about 15% and 5%, respectively. The tensile strength of PA6/NBR composite is 25.6, whereas the prediction models showed that under optimal conditions of laser power of 105 W, scan velocity of 300 mm/min and stand-off-distance of 4 mm, the maximum tensile strength of PA6/NBR nanocomposite with 1, 3 and 5 % nanoclay are 27.2 MPa, 27.6 MPa and 24.7 MPa, respectively. These tensile strengths are about 99, 89 and 73% of the strength of these nanocomposites before welding.
Catalysis
Haif Alshammari; Helmut G. Alt
Abstract
A series of dissymmetric dinuclear complexes were synthesized, as dual site catalysts in ethylene polymerization, by coupling the allylated a-diimine complexes of the metals Ti, Zr, V, Ni and Pd with the ansa-zirconocene complex [C5H4-SiH(Me)-C5H4]ZrCl2 possessing a hydride silane moiety. The different ...
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A series of dissymmetric dinuclear complexes were synthesized, as dual site catalysts in ethylene polymerization, by coupling the allylated a-diimine complexes of the metals Ti, Zr, V, Ni and Pd with the ansa-zirconocene complex [C5H4-SiH(Me)-C5H4]ZrCl2 possessing a hydride silane moiety. The different stages of syntheses included the formation of bis(cyclopentadienide)methyl silane which was utilized to prepare the silyl-bridged zirconocene complexes. The dinuclear complexes were prepared by mixing the latter complexes with allylated alpha-diimine via a hydrosilylation reaction using the Karstedt catalyst, platinum (0)1,3 divinyl-1,1,3,3,-tetramethyldisiloxane to react at room temperature for 40 h. These dinuclear complexes were activated with methylaluminoxane (MAO) and tested for the polymerization of ethylene. The dinuclear catalysts showed various activities depending on the nature of the metals and produced polyethylenes with broad or bimodal molecular weight distributions. The trend in polymerization activities was: Ni>Pd>V>Zr>Ti. The ethylene polymerization activities of the dinuclear catalysts were almost double the activities of their analogous alpha-diimine precursors.
Polyolefin degradation
Abbas Kebritchi; Mehdi Nekoomanesh; Fereidoon Mohammadi; Hossein Ali Khonakdar
Abstract
In this work, the role of comonomer content of 1-hexene-medium density polyethylene (MDPE) copolymer, synthesized using Phillips catalyst, on thermal behavior parameters such as: crystallization, melting temperature and thermal degradation was investigated in detail. The copolymer was fractionated to ...
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In this work, the role of comonomer content of 1-hexene-medium density polyethylene (MDPE) copolymer, synthesized using Phillips catalyst, on thermal behavior parameters such as: crystallization, melting temperature and thermal degradation was investigated in detail. The copolymer was fractionated to homogenous short-chain branching (SCB) fractions by "preparative temperature rising elution fractionation" (P-TREF) method and then it was subjected to thermal analyses. A broad chemical composition distribution (CCD) in terms of SCB content and molecular weight (Mw) was observed by P-TREF and gel permeation chromatography (GPC), respectively. Based on P-TREF results, a parabolic relationship between methylene sequence length (MSL) and elution temperature (ET) was presented. Differential scanning calorimetry (DSC) showed distinct, well-defined melting peaks over a 22 °C temperature range for SCB contents of about 3-12 (br/1000 C). The variations in physical characteristics such as melting temperature (Tm), crystallinity (Xc), crystallization temperature (Tc) and lamellae thickness (Lc) against SCB content were correlated. Thermogravimetric analysis (TGA) suggested linear relationships between the temperature at maximum degradation rate (Tmax) as well as the degradation initiation temperature (T5%) versus SCB content. Moreover, the TGA curves exhibited distinct differences at both initiation and propagation stages of thermal degradation at dissimilar comonomer contents.
Ali Behboudi; Yoones Jafarzadeh; Reza Yegani; Ali Akbari
Abstract
Grinded glass fiber (GGF) embedded high density polyethylene (HDPE) membranes were prepared via thermally induced phase separation method. FESEM images showed that all the membranes had leafy structure, indicating a solid-liquid mechanism during phase separation. The results of EDX and TGA analyses confirmed ...
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Grinded glass fiber (GGF) embedded high density polyethylene (HDPE) membranes were prepared via thermally induced phase separation method. FESEM images showed that all the membranes had leafy structure, indicating a solid-liquid mechanism during phase separation. The results of EDX and TGA analyses confirmed that the fibers were dispersed in the HDPE matrix uniformly. Normalized water flux of the membranes increased from 1 for the neat HDPE membrane to more than 4 for 10 wt% GGF/HDPE membrane. Moreover, the contact angle decreased from 129° to 94° as the GGF content increased in the membranes, showing an improvement in the surface hydrophilicity of the membranes. The AFM results revealed that the surface roughness of the membranes was increased with increasing the GGF content. The results of abrasion test revealed that the GGF/HDPE membranes had a more abrasion resistance than the neat HDPE membrane. Finally, the fouling behavior of the membranes was investigated by the filtration of BSA protein solution and the results showed that with increasing the glass fiber content, total fouling ratio decreased from 90% for the neat HDPE membrane to 62% for 10 wt% GGF/HDPE membrane, indicating that the antifouling properties of the membranes were improved due to the presence of glass fiber.
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.
Nanoth Rasana; Karingamanna Jayanarayanan
Abstract
Nano, micro and hybrid filler-reinforced polypropylene (PP) composites were prepared via melt compounding technique using a twin screw extruder. The nano scale MWCNTs and micro scale glass fibers were used as reinforcements. In addition to the individual effect of nano and micro scale reinforcements ...
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Nano, micro and hybrid filler-reinforced polypropylene (PP) composites were prepared via melt compounding technique using a twin screw extruder. The nano scale MWCNTs and micro scale glass fibers were used as reinforcements. In addition to the individual effect of nano and micro scale reinforcements in virgin PP, the dual effect of multiscale (MWCNT/glass fiber) fillers was also elucidated. Morphological images revealed the effectiveness of dispersion of the fillers in the matrix and it was observed that the functionalized composites showed increased filler dispersion. The static mechanical properties of the non-functionalized and functionalized samples were compared and the hybrid composite with 2 wt.% MWCNTs showed the highest tensile strength without modulus reduction. The strong bonding between carboxyl-treated MWCNTs and maleic anhydride-grafted PP was well revealed in the FTIR spectra. In hybrid composites, the effect of silane-treated glass fibers was revealed and the siloxane linkages occurred between the glass fiber surface and silanol groups were confirmed by the FTIR spectra.
Characterization
Tao Zheng; Qian Li; Qian Zhou; Huayi Li; Qian Xing; Liaoyun Zhang; Youliang Hu
Abstract
9,10-Dihydro-9,10-ethano-anthracene-11,12-dicarboxylic acid disodium salt (DHEAS) was synthesized and used as a nucleating agent for poly(1-butene) (iPB). The isothermal crystallization kinetics of iPB having different nucleating agents were investigated by differential scanning calorimetry (DSC) and ...
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9,10-Dihydro-9,10-ethano-anthracene-11,12-dicarboxylic acid disodium salt (DHEAS) was synthesized and used as a nucleating agent for poly(1-butene) (iPB). The isothermal crystallization kinetics of iPB having different nucleating agents were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The results showed that the nucleating agents increased the crystallization temperature and the crystallization rate and shortened the crystallization half-time (t1/2). As well, the nucleating agents could be used as heterogeneous nuclei in the iPB matrix and decreased the size of iPB. When the nucleating agent was DHEAS, the crystallization temperature of iPB was up to 93.6°C which was higher than that of other nucleating agents for iPB and pure iPB. The crystallization half-time in the presence of DHEAS was 0.58 min which was less than that of other nucleating agents for iPB and pure iPB. In this case, the spherulitic size of iPB was the smallest and the morphology was changed, which indicated that DHEAS displayed better nucleation effect among the studied nucleating agents.
Polyolefin degradation
Mehrdad Seifali Abbas-Abadi; Mehdi Nekoomanesh Haghighi; Armando G. McDonald; Hamid Yeganeh
Abstract
Pyrolysis of low density polyethylene (LDPE) by equilibrium fluid catalytic cracking (FCC) was studied in a stirred reactor under different process parameters. In this work, the effect of process parameters such as degradation temperature (420-510°C), catalyst/polymer ratio (0-60%), carrier gas type ...
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Pyrolysis of low density polyethylene (LDPE) by equilibrium fluid catalytic cracking (FCC) was studied in a stirred reactor under different process parameters. In this work, the effect of process parameters such as degradation temperature (420-510°C), catalyst/polymer ratio (0-60%), carrier gas type (H2, N2, ethylene, propylene, Ar and He), residence time and agitator speed (0-300 rpm) on the condensate yield (liquid, gas and coke) and product composition were considered. Reaction products were determined by GC analysis and shown to contain naphthenes (cycloalkanes), paraffins (alkanes), olefins (alkenes) and aromatics. Higher temperature and more catalyst amount enhanced LDPE cracking. The maximum “fuel like” condensed product yield was attained at 450°C and 10% catalyst, respectively and gaseous products increased with increases in temperature. Hydrogen as a reactive carrier gas increased the condensed and paraffinic product yield. Appropriate heat transfer (by stirring) increased the catalyst efficiency in a stirred reactor.
Polymer processing
Milad Moradian; Taher Azdast; Ali Doniavi
Abstract
Polyolefins have been widely used in the electrical insulation and cable industry in recent years. One of the main usages of these materials is dielectric insulation in coaxial cables. Low attenuation and high signal transmission speed are among the desired features in coaxial cables. The role of polyethylene ...
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Polyolefins have been widely used in the electrical insulation and cable industry in recent years. One of the main usages of these materials is dielectric insulation in coaxial cables. Low attenuation and high signal transmission speed are among the desired features in coaxial cables. The role of polyethylene foam on signal transmission speed in the coaxial cables is the main focus of this study. In the present study, the velocity factor of coaxial samples with different dielectric structures is investigated in both theoretical and experimental approaches. In theoretical formulation, only the void fraction of foam is taken into consideration and other foam properties such as cell density, cell size, and foam structure are neglected. This is the reason for the difference observed between theoretical and experimental results. In theoretical results, a linear increase in the velocity factor is witnessed with the increase of the void fraction while in experimental results there are some exceptions. The foaming degree of the samples was reached 63% causing a 37.7% decrease in theoretical relative permittivity and consequently a 26.8% increase in theoretical velocity factor. On the other hand, up to 36% increase is observed in the experimentally measured velocity factor of foamed dielectric samples compared to the samples with solid polyethylene dielectric.
Simulation & Modeling
Rezvan Yavari; Hamid Khorsand; Mehran Sardarian
Abstract
During the recent years powder processing technologies have gained much attention due to the less energy consumption and recyclable powders. Manufacturing of complicated parts by the conventional powder metallurgy (PM) method is hard due to the uniaxial pressure, which leads to the low design flexibility. ...
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During the recent years powder processing technologies have gained much attention due to the less energy consumption and recyclable powders. Manufacturing of complicated parts by the conventional powder metallurgy (PM) method is hard due to the uniaxial pressure, which leads to the low design flexibility. In order to prevail these constraints, powder injection molding (PIM) process, which includes powder metallurgy and injection molding processes, is introduced. In powder injection molding, simulations are a very useful tool to predict each step of process and design the mold. By this way, design can already be optimized and mistakes are avoided. In this review a detailed study of simulation of different steps in the powder injection molding process of macro and micro components produced by this method is presented. Simulation investigations of mixing, injection, debinding, and sintering of various researchers are given. The computer simulation tools available for all steps of the PIM process are surveyed and results are presented.
Polymer processing
Fatemeh Hassan; Mehdi Entezam
Abstract
Irradiation of polymers is one of the most effective and economical methods for modifying their properties and for changing their applications. In this study, an extrusion grade polypropylene (PP) was treated by electron beam irradiation to produce a PP suitable for injection molding. Irradiation was ...
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Irradiation of polymers is one of the most effective and economical methods for modifying their properties and for changing their applications. In this study, an extrusion grade polypropylene (PP) was treated by electron beam irradiation to produce a PP suitable for injection molding. Irradiation was carried out at different doses (0-80 kGy) under atmosphere air and at ambient temperature. Melt flow index (MFI) measurements showed PP samples irradiated in the range of 10 to 40 kGy are suitable to use in injection molding. Electron beam irradiation decreased the viscosity and the shear thinning rheological behavior of PP. The differential scanning calorimetry (DSC) analysis revealed that electron beam irradiation increased the crystallinity percentage and temperature of PP, but decreased the melting temperature. Among all treated samples, the PP20, irradiated at the dose of 20 kGy, showed the highest impact resistance. It had higher Young’s modulus and tensile strength, but lower elongation-at-break in comparison with untreated PP.
Catalysis
He-Xin Zhang; Seung-Ri Lee; Dong-Ho Lee; Xue-Quan Zhang; Keun-Byoung Yoon
Abstract
Despite the great potential of graphene as a nanofiller, achieving homogeneous dispersion remains the key challenge for effectively reinforcing polyolefin (such as polyethylene (PE) and polypropylene (PP)) nanocomposites. Therefore, in this research, we report a facile combined in situ polymerization ...
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Despite the great potential of graphene as a nanofiller, achieving homogeneous dispersion remains the key challenge for effectively reinforcing polyolefin (such as polyethylene (PE) and polypropylene (PP)) nanocomposites. Therefore, in this research, we report a facile combined in situ polymerization and masterbatch method for fabricating PP/reduced graphene oxide (rGO) nanocomposites. In the polymerization stage, the synthesized catalyst exhibited a very high activity toward propylene polymerization, while the resultant PP/rGO with a very high isotactic index (I.I. = 99.3), broad molecular weight distribution (Mw/Mn = 14.9), and thermal stability was produced. After meltblending with commercial PP, a significantly increased modulus along with no observable change in tensile strength and elongation-at-break were achieved via the addition of a very small amount of rGO; these properties resulted from the suitable dispersion and good interface adhesion of the graphene sheet and PP matrix. Thus, this work provides a method for production of high performance PP.
Catalysis
Hongfan Hu; Rongqing Ma; Chenxi Cui; Guoliang Mao; Shixuan Xin
Abstract
Due to the large ionic radius and high electro-positivity nature, rare earth metal complexes are difficult to stabilize and undergo pathways like ligand redistribution and intramolecular C-H activation. To solve such problems and retain reactive versatility, rare earth complexes supported by a variety ...
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Due to the large ionic radius and high electro-positivity nature, rare earth metal complexes are difficult to stabilize and undergo pathways like ligand redistribution and intramolecular C-H activation. To solve such problems and retain reactive versatility, rare earth complexes supported by a variety of tridentate PNP pincer ligands have been explored. Such complexes can serve as perfect precursors for preparing ultra-active rare earth species containing two metal-carbon bands, let alone Ln=N and Ln=P multiple bonds. In addition, the combined stability and activity of the cation rare earth mediates made them the best catalysts for the polymerization of olefins and other non-polar hydrocarbon monomers, especially conjugated dienes. The practical utilization of rare earth metal catalysts for new materials production have also extensively explored by experts from the academic and industries.
Characterization
Sepideh Gomari; Ismaeil Ghasemi; Mohammad Karrabi; Hamed Azizi
Abstract
Nanocomposites based on polyamide 6 (PA6) and poly(ethylene-co-1-butene)-graft-maleic anhydride (EB-g- MAH) blends have been prepared via melt mixing. The effect of blend ratio and organoclay concentration on the crystallization and melting behavior of specimens were studied. Three types of commercial ...
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Nanocomposites based on polyamide 6 (PA6) and poly(ethylene-co-1-butene)-graft-maleic anhydride (EB-g- MAH) blends have been prepared via melt mixing. The effect of blend ratio and organoclay concentration on the crystallization and melting behavior of specimens were studied. Three types of commercial organo-modified clay (Cloisite 30B, Cloisite 15A and Cloisite 20A) were employed to assess the importance of the nanoclay polarity and gallery distance. The crystallization behavior was investigated using differential scanning calorimetry (DSC) and wide angle X-ray diffraction spectroscopy (WAXD). The strong interactions between amine end groups of PA6 and maleic anhydride groups of EB-g-MAH led to complete inhibition of EB-g-MAH crystallization according to the DSC results. A transformation from the α form to the γ form crystals of PA6, induced by both organoclays and EB-g-MAH, was monitored by WAXD and DSC. Small angle X-ray scattering (SAXS) was used to evaluate the morphology of nanocomposites. Moreover, transmission electron microscopy (TEM) was conducted to determine the location of organoclays and indicated that the organoclays mainly present in the PA6 matrix and rarely distribute in the EB-g-MAH phase in the case of low polarity organoclays. It was also evidenced that the organoclay with the most affinity to PA6 (Cloisite 30B) had the largest effect on the thermal and crystallization behavior of this phase in the blend.
Catalysis
Ting Fu; Ruihua Cheng; Xuelian He; Zhen Liu; Zhou Tian; Boping Liu
Abstract
A novel imido-modified SiO2-supported Ti/Mg Ziegler-Natta catalyst for ethylene and ethylene/1-hexene polymerization is investigated. The catalyst is prepared by modification of (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts via supporting vanadium species followed by reaction with p-tolyl isocyanate ...
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A novel imido-modified SiO2-supported Ti/Mg Ziegler-Natta catalyst for ethylene and ethylene/1-hexene polymerization is investigated. The catalyst is prepared by modification of (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts via supporting vanadium species followed by reaction with p-tolyl isocyanate as imido agents, to get the merits from both the SiO2-supported imido vanadium catalyst and the (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalyst. The effects of cocatalyst amount, hydrogen and dosage of 1-hexene on polymerization behavior and the microstructures of their polymers are systematically investigated. Compared with (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts and vanadium-modified (SiO2/MgO/MgCl2)TiClx Ziegler-Natta catalysts, the imido-modified SiO2-supported Ti/Mg catalysts show lower but more stable activity including homopolymerization, polymerization with hydrogen and copolymerization owing to imido ligands, indicating that p-Tolyl isocyanate was unfavorable to improving catalytic activity but benefited the stability, and the products of all catalysts show lower 1-hexene incorporation but much higher molecular weight (MW) with medium molecular weight distribution (MWD). The most unique feature of the novel catalysts is the excellent hydrogen response without lowering the polymerization activity, showing great potential for industrial application.
Olefin synthesis
Mohamad Hafizi Zakria; Mohd Ghazali Mohd Nawawi; Mohd Rizal Abdul Rahman; Mohd Anas Saudi
Abstract
The research was carried out in a large-scale olefin process to see how different variables affect ethylene yield in an actual fluctuating plant condition. Regression analysis was adopted using Minitab Software Version 18 to create a reliable ethylene yield model. Regression analysis is a robust, practical, ...
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The research was carried out in a large-scale olefin process to see how different variables affect ethylene yield in an actual fluctuating plant condition. Regression analysis was adopted using Minitab Software Version 18 to create a reliable ethylene yield model. Regression analysis is a robust, practical, and advanced tool that is used in various applications as an alternative to the complex, expensive, and restricted simulation software that is specifically designed for the olefin process. The 1688 data taken from the studied plant underwent outliers and residuals removal utilizing normality and stability tools in Minitab for the analysis to be conducted as normal data. The Regression was conducted a few times until all variables satisfactorily met the multicollinearity criteria with Variance Inflation Factor (VIF) < 10 and 95% confidence level criteria with P-Value < 0.05. The final Regression model established 4 significant variables which were Hearth Burner Flow, Integral Burner Flow, Super High- Pressure Steam (SHP) Temperature, and Naphtha Feed Flow by factors of -0.001266, 0.04515, -0.0795, and 0.2105, respectively. The maximum ethylene yield was calculated at 31.75% using Response Optimizer with the recommended operating conditions at 9908.50 kg/h Hearth Burner Flow, 600.39 kg/h Integral Burner Flow, 494.65°C SHP Temperature, and 63.50 t/h Naphtha Feed Flow.
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.
Catalysis
Gregory G. Arzoumanidis
Abstract
The commercial profile of the Amoco CD MgCl2 supported polypropylene catalyst is presented. The development, the unique method of preparation/production, with emphasis on particle morphology, and the parameters affecting particle size (PS), particle size distribution (PSD), and particle shape ...
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The commercial profile of the Amoco CD MgCl2 supported polypropylene catalyst is presented. The development, the unique method of preparation/production, with emphasis on particle morphology, and the parameters affecting particle size (PS), particle size distribution (PSD), and particle shape are discussed in detail. The outstanding performance of the catalyst, tailoredmade for the Amoco-Chisso gas phase process, is attributable to synergistic effects, originating from catalyst and process design factors. Catalyst median particle size (d50) may be controlled in the 7-100 microns range. Parameters affecting PS and PSD during catalyst support preparation include: agitation speed, temperature, organic reagent to Mg ratios, morphology controlling agents, and deliberate spiking of the aromatic solvent used with appropriate contaminants. Particle shape variation between the cubic and spheroidal is affected by the types of reagents used, the ratios of these reagents to Mg, the time/temperature profile of the procedure, and the sequence of reagent addition during catalyst support preparation. Catalyst activation takes place in several steps by thermal treatment of the support with TiCl4/toluene solutions. Cost-effective TiCl4/toluene reuse system from the activation streams has been put in place to reduce waste material considerably. There is an optimum temperature of activation close to 120˚C. The progress of activation as well as catalyst quality may be monitored by IR spectroscopy, expressed in easily identifiable IR fingerprint patterns, which correlate well with the catalyst performance. More recently a new concept of supported catalysts based on the CD technology has been developed. It features organometallic complexes instead of just TiCl4 as the polymerization active centers. The new catalysts show improved performance and advantageous polymer product properties. We suggest that the newly invented organometallic complexes may open a new era in polyolefin catalysis, including polyethylene copolymers. The success of the CD and Amoco-Chisso process is illustrated by the two dozen commercial plants worldwide that use the technology, and the recent licensing advances by Ineos, the successor of Amoco, for this polypropylene technology.
Structure and property relationship
Somaye Akbari; Niloofar Eslahi; Mohammad Haghighat Kish
Abstract
The present study investigates the hydrophilic properties of acrylonitrile/acrylic acid P(AN/AA) copolymer films with various acrylic acid (AA) contents dendrigrafted with citric acid from zero to fourth generation numbers. It was found that the hydrophilicity of the dendrigrafted films was a complicated ...
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The present study investigates the hydrophilic properties of acrylonitrile/acrylic acid P(AN/AA) copolymer films with various acrylic acid (AA) contents dendrigrafted with citric acid from zero to fourth generation numbers. It was found that the hydrophilicity of the dendrigrafted films was a complicated phenomenon. Various parameters such as intermolecular hydrogen bonding, roughness and active functional groups affected the wettability of the film samples measured via static contact angle. The results revealed that the hydrophilicity decreased with increasing the generation number owing to the steric hindrance of terminal groups. However, active functional group increased by rising generation numbers which was confirmed using zeta potential measurement. Furthermore, the percentage conversion of the reactions showed a reduction with increasing generation number and AA content which was in agreement with the reduction in wettability corresponding to the higher contact angle. On the other hand, zeta potential as well as roughness of the films increased with successive generations.
