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Polyolefins - Volume:6 Issue: 1, Winter 2019

Polyolefins Journal
Volume:6 Issue: 1, Winter 2019

  • تاریخ انتشار: 1397/10/15
  • تعداد عناوین: 9
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  • Ali Foroozan, Tahereh Behboodi, Yousef Jahani * Pages 1-11
    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.
    Keywords: Long chain branching, extensional rheometry, polybutene-1, TMPTMA, branching index
  • Rezgar Hasanzadeh, Taher Azdast *, Ali Doniavi, Richard Eungkee Lee Pages 13-21
    The loss of energy especially in industrial and residential buildings is one of the main reasons of increased energy consumption. Improving the thermal insulation properties of materials is a fundamental method for reducing the energy losses. Polymeric foams are introduced as materials with excellent thermal insulation properties for this purpose. In the present study, a deep theoretical investigation is performed on the overall thermal conductivity of low-density polyethylene (LDPE) foams. The thermal conductivity by radiation is predicted using two different methods. The most appropriate model is selected in comparison with experimental results. The results show that the theoretical model has an appropriate agreement with the experimental results. The effects of foam characteristics including foam density, cell size, and cell wall thickness on the overall thermal conductivity are investigated. The results indicate that by decreasing the cell size and increasing the cell wall thickness, the overall thermal conductivity is decreased significantly. Also, there is an optimum foam density in order to achieve the smallest thermal conductivity. The lowest overall thermal conductivity achieved in the studied ranges is 30 mW/mK at foam density of 37.5 kg.m-3, cell size of 100 μm, and cell wall thickness of 6 μm.
    Keywords: LDPE, Radiated thermal conductivity, Thermal-insulation, Polymeric foams
  • Dragoslav Stoiljkovic *, Slobodan Jovanovi Pages 23-41
    At low pressure, ethylene gas consists of single translating and rotating molecules and behaves as an ideal gas. With decrease of free volume by compression, various rotating supramolecular particles are formed, which require less space for the movement: molecular pairs, bimolecules and oligomolecules. The appearance of a new kind of particles is manifested as a phase transition of the second or third order. An ideal gas consists of single translating and rotating molecules. α phase consists of rotating single molecules and rotating molecular pairs and it exists when the volume V is reduced to Vc<V<2Vc. (Vc is critical volume). β phase consists of molecular pairs and bimolecules and it exists when VSc. (Sc is critical entropy). γ phase and liquid ethylene consist of bimolecules and oligomolecules and they exist when S<Sc. The main goal of this article is to publish how we developed that model and what were thermodynamical, physical and chemical evidences which confirmed its validity. Instead of the classical theory of radical polymerization, we applied Kargin and Kabanov theory of polymerization of organized monomer to interpret high pressure free radical polymerization of ethylene. The arrangement of monomer molecules in individual supramolecular particles and the supramolecular organization of whole system have decisive effects on the mechanism and kinetics of polymerization and on the formation of polymer structure and properties, i.e. molecular mass and its distribution, branching, density, etc. There is isentropic rule: the same structures and properties are obtained for polyethylene if the entropy of ethylene under polymerization conditions is the same, regardless the differences in other polymerization conditions, i.e. reactor type, pressure, temperature and method of initiation. Mathematical models of the effect of ethylene entropy on polyethylene structure and density enable practical design of polyethylene with desired characteristics. Finally, it is mentioned that we expanded the model of ethylene to other gases and liquids as well as to other polymerization cases, including liquid monomers and olefins polymerization by Ziegler-Natta, metallocene and Phillips catalysts.
    Keywords: Ethylene gas compression, ethylene supramolecular organization, ethylene supercritical phase state, ethylene free radical polymerization, low density polyethylene, polyethylene structure
  • Zaher Tamri, Ali Vaziri Yazdi *, Mehdi Nekoomanesh Haghighi, Mehrdad Seifali Abbas, Abadi, Amir Heidarinasab Pages 43-52
    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.
    Keywords: High impact polystyrene, temperature, heating rate, catalyst, TGA
  • Fatemeh Hassan, Mehdi Entezam * Pages 53-61
    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.
    Keywords: polypropylene, electron beam irradiation, rheological properties, mechanical properties, thermal properties
  • Shahab Hoseinpour , Yoones Jafarzadeh *, Reza Yegani , Sepideh Masoumi Pages 63-74
    The aim of the present work is to enhance the antifouling properties of polypropylene (PP) membrane based on hydrophilicity improvement. Different contents of neat and modified nanodiamond (0.25, 0.50, 0.75 and 1.00 wt.%) were embedded into PP membranes. Nanodiamond nanoparticles were carboxylated by heat treatment method and the presence of carboxyl functional groups on the surface of nanoparticles was confirmed by FTIR analysis. Membranes were then characterized by FESEM, contact angle and tensile strength tests. At the same content of nanoparticles, hydrophilicity, pure water flux and tensile strength of PP/ND-COOH membranes were more than those of PP/ND membranes. Membranes embedded with 0.75 wt. % of neat and modified nanoparticles were used in a submerged membrane bioreactor (SMBR) system along with neat PP membrane. The results showed that critical flux values for neat PP, PP/ND and PP/ND-COOH membranes were 7, 18 and 22 L/(m2.h), respectively. Analysis of fouling mechanisms revealed that antifouling properties of 0.75 wt. % PP/ND-COOH membrane were higher than those of other two ones so that irreversible fouling ratio decreased from 88.9% for neat PP to 47.8% for PP/ND-COOH membrane.
    Keywords: polypropylene, nanodiamond, membrane, MBR, fouling
  • Majid Habibollahi, Morteza Ehsani *, Jalil Morshedian Pages 75-83
    In this study, poly carbonate (PC) and poly (ethylene terephthalate) (PET) were reactive melt-blended under two different conditions to produce PC/PET copolymers. For each condition, samples were taken at specified mixing times representative a specific structure of copolymers and each one employed to physically compatibilize a PC/PET blend with a fixed composition. Reactive blending and copolymer structure are described by solubility analysis results. Continues declining and going through a minimum are two trends of solubility versus mixing time depending on reactive blending condition. Decreasing and increasing patterns of solubility curves were attributed to the formation of copolymers with longer and shorter block lengths, respectively, and the level of solubility was related to the amount of produced copolymers. Differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) techniques were employed to investigate blend compatibility. The content and structure of copolymers showed favorable correlation of Tg differences of blend components and PET crystallinity. As expected, Tg of blend components approached to each other by the addition of copolymers, and the copolymers with longer block length caused less Tg differences. The melting point and crystallinity of PET were affected by introducing the copolymers too. In addition to the main melting endotherm, melting endotherm peaks of compatibilized blends had a shoulder that its corresponding melting point and crystallinity are related to the copolymer structure so that the longer length of block copolymer or higher its amount leads to the higher melting points. The SEM micrographs showed that, after the addition of the copolymer, smaller PET particles formed and uniformly dispersed in the PC matrix. A strong correlation between the blend morphology and the level of blend compatibility was demonstrated. The more compatibilized PC/PET blend, the better dispersion of PET particles in the PC matrix was obtained. The results of this study could be a basis for designing and production of compatibilizers suitable to achieve a desired level of compatibility in PC and polyester blends, specially in PC/PET blend.
    Keywords: PET, PC, trans-esterification, compatibility, crystallinity
  • Mojtaba Farrokhi, Mahdi Abdollahi * Pages 85-94
    Polystyrene (PSt) has been known as one of the important polymers with a wide range of applications. Ability to synthesize PSt with different but predictable molecular weights for various applications is very important in the laboratories and industries. In this study, using various simple and inexpensive techniques with only free radical mechanism, it was tried to synthesize PSt with different low (< 2×104 g mol-1) to high (> 105 g mol-1) molecular weights. PSts with high and moderate molecular weights (2×104-105 g mol-1) were synthesized using thermal and conventional free radical polymerizations, respectively. Reverse iodine transfer radical polymerization (RITP) was utilized to synthesize PSt with a low and controlled molecular weight. Conversion, molecular weight distribution and PSt structure were analyzed using 1H-NMR spectroscopy and size exclusion chromatography (SEC), respectively. Moreover, ω-iodo poly(dimethylsiloxane), i.e. PDMS-I, was also used as a macrotransfer agent for ITP of styrene. Diblock copolymer of PDMS-b-PSt was characterized by 1H-NMR and SEC analyses.
    Keywords: Polystyrene, low to high molecular weights, thermal polymerization (TP), free-radical polymerization, (reverse) iodine transfer radical polymerization ((R)ITP)
  • Hossein Ebrahimi, Ahmad Ramazani S.A *, Seyed Mohammad Davachi Pages 95-106
    Rheological models for polymer solutions and melts based on the finitely extensible non-linear elastic (FENE) dumbbell theory are reviewed in this study. The FENE-P model that is a well-known Peterlin approximation of the FENE model, indicates noticeable deviation from original FENE predictions and also experimental results, especially in the transient flow. In addition, both FENE and FENE-P models have some shortcomings from the point of view of theory. To overcome these shortcomings, a new approximation of the FENE spring force has been established. It has been used to develop a modified constitutive rheological model for polymeric fluids. In the procedure of modeling, the effect of non-affine deformation is introduced into the new model. Comparison between the model predictions and experimental data presented in the literature for transient and steady shear flow of polystyrene indicates that this modified model can predict the rheological behavior of polymeric fluids with a great accuracy. The newly developed modified model could predict different slopes that can cover the behavior of most of the polymeric fluids.
    Keywords: Rheological modeling, spring force approximation, FENE model, FENE-P model, FENE-M2 model, FENE modification