Catalysis
Najmeh Hadian; Shokoofeh Hakim; Mehdi Nekoomanesh-Haghighi; Naeimeh bahri-Laleh
Abstract
Primary MgCl2.3.3EtOH adduct (PCT1) was prepared by melt quenching method and then submitted into a programmed thermal dealcoholation project using a fluidized bed reactor. During thermal dealcoholation program, different MgCl2.nEtOH support samples with n= 3.0, 2.7, 2.4, and 2.1 were selected and named ...
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Primary MgCl2.3.3EtOH adduct (PCT1) was prepared by melt quenching method and then submitted into a programmed thermal dealcoholation project using a fluidized bed reactor. During thermal dealcoholation program, different MgCl2.nEtOH support samples with n= 3.0, 2.7, 2.4, and 2.1 were selected and named as PCT2 to PCT5, respectively. Structural analysis of the support samples showed a significant increase in the surface area, from 7.4 m2/g to 12.8 m2/g, together with the decrease in peaks height at 2θ≈ 8.9 and 9.7˚ by moving from PCT1 to PCT5. After characterization of support samples, final catalysts were prepared by reacting these samples with TiCl4 and examined in slurry phase propylene polymerization. Prepared catalysts showed similar stereospecifities but different activities in the polymerization experiments, so that, with proceeding dealcoholation from PCT1 to PCT2 catalyst activity was reached a maximum amount of 2.9 kgPP/g Cat.h, and then by further dealcoholation, from PCT2 to PCT5, catalyst activity decreased gradually. In the last section, effect of time interval between thermal dealcoholation and catalyst preparation, which is called storage time, on the crystal and morphological characteristics of the two of the best adduct samples, namely MgCl2.2.4EtOH and MgCl2.3.0EtOH, was studied, as well. Storage time greatly affected the characteristics of the adducts together with resulted catalysts, and the best catalyst activity was achieved for the ones prepared immediately after adduct preparation.
Mariana del Valle Bernard; Verónica Viviana Nicolau; Miriam Cristina Strumia
Abstract
Industrially used polymers derived from fossil fuels have a negative environmental impact when being disposed of. They could be efficientlyreplaced by natural polymers, which are potentially degradable and which can match or even surpass them in mechanical performance. In this work, a rigid thermosetting ...
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Industrially used polymers derived from fossil fuels have a negative environmental impact when being disposed of. They could be efficientlyreplaced by natural polymers, which are potentially degradable and which can match or even surpass them in mechanical performance. In this work, a rigid thermosetting polymer is obtained by copolymerization of maleinated acrylated epoxidized soybean oil (MAESO) with styrene (St). MAESO is synthetized by epoxidation, acrylation and maleinization from industrial soybean oil (SO). Resin characterization is performed using FT-IR, 1H NMR and SEC, while copolymer characterization includes a mechanical test, degradation test and SEM. The aim of this work is the replacement of unsaturated polyester (UP) and the optimization of the SO modificationreaction in MAESO. The replacement of UP by 25, 50 and 100% of MAESO enables improvements in the mechanical properties. Additionally, it is assessed whether the replacement of UP by MAESO is enough to improve the degradation properties, and the effect of degradation on the mechanical properties is analyzed. MAESO-St copolymers improve the degradation process in relation to UP, and 240 days of in vitro degradation in the presence of Aspergillus niger and Alternaria alternata fungi causes cracks, surface damage and changes in the mechanical properties of the degraded copolymer.
Catalysis
Goond Hongmanee; Patchanee Chammingkwan; Toshiaki Taniike; Minoru Terano
Abstract
Mg(OEt)2 with spherical morphology is one of the most important precursors for the preparation of industrial Ziegler-Natta catalysts. In the present article, morphology evolution of Mg(OEt)2 particles is studied in the course of the synthesis. The morphology of Mg(OEt)2 particles is observed throughout ...
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Mg(OEt)2 with spherical morphology is one of the most important precursors for the preparation of industrial Ziegler-Natta catalysts. In the present article, morphology evolution of Mg(OEt)2 particles is studied in the course of the synthesis. The morphology of Mg(OEt)2 particles is observed throughout the process by SEM. The results show that Mg(OEt)2 particles are formed through i) seed generation on Mg surfaces, ii) seed growth and isolation as independent particles, and iii) further growth and shaping into smoother and more spherical particles. The size of Mg sources greatly affects the rates of these processes to different extents. A larger size of Mg leads to slower seed formation and growth, and detachment of clustered seeds, making the final particles larger and less spherical, respectively. The crystal growth of Mg(OEt)2 is also affected by the size of Mg sources, which in turn differentiates the pore size distribution to affect the catalyst composition and performance.
Polymeric foams
Christophe Daniel; Simona Longo; Gaetano Guerra
Abstract
Monolithic aerogels of high molecular weight polyethylene (Mw= 3x106- 6x106 g/mol) have been prepared by solvent extraction with supercritical carbon dioxide from thermoreversible gels prepared in decalin. These low density and highly porous aerogels present an apparent porosity up to 90%. The aerogel ...
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Monolithic aerogels of high molecular weight polyethylene (Mw= 3x106- 6x106 g/mol) have been prepared by solvent extraction with supercritical carbon dioxide from thermoreversible gels prepared in decalin. These low density and highly porous aerogels present an apparent porosity up to 90%. The aerogel morphology observed by scanning electron microscopy (SEM) is characterized by spherulitic structures being interconnected by fibers. X-ray diffraction experiments show that PE aerogels are highly crystalline with a degree of crystallinity of c.a. 80% and PE chains being packed into the typical orthorombic unit cell. Combined SEM and N2 sorption investigations show that PE aerogels are essentially macroporous with a small amount of mesopores. The oil-sorption performance of polyethylene aerogels has been also evaluated in this study in order to assess a possible use of these materials for oil spillage recovery and results show that aerogel macropores allow a very fast sorption kinetics with a 100% oil weight uptake obtained in less than 1 minute.
Polyolefins Functionalization
Shohei Tanaka; Kenta Adachi
Abstract
Organocatalysts have attracted enormous interest in the water-crosslinking reaction in silane-grafted polyolefins (SGPOs) system owing to their simplicity, low toxicity and environmentally benign nature compared to organotin catalysts, which are most used in SGPOs system. We focus on organophosphorus ...
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Organocatalysts have attracted enormous interest in the water-crosslinking reaction in silane-grafted polyolefins (SGPOs) system owing to their simplicity, low toxicity and environmentally benign nature compared to organotin catalysts, which are most used in SGPOs system. We focus on organophosphorus compounds including four structure types as organocatalysts; phosphoric acids, phosphoric esters, phosphine oxides and phosphine. The catalytic activities of them for the water-crosslinking reaction in 3-methacryloxypropyltrimethoxysilane grafted ethylene-propylene copolymer (EPR-g-MTMS) system were evaluated using the ATR-FTIR technique and gel-fraction method. The phosphine oxides, phosphoric acids, and phosphoric esters possessing an O=PR3 or O=P(OR)3 unit were found to be an excellent catalyst for the water-crosslinking reaction in EPR-g-MTMS system, while phosphine (PR3) showed no catalytic activity on water-crosslinking reaction in this system, indicating the phosphoryl (P=O) moiety played the important role on catalytic performance of these compounds. In comparison, phosphine oxides showed considerably higher catalytic activities than phosphoric acids / esters. Density functional theory (DFT) calculations demonstrated that the difference of catalytic activity could be attributed to an electron density at P=O moiety making the activation for water through hydrogen-bonding. Finally, the possible catalytic mechanism for the phosphoryl compounds in the EPR-g-MTMS system was proposed on the basis of these results and the SN2-Si pathway in silicate sol-gel chemistry.
Polymer processing
Shahab Hoseinpour; Yoones Jafarzadeh; Reza Yegani; Sepideh Masoumi
Abstract
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 ...
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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.
Polyolefin degradation
Nikoo Karami; Reza Jahanmardi
Abstract
The present work is aimed to find a new and efficient type of antioxidants for polypropylene. Hence, effects of 3,3-bis(4-hydroxy-2-methyl-5-propan-2-ylphenyl)-2-benzofuran-1-one, generally known as thymolphthalein, on thermo-oxidative stability of polypropylene in solid and melt states were evaluated ...
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The present work is aimed to find a new and efficient type of antioxidants for polypropylene. Hence, effects of 3,3-bis(4-hydroxy-2-methyl-5-propan-2-ylphenyl)-2-benzofuran-1-one, generally known as thymolphthalein, on thermo-oxidative stability of polypropylene in solid and melt states were evaluated and compared with those of SONGNOX 1010, an efficient commercially used antioxidant for the polymer. Oven ageing experiments followed by Fourier transform infrared (FTIR) spectroscopy showed that thymolphthalein increased thermo-oxidative stability of the polymer outstandingly in the solid state and its stabilization efficiency was comparable to that of SONGNOX 1010. In addition, measurements of oxidative induction time (OIT) and oxidation onset temperature (OOT) revealed that thymolphthalein improved thermo-oxidative stability of the polymer in the melt state significantly. It was also observed that thymolphthalein did not interfere with the stabilization action of SONGNOX 1010 in the polymer neither in melt nor in solid state. On the basis of the obtained results, a probable mechanism for the stabilization action of thymolphthalein in the polymer is proposed.
Computational chemistry & molecular modeling
Parisa Alamdari; Farhad Sharif; Saeedeh Mazinani
Abstract
The effect of structural defects on graphene interaction with other molecules is of high interest. In this study, the interaction of ethylene molecules with pristine graphene (PG) and defective graphenes including single (SVG) and double (DVG) vacancies, were investigated using dispersion-corrected periodic ...
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The effect of structural defects on graphene interaction with other molecules is of high interest. In this study, the interaction of ethylene molecules with pristine graphene (PG) and defective graphenes including single (SVG) and double (DVG) vacancies, were investigated using dispersion-corrected periodic density functional theory (DFT). We used various pairs of pseudopotentials and dispersion-corrected methods to calculate the exchange-correlation energies and long-range energies, respectively. We conducted the calculations in the ethylene-graphene equilibrium distance where vdW interaction as a long-range interaction was dominant. Both adsorption and deformation energies were calculated to examine the possibility of ethylene chemisorption. It was found that there is a critical distance from the graphene surface, where the nature of adsorption of adsorbate molecule changes from physisorption to the possible chemisorption depending on the energetical costly distortion induced in adsorbate molecule. In the case of ethylene adsorption on the graphene structures studied here, the mentioned critical distances follow the order SVG < DVG < PG. However, in the range of vdW domination and in comparison with PG, ethylene interacts more with SVG due to the presence of a dangling bond and interacts less with DVG due to the presence of a hole. Furthermore, the interactions of ethylene with reconstructed trivacancy were studied. Moreover, all possible orientations for ethylene adsorption on graphene structures were considered and energetically compared. All calculations were done on fully optimized reconstructed geometries of vacancies with structural characteristics, i.e., reconstruction length and formation energies comparable to those reported in the literature.
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.
Polymer processing
Shirin Shokoohi; Ghasem Naderi
Abstract
Elastomer vulcanizates based on natural rubber (NR), NR reclaim (NRR) and layered silicates were compounded in an internal mixer and cured on a two-roll mill. Cure characteristics and mechanical properties of samples based on 50NR/50NRR reinforced with Cloisite 20A, Cloisite 30B and Nanolin DK1 were ...
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Elastomer vulcanizates based on natural rubber (NR), NR reclaim (NRR) and layered silicates were compounded in an internal mixer and cured on a two-roll mill. Cure characteristics and mechanical properties of samples based on 50NR/50NRR reinforced with Cloisite 20A, Cloisite 30B and Nanolin DK1 were compared to those of conventional NR/NRR/kaolin microcomposites. Due to the light/soft nature of organoclays suppressing the friction forces, the minimum torque values decreased in the presence of organoclays, whereas the crosslink density, evidenced by the difference between the maximum and minimum torque values, increased in all samples and scorch times shortened by 37% to a minimum in the presence of Nanolin alkaline/catalytic role in the cure reaction. Fatigue resistance improved by about 10% benefiting the crack tips blunting/energy consuming hysteresis mechanisms motivated by the organoclays among which Nanolin DK1 provides the most efficient dispersion/distribution of nanolayers by faster intragallery crosslinking reactions that pushes the stacks apart. Higher states of dispersion in this sample would also promote strain-induced crystallization under deformation responsible for the improvements seen in the modulus and elongation-at-break. Two-step mixing sequence further improved the compound performance due to the dispersion state progress confirmed by X-ray diffraction and transmission electron microscopy (20% in fatigue resistance and 53% in tensile modulus). In-situ compatibilization through bis(triethoxysilylpropyl)tetrasulfide bi-functional silane coupling agent also promoted modulus and fatigue resistance. However, a prolonged scorch time was observed due tothe blinded NR cure-reactive sites as well as steric hindrance of large functional groups in the presence of this coupling agent.
Characterization
Sampat Bhati; Tibor Macko; Robert Brüll
Abstract
Hyphenating High Temperature High Performance Liquid Chromatography (HT-HPLC) with High Temperature Size Exclusion Chromatography (HT-SEC) (High Temperature Two Dimensional Liquid Chromatography (HT-HPLC x HT-SEC or HT 2D-LC)) leads to an isocratic elution in the second dimension, which in turn enables ...
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Hyphenating High Temperature High Performance Liquid Chromatography (HT-HPLC) with High Temperature Size Exclusion Chromatography (HT-SEC) (High Temperature Two Dimensional Liquid Chromatography (HT-HPLC x HT-SEC or HT 2D-LC)) leads to an isocratic elution in the second dimension, which in turn enables to use IR detector (quantitative detection) for monitoring the eluting polymers. Experimental data obtained from HT 2D-LC with IR detector are usually presented as contour plots, which can be mathematically described in matrices. Quantitative data about chemical composition, molar mass and concentration of all the segments, which are present in a polymer, can be obtained, after calibrating the HPLC separation (HPLC elution volume vs chemical composition), SEC separation (SEC separation vs molar mass) and response of the IR detector (IR response vs mass of the polymer). A new procedure based on subtraction and addition of matrices is described, which enables quantitative comparison of different polymer materials. This procedure enables to determine, which components are present in both materials (i.e., identical components or segments) and which are present only in one from both the materials (i.e., unique segments). Moreover, molar mass distribution, as well as chemical composition distribution of both identical and unique segments is evaluated from experimental data. The procedure was applied on two different ethylene-propylene copolymer samples.
Seyed Mehdi Ghafelebashi Zaranda; Ali Safinejad
Abstract
In this study, slurry polymerization kinetics of ethylene with TiCl4/Mg(OEt)2/AlR3 Ziegler-Natta catalysts in various conditions using the model of sum square error (SSE) (method I) and model of least square error (LSE) (Method II) was investigated. For this purpose the molecular weight distributions ...
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In this study, slurry polymerization kinetics of ethylene with TiCl4/Mg(OEt)2/AlR3 Ziegler-Natta catalysts in various conditions using the model of sum square error (SSE) (method I) and model of least square error (LSE) (Method II) was investigated. For this purpose the molecular weight distributions of the samples were deconvoluted to the minimum number of Flory type distributions where each represents a different active center type of Ziegler-Natta catalyst. The first method used to determine the leading apparent polymerization kinetic constants for each site in absence of hydrogen by simultaneously fitting the instantaneous polymerization rate, cumulative polymer yield, and molecular weight distribution measured for various samples with various conditions. Second method was used to determine all kinetics parameters such as initiation, propagation, termination and transfer to monomer reaction in absence and also in the presence of hydrogen. For the later, transfer to hydrogen also determined. The results showed that this simulation package is a powerful tool for design and scale up this kind of processes.
Computational chemistry & molecular modeling
Naeimeh bahri-Laleh; Laura Falivene; Luigi Cavallo
Abstract
In this study we have tested the ability of a standard DFT computational protocol to reproduce the experimentally obtained stereoselectivity of 26 different C2-symmetric zirconocene catalysts active in propylene polymerization. The catalysts were chosen for their relevance in metallocene catalyzed ...
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In this study we have tested the ability of a standard DFT computational protocol to reproduce the experimentally obtained stereoselectivity of 26 different C2-symmetric zirconocene catalysts active in propylene polymerization. The catalysts were chosen for their relevance in metallocene catalyzed polymerization of propylene. To this end, primary insertion of both si- and re-propylene enantiofaces into the Zr-CH2-CH(CH3)2 bond was considered to simulate the growing chains step. The energy difference between these two transition states, ΔEre-si, was taken as a measure of the stereoselectivity (pentad: mmmm%) of different catalysts. The results clearly indicated that there was a good agreement between ΔEre-si and the mmmm% values, so that greater ΔEre-si could correspond to higher mmmm%. A model was fitted to the experimentally obtained mmmm% against theoretical ΔEre-si. The coefficient of determination (R2) of the resultant plot was 0.9793, which indicated a good accuracy of the model. Finally, to quantify the steric role of the studied ligands in the observed stereoselectivity, the analysis of the buried volume (VBur) and of the steric maps was performed for two representative complexes. The images revealed that a greater asymmetric localization of the %VBur around the metal center led to a higher mmmm% in the resultant polymer.
Catalysis
Qiaoqiao Sun; Ruihua Cheng; Zhen Liu; Xuelian He; Ning Zhao; Boping Liu
Abstract
Chromium-vanadium (Cr-V) bimetallic catalysts are prepared by the introduction of vanadium into the Phillips catalyst which is one of the most significant industrial ethylene polymerization catalysts for tuning the Phillips catalyst performances and improving polyethylene properties. In the present work, ...
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Chromium-vanadium (Cr-V) bimetallic catalysts are prepared by the introduction of vanadium into the Phillips catalyst which is one of the most significant industrial ethylene polymerization catalysts for tuning the Phillips catalyst performances and improving polyethylene properties. In the present work, titanium species were introduced into the fluorine-modified chromium-vanadium bimetallic catalysts (Cr-V-F) and the prepared catalysts were systematically explored. The element content results of multi-component catalysts showed that a competitive inhibition interaction existed between chromium and vanadium, whereas chromium was more preferable to attach to the Ti-SiO2 than vanadium. In addition, ethylene homopolymerization and ethylene/1-hexene copolymerization were carried out and examined with different catalysts. The introduction of titanium into fluorine-modified bimetallic catalysts enhanced the molecular weight (MW) and broadened the molecular weight distribution (MWD) of polyethylene. The MW of the titanium- and fluorine-modified bimetallic catalysts (Cr-V-F/Ti) firstly rose up and then dropped down with the increasing of the Al/Cr molar ratio. The Cr-V-F/Ti catalysts showed slightly depressed hydrogen response and incorporation of 1-hexene. The short-chain branch distribution (SCBD) results, which were characterized by TREF/SSA, showed that the introduction of the titanium species increased the SCB content in low MW fractions and decreased the SCB content in the high Mw fractions of ethylene/1-hexene copolymers obtained from (Cr-V-F/3Ti)600 in contrast to that from (Cr-V-F)600.
Catalysis
Giovanni Ricci; Giuseppe Leone
Abstract
The stereospecific polymerization of conjugated dienes began in 1954 with the first catalysts obtained by combining TiCl4 or TiCl3 with aluminum-alkyls, i.e. the catalytic systems previously employed for ethylene and propylene polymerizations. Subsequently, many other catalytic systems were obtained ...
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The stereospecific polymerization of conjugated dienes began in 1954 with the first catalysts obtained by combining TiCl4 or TiCl3 with aluminum-alkyls, i.e. the catalytic systems previously employed for ethylene and propylene polymerizations. Subsequently, many other catalytic systems were obtained and examined by a combination of transition metal or lanthanide compounds with appropriate alkylating agents. With the advent of MAO as alkylating agent, at the beginning of the 1980s, new catalytic systems were introduced, in some cases much more active and stereospecific than those based on common aluminum-alkyls. Starting from the 2000s, in the wake of what happened in the case of mono-olefins, a new generation of catalysts based on complexes of transition ,metals and lanthanides with various ligands containing donor atoms such as P, N, O (e.g., phosphines, imines imino-pyridines, cheto-imines) has been introduced. These systems have proved particularly active and able to (provide polymers with controlled microstructure (i.e., cis-1,4; 1,2; mixed cis-1,4/1,2 with a variable 1,2 content ,from several types of 1,3-dienes, permitting indeed to establish new correlations between the catalyst structure the monomer structure and the polymer microstructure, and to improve our knowledge on the polymerization mechanism of 1,3-dienes. This paper provides an exhaustive overview of the latest developments in the field of stereospecific polymerization of 1,3-butadiene.
Catalysis
Toshiaki Taniike; Keisuke Goto; Minoru Terano
Abstract
Heterogeneous Ziegler-Natta and homogeneous metallocene catalysts exhibit greatly different active sitenature in olefin polymerization. In our previous study, it was reported that MgCl2-supported titanocenecatalysts can generate both Ziegler-Natta-type and metallocene-type active sites according to the ...
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Heterogeneous Ziegler-Natta and homogeneous metallocene catalysts exhibit greatly different active sitenature in olefin polymerization. In our previous study, it was reported that MgCl2-supported titanocenecatalysts can generate both Ziegler-Natta-type and metallocene-type active sites according to the type of activators.The dual active site nature of the supported titanocene catalysts was further explored in the present study: The influence of the ligand structure of titanocene precursors was studied on the nature of active sites when supported on MgCl2 in ethylene and propylene homopolymerization, and ethylene/1-hexene copolymerization. It was found that the reducibility of titanocene precursors by alkylaluminum is closely related to the appearance of the dual active site nature, while the kind of olefin did not affect the type of active sites formed during polymerization. The Ziegler-Natta-type active sites produced poorly isotactic polypropylene and less branched polyethylene, while the metallocene-type active sites produced atactic polypropylene and exhibited much higher incorporation efficiency for 1-hexene.
Polyolefin degradation
Larissa Montagna; Andre Luis Catto; Maria Madalena Forte; Ruth Marlene Santana
Abstract
In this study, PP films were modified with an organic pro-degradant in different concentrations (1, 2 and 3 wt.%), exposed in the first step of degradation to natural ageing for 100 days followed by biodegradation in simulated soil in the respirometric test for 100 days. At the end of the combined degradation ...
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In this study, PP films were modified with an organic pro-degradant in different concentrations (1, 2 and 3 wt.%), exposed in the first step of degradation to natural ageing for 100 days followed by biodegradation in simulated soil in the respirometric test for 100 days. At the end of the combined degradation process the PP samples were characterized according to their morphological and physical properties and the CO2 generated during the biodegradation in soil was monitored. The CO2 production by the PP films modified with the organic pro-degradant was proportional to the oxidation rate and weight loss of the samples. The reduction in the average viscosimetric molecular weight could be attributed to chain scission due to the weathering conditions to which the samples were exposed (natural ageing followed by biodegradation in soil). Scanning electron microscopy (SEM) of the PP films revealed surface deterioration of the films with the organic pro-degradant after the combined degradation process.
Membrane
Saba Raveshiyan; Parya Amirabedi; Reza Yegani; Behzad Pourabbas; Akram Tavakoli
Abstract
Wetting of polymeric hollow fiber membranes by chemical absorbents is one of the main challenges of gasliquid membrane contactors. This study explored an appropriate method to fabricate a superhydrophobic polypropylene (PP) hollow fiber membrane by incorporating fluorinated silica nanoparticles (fSiO2 ...
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Wetting of polymeric hollow fiber membranes by chemical absorbents is one of the main challenges of gasliquid membrane contactors. This study explored an appropriate method to fabricate a superhydrophobic polypropylene (PP) hollow fiber membrane by incorporating fluorinated silica nanoparticles (fSiO2 NPs) on the PP membrane surface. The effect of the hydrophobic agent on the water repellent properties of the composite membrane was studied by varying (1H,1H,2H,2H-perfluorooctyltriethoxysilane/ tetraethylorthosilicate) (PFOTES/TEOS) molar ratio from 0 to 1. The composite membranes were characterized using field emission scanning electron microscopy (FESEM), attenuated total reflection-Fourier transform infrared (ATR-FTIR), contact angle, mechanical strength and static wettability. The obtained results showed that the surface hydrophobicity and mechanical strength of the composite membranes increased compared to pure ones. The contact angle of 156° was obtained when the (PFOTES/ TEOS) molar ratio was 0.5. Furthermore, the CO2 absorption experiment was done to evaluate the performance of the fabricated membranes in a gas-liquid membrane contactor. The obtained results showed that the PP/fSiO2 composite membrane has more potential to be used in gas-liquid membrane contactors than commonly used polymeric membranes
Structure and property relationship
Majid Habibollahi; Morteza Ehsani; Jalil Morshedian
Abstract
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 ...
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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.
Catalysis
Valentina Nikolaevna Panchenko; Ludmila Viktorovna Vorontsova; Vladimir Aleksandrovich Zakharov
Abstract
The interaction of the external donor (propyltrimethoxysilane - PTMS) with titanium-magnesium catalysts (TMCs) containing dibutylphthalate (DBP) as internal donor, which were prepared in different ways, was studied by chemical analysis and infrared diffuse reflectance spectroscopy (DRIFTS). The chemical ...
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The interaction of the external donor (propyltrimethoxysilane - PTMS) with titanium-magnesium catalysts (TMCs) containing dibutylphthalate (DBP) as internal donor, which were prepared in different ways, was studied by chemical analysis and infrared diffuse reflectance spectroscopy (DRIFTS). The chemical composition of the catalysts after their interaction with heptane solutions of PTMS, PTMS/AlEt3 or AlEt3 during 1h at 70°C showed that this interaction led to removal of both TiCl4 and DBP from the catalysts. The fractions of DBP and Ti extracted, as well as the amounts of PTMS and AlEt3 bound, depended on the method of synthesizing the catalysts. DRIFT spectroscopy data concerning the state of DBP in the catalysts, before and after treatment with heptane solutions of PTMS or PTMS/AlEt3 during 1h at 70°C, showed that PTMS could substitute both TiCl4 and DBP, while adsorbing on coordinatively unsaturated Ti and Mg ions in the catalyst. The presence of AlEt3 played a key role in the interaction of PTMS with the catalyst. Activity data for propylene polymerization showed that treatment of TMC catalysts with PTMS before polymerization led to a sharp activity decrease due to deactivation of active sites, while the interaction of the catalyst with PTMS in the presence of AlEt3 led only to a slight decrease of activity, probably due to deactivation of non-stereospecific active centers.
Reaction engineering
Marzieh Nouri; Mahmoud Parvazinia; Hassan Arabi; Mohsen Najafi
Abstract
A two-dimensional (2D) single particle model for the copolymerization of propylene-ethylene with heterogeneous Ziegler-Natta catalyst is developed. The model accounts for the effects of the initial shape of the catalyst and carck/ pore patterns on the copolymer composition, polymerization rate and the ...
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A two-dimensional (2D) single particle model for the copolymerization of propylene-ethylene with heterogeneous Ziegler-Natta catalyst is developed. The model accounts for the effects of the initial shape of the catalyst and carck/ pore patterns on the copolymer composition, polymerization rate and the average molecular weight properties. The spherical and oblate ellipsoidal shapes of catalyst particle and four different pattern distributions of cracks and pores in a growing particle are studied in this simulation. It is assumed that the diffusion coefficient of monomers in the cracks/pores is 10 times higher than the compact zone of the particle.In other word, the cracks are distinguished from parts with higher monomer diffusion coefficient.The dynamic 2D monomer diffusion-reaction equation is solved together with a two-site catalyst kinetic mechanism using the finite element method. Simulation results indicate that the initial shape of catalyst changes the average copolymer composition only in the early stage of polymerization, but the crack/pore patterns in the growing particle have a strong impact on the copolymer composition in the polymer particles due to the change ofmass transfer limitations.
Simulation & Modeling
Mehrsa Emami; Farzin Hormozi; Hossein Abedini
Abstract
Bulk phase polymerization of propylene with a 4th generation of Ziegler-Natta catalyst was kinetically investigated by means of heat flow calorimetry. The assumptions and modifications on isothermal calorimetric method were demonstrated. Our calibration method showed that heat exchange with the reactor ...
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Bulk phase polymerization of propylene with a 4th generation of Ziegler-Natta catalyst was kinetically investigated by means of heat flow calorimetry. The assumptions and modifications on isothermal calorimetric method were demonstrated. Our calibration method showed that heat exchange with the reactor cover plate is not constant over time. Therefore, the dynamic of cover plate temperature was considered in the calorimetric method. The polymerization rate profiles depending on hydrogen and external electron donor concentration have been investigated. Normalized polymerization profiles (Rp /Rpmax) are plotted and expressed as an exponential function of time. Effects of hydrogen and external electron donor (ED) concentration on Rpmax and polymerization rate were investigated as well. The results showed that by increasing hydrogen concentration, initial polymerization rate (Rpmax) increased. Hydrogen increased productivity by increasing the initial polymerization rate, while it had no negative effect on the rates of decay or its effect was small. The ED concentration was optimized so that the catalyst deactivation rate was at its lowest level. Also, changes in the ratio of activation to inactivation with ED concentration were examined, and a proportional change was observed.
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.
Characterization
Setareh Heidari; Yoones Jafarzadeh; Mahdi Seyfollahi Samarin; Reza Yegani
Abstract
In this study, neat HDPE and HDPE/PE-g-MA/EVA blend membranes were fabricated via thermally induced phase separation (TIPS) method and their fouling behaviors were examined using filtration of BSA protein. Membranes were characterized using FESEM, AFM, ATR-FTIR analyses and porosity measurement. Fouling ...
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In this study, neat HDPE and HDPE/PE-g-MA/EVA blend membranes were fabricated via thermally induced phase separation (TIPS) method and their fouling behaviors were examined using filtration of BSA protein. Membranes were characterized using FESEM, AFM, ATR-FTIR analyses and porosity measurement. Fouling behavior of membranes was analyzed using the resistance-in-series (RIS), classic and combined pore blocking models. The results of RIS model revealed that the magnitude of inherent, reversible and irreversible resistances decreased from 0.611 ×1013m-1 and ,1.578 ×1013m-1 and 0.525 ×1013m-1 for the neat membrane to 0.237 ×1013m-1, 0.789 ×1013m-1 and 0.154×1013m-1 for the blend membrane, respectively. None of the classical Hermia’s models were able to accurately predict fouling during the entire filtration run. The results obtained from the combined pore blocking model indicated that the combined cake formation-intermediate blocking model provided good prediction of fouling mechanism for both the membranes. However, comparison between fitted parameters showed that much greater fouling occurred for pure HDPE membrane. The key reasons for such different fouling behaviors were mainly attributed to the difference in hydrophobicity as well as the distribution of pore size on the surface of the pure and blend membranes.
Catalysis
Laura Boggioni; Incoronata Tritto
Abstract
Highly active metallocenes and other single site catalysts have opened up the possibility of polymerizing cycloolefins such as norbornene (N) or of copolymerizing them with ethene (E) or propene (P). The polymers obtained show exciting structures and properties. E-N copolymers are industrially produced ...
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Highly active metallocenes and other single site catalysts have opened up the possibility of polymerizing cycloolefins such as norbornene (N) or of copolymerizing them with ethene (E) or propene (P). The polymers obtained show exciting structures and properties. E-N copolymers are industrially produced materials, with variable and high glass transitions depending on the wide range of their microstructures. By realizing the possibility in great variety of stereoregularity of propene and norbornene units and the difference in comonomer distribution, P-N copolymers were expected to have fine tuned microstructures and properties. Moreover, P-N copolymers should be characterized by higher Tg-values than E-N copolymers with the same norbornene content and molar mass. A review of the state of the art of P-N copolymerization by ansa-metallocenes of C2 symmetry, namely rac-Et(Ind)2ZrCl2 (I-I) and rac-Me2Si(Ind)2ZrCl2 (I-II), and rac-Me2Si(2-Me-Ind)2ZrCl2 (I-III), and of catalysts of Cssymmetry, namely (tBuNSiMe2Flu)TiMe2 (IV-I) and derivatives, is given here. Special emphasis is given to microstructural studies of P-N copolymers, including stereo- and regioregularity of propene units as well as of comonomer distribution, stereoregularity of norbornene units, and the structure of chain end-groups. This information allows us to find a rationale for the catalytic activities and the copolymer properties.
