Search results for: olefin polymerization

Authors: R. Marandi, H. Shahrir, T. Nejad Ghaffar Borhani, M. Kamaruddin

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In the present study, a steady state population balance model was developed to predict the polymer particle size distribution (PSD) in ethylene gas phase fluidized bed olefin polymerization reactors. The multilayer polymeric flow model (MPFM) was used to calculate the growth rate of a single polymer particle under intra-heat and mass transfer resistance. The industrial plant data were used to calculate the growth rate of polymer particle and the polymer PSD. Numerical simulations carried out to describe the influence of effective monomer diffusion coefficient, polymerization rate and initial catalyst size on the catalyst particle growth and final polymer PSD. The results present that the intra-heat and mass limitation is important for the ethylene polymerization, the growth rate of particle and the polymer PSD in the fluidized bed reactor. The effect of the agglomeration on the PSD is also considered. The result presents that the polymer particle size distribution becomes broader as the agglomeration exits.

Keywords: population balance, olefin polymerization, fluidized bed reactor, particle size distribution, agglomeration

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Authors: Joanna Drzeżdżon, Marzena Białek

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Polyolefins are a group of materials used today in all areas of life. They are used in the food, domestic and other industries. In particular, polyethylene and polypropylene have found application in the production of packaging materials, pipes, containers, car parts as well as elements of medical equipment, e.g. syringes. Optimization of the polymerization and oligomerization processes of selected olefins is a very important stage before the technological implementation of polyolefin production. The purpose of the studies is to determine the conditions for ethylene polymerization as well as 3-buten-2-ol and 2-chloro-2-propen-1-ol oligomerization with the use of oxovanadium(IV) dipicolinate complexes with N-heterocyclic ligands. Additionally, the studies aims to determine the catalytic activities of the dipicolinate oxovanadium(IV) complexes with N-heterocyclic ligands in the studied polymerization and oligomerization processes.

Keywords: buten-2-ol, dipicolinate, ethylene, polymerization, oligomerization, vanadium

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Authors: Yuling Xu, Haibo Wang, Dong Xie

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A photopolymerizable dimethacrylamide was synthesized and copolymerized with the selected (meth)acrylates. The polymerization rate, degree of conversion, gel time, and compressive strength of the formed neat resins were investigated. The results show that in situ photo-polymerization of the synthesized dimethacrylamide with comonomers having an electron-withdrawing and/or acrylate group dramatically increased the polymerization rate, degree of conversion, and compressive strength. On the other hand, an electron-donating group on either carbon-carbon double bond or the ester linkage slowed down the polymerization. In contrast, the triethylene glycol dimethacrylate-based system did not show a clear pattern. Both strong hydrogen-bonding between (meth)acrylamide and organic acid groups may be responsible for higher compressive strengths. Within the limitation of this study, the photo-polymerization of dimethacrylamide can be greatly accelerated by copolymerization with monomers having electron-withdrawing and/or acrylate groups. The monomers with methacrylate group can significantly reduce the polymerization rate and degree of conversion.

Keywords: photopolymerization, dimethacrylamide, the degree of conversion, compressive strength

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Authors: Mehdi Seifollahi, Ashkan Forootan, Sajjad Bahrami Reyhan

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Due to the complexity of olefinic plants, various environmental pollutants exist such as NO_x, CO₂, Tar Water, and most importantly Spent Caustic. In this paper, instead of investigating ways of treating this pollutant, we evaluated the production in relation to plant’s variable items. We primarily discussed the factors affecting the quality of the output spent caustic such as impurities in the feed of olefin plant, the amount of injected dimethyl disulfide (DMDS) in furnaces, variation in feed composition, differences among gas temperatures and the concentration of caustic solution at the bottom of the tower. The results of the laboratory proved that in the formation of Red Oil, 1,3butadiene and acetaldehyde followed free radical and aldol condensation mechanism respectively. By increasing the injection rate of DMDS, Mercaptide amount increases in the effluent. In addition, pyrolysis gasoline accumulation is directly related to caustic concentration in the tower. Increasing naphtenes in the liquid feed augments the amount of 1,3butadiene, as one of the sources of Red Oil formation. By increasing the oxygenated compound in the feed, the rate of acetaldehyde formation, as the main source of Red Oil formation, increases.

Keywords: olefin, spent caustic, red oil, caustic wash tower

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Authors: Kun Qi, Yuman Zhou, Jianxin He

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A facile fabrication strategy via electrospinning and followed by in situ polymerization to fabricate a highly stretchable and conductive Poly(3,4-ethylenedioxythiophene)/Polyurethane (PEDOT/PU) nanofibrous membrane is reported. PU nanofibers were prepared by electrospinning and then PEDOT was coated on the plasma modified PU nanofiber surface via in-situ polymerization to form flexible PEDOT/PU composite nanofibers with conductivity. The results show PEDOT is successfully synthesized on the surface of PU nanofiber and PEDOT/PU composite nanofibers possess skin-core structure. Furthermore, the experiments indicate the optimal technological parameters of the polymerization process are as follow: The concentration of EDOT monomers is 50 mmol/L, the polymerization time is 24 h and the temperature is 25℃. The PEDOT/PU nanofibers exhibit excellent electrical conductivity ( 27.4 S/cm). In addition, flexible sensor made from conductive PEDOT/PU nanofibers shows highly sensitive response towards tensile strain and also can be used to detect finger motion. The results demonstrate promising application of the as-obtained nanofibrous membrane in flexible wearable electronic fields.

Keywords: electrospinning, polyurethane, PEDOT, conductive nanofiber, flexible senor

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Authors: H. Kazemi Esfeh, V. Akbari, M. Ehdaei, T. N. G. Borhani, A. Shamiri, M. Najafi

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In an industrial fluidized bed polymerization reactor, particle size distribution (PSD) plays a significant role in the reactor efficiency evaluation. The computational fluid dynamic (CFD) models coupled with population balance equation (CFD-PBM) have been extensively employed to investigate the flow behavior in the poly-disperse multiphase fluidized bed reactors (FBRs) utilizing ANSYS Fluent code. In this study, an existing CFD-PBM/ DQMOM coupled modeling framework has been used to highlight its potential to analyze the industrial-scale gas phase polymerization reactor. The predicted results reveal an acceptable agreement with the observed industrial data in terms of pressure drop and bed height. The simulated results also indicate that the higher particle growth rate can be achieved for bigger particles. Hence, the 2D CFD-PBM/DQMOM coupled model can be used as a reliable tool for analyzing and improving the design and operation of the gas phase polymerization FBRs.

Keywords: computational fluid dynamics, population balance equation, fluidized bed polymerization reactor, direct quadrature method of moments

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Authors: A. Belmokhtar, A. Yahiaoui, A. Benyoucef, M. Belbachir

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We reported the synthesis and characterization of nanocomposite poly (4,4’ methylenedianiline) via chemical polymerization of monomers 4,4’ methylenedianiline by ammonium persulfate (APS) at room temperature catalyzed by Maghnite-H+. A facile method was demonstrated to grow poly (4,4’ methylenedianiline) nanocomposite, which was carried out by mixing Ammonium Persulfate (APS) aqueous and 4,4’ methylenedianiline solution in the presence of Maghnite-H+ at room temperature The effect of amount of catalyst and time on the polymerization yield of the polymers was studied. Structure was confirmed by elemental analysis, UV vis, RMN-1H, and voltammetry cyclique.

Keywords: charaterization, maghnite-h+, polymerization, poly (4, 4’ methylenedianiline)

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Authors: M. G. Smitha, M. V. Murugendrappa

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Perovskite manganite La_0.7Ca_0.3MnO₃ was synthesized by Sol-gel method. Polymerization of pyrrole was carried by in-situ polymerization method. The composite of pyrrole (Py)/La_0.7Ca_0.3MnO₃ composite in the presence of oxidizing agent ammonium per sulphate to synthesize polypyrrole (PPy)/La_0.7Ca_0.3MnO₃ (LCM) composite was carried out by the same in-situ polymerization method. The PPy/LCM composites were synthesized with varying compositions like 10, 20, 30, 40, and 50 wt.% of LCM in Py. The surface morphologies of these composites were analyzed by using scanning electron microscope (SEM). The images show that LCM particles are embedded in PPy chain. The impedance measurement of PPy/LCM at different temperature ranges from 30 to 180 °C was studied using impedance analyzer. The study shows that impedance is frequency and temperature dependent and it is found to decrease with increase in frequency and temperature.

Keywords: polypyrrole, sol gel, impedance, composites

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Authors: Hande Taşdemir, Meral Şahin, Mehmet Saçak

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Conductive composite materials obtained by physical or chemical mixing of two or more components having conducting and insulating properties have been increasingly attracted. Kaolinite in kaolin clays is one of silicates with two layers of molecular sheets of (Si2O5)2− and [Al2(OH)4]2+ with the chemical composition Al2Si2O5(OH)4. The most abundant hydrophillic kaolinite is extensively used in industrial processes and therefore it is convenient for the preparation of organic/inorganic composites. In this study, conductive poly(N-ethylaniline)/kaolinite composite was prepared by chemical polymerization of N-ethyl aniline in the presence of kaolinite particles using ammonium persulfate as oxidant in aqueous acidic medium. Poly(N-ethylaniline) content and conductivity of composite prepared were systematically investigated as a function of polymerization conditions such as ammonium persulfate, N-ethyl aniline and HCl concentrations. Poly(N-ethylaniline) content and conductivity of composite increased with increasing oxidant and monomer concentrations up to 0.1 M and 0.2 M, respectively, and decreased at higher concentrations. The maximum yield of polymer in the composite (15.0%) and the highest conductivity value of the composite (5.0×10-5 S/cm) was achieved by polymerization for 2 hours at 20°C in HCl of 0.5 M. The structure, morphological analyses and thermal behaviours of poly(N-ethylaniline)/kaolinite composite were characterized by FTIR and XRD spectroscopy, SEM and TGA techniques.

Keywords: kaolinite, poly(N-ethylaniline), conductive composite, chemical polymerization

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Authors: Khalid A. Rabaeh, Belal Moftah, Ahmed A. Basfar, Akram A. Almousa

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Polymer gel dosimeters are tissue equivalent martial that fabricated from radiation sensitive chemicals which, upon irradiation, polymerize as a function of absorbed radiation dose. Polymer gel dosimeters can uniquely record the radiation dose distribution in three-dimensions (3D). A novel composition of normoxic polymer gel dosimeters based on radiation-induced polymerization of N-(Hydroxymethyl)acrylamide (NHMA) is introduced in this study for radiotherapy treatment planning. The dosimeters were irradiated by 10 MV photon beam of a medical linear accelerator at a constant dose rate of 600 cGy/min with doses up to 30 Gy. The polymerization degree is directly proportional to absorbed dose received by the polymer gel. UV/Vis spectrophotometer was used to investigate the degree of white color of irradiated NHMA gel which is associated to the degree of polymerization of polymer gel dosimeters. The absorbance increases with absorbed dose for all gel dosimeters in the dose range between 0 and 30 Gy. Dose rate , energy of radiation and the stability of the polymerization after irradiation were investigated. No appreciable effects of these parameters on the performance of the novel gel dosimeters were observed.

Keywords: dosimeter, gel, spectrophotometer, N-(Hydroxymethyl)acrylamide

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Authors: Amine Harrane, Mahmoud Belalia

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During the last decade, polymer layered silicate nanocomposites have received increasing attention from scientists and industrial researchers because they generally exhibit greatly improved mechanical, thermal, barrier and flame-retardant properties at low clay content in comparison with unfilled polymers or more conventional micro composites. Poly(ε-caprolactone) (PCL)-layered silicate nanocomposites have the advantage of adding biocompatibility and biodegradability to the traditional properties of nanocomposites. They can be prepared by in situ ring-opening polymerization of ε-caprolactone using a conventional initiator to induce polymerization in the presence of an organophilic clay, such as organomodified montmorillonite. Messersmith and Giannelis used montmorillonite exchanged with protonated 12-amino dodecanoic acid and Cr3+ exchanged fluorohectorite, a synthetic mica type of silicate. Sn-based catalysts such as tin (II) octoate and dibutyltin (IV) dimethoxide have been reported to efficiently promote the polymerization of ε-caprolactone in the presence of organomodified clays. In this work, we have used an alternative method to prepare PCL/montmorillonite nanocomposites. The cationic polymerization of ε-caprolactone was initiated directly by Maghnite-TOA, organomodified montmorillonite clay, to produce nanocomposites (Scheme 1). Resulted from nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), force atomic microscopy (AFM) and thermogravimetry.

Keywords: polycaprolactone, polycaprolactone/clay nanocomposites, biodegradables nanocomposites, Maghnite, Insitu polymeriation

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Authors: Nesrin Köken, Esin A. Güvel, Nilgün Kızılcan

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This work presents synthesis of α,ω-dithienyl terminated poly(ethylene glycol) (PEGTh) capable for further chain extension by either chemical or electrochemical polymerization. PEGTh was characterized by FTIR and 1H-NMR. Further, copolymerization of PEGTh and pyrrole (Py) was performed by chemical oxidative polymerization using ceric (IV) salt as an oxidant (PPy-PEGTh). PEG without end group modification was used directly to prepare copolymers with Py by Ce (IV) salt (PPy-PEG). Block copolymers with mole ratio of pyrrole to PEGTh (PEG) 50:1 and 10:1 were synthesized. The electrical conductivities of copolymers PPy-PEGTh and PPy-PEG were determined by four-point probe technique. Influence of the synthetic route and content of the insulating segment on conductivity and yield of the copolymers were investigated.

Keywords: chemical oxidative polymerization, conducting polymer, poly(ethylene glycol), polypyrrole

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Authors: Faezeh Aghazadeh, Mohammad Javad Sharifi

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The application of neural networks to model a full-scale industrial acetylene hydrogenation in olefin plant has been studied. The operating variables studied are the, input-temperature of the reactor, output-temperature of the reactor, hydrogen ratio of the reactor, [C₂H₂]input, and [C₂H₆]input. The studied operating variables were used as the input to the constructed neural network to predict the [C₂H₆]output at any time as the output or the target. The constructed neural network was found to be highly precise in predicting the quantity of [C₂H₆]output for the new input data, which are kept unaware of the trained neural network showing its applicability to determine the [C₂H₆]output for any operating conditions. The enhancement of [C₂H₆]output as compared with [C₂H₆]input was a consequence of low selective acetylene hydrogenation to ethylene.

Keywords: acetylene hydrogenation, Pd-Ag/Al₂O₃, artificial neural network, modeling, optimal design

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Authors: Görkem Ülkü, Nesrin Köken, Esin A. Güvel, Nilgün Kızılcan

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Ethoxylated nonyl phenols (ENP) and ceric ammonium nitrate redox systems have been used for the polymerization of vinyl and acrylic monomers. In that case, ENP acted as an organic reducing agent in the presence of Ce (IV) salt and a radical was formed. The polymers obtained with that redox system contained ENP chain ends because the radicals are formed on the reducing molecules. Similar copolymer synthesis has been reported using poly(ethylene oxide) instead of its nonyl phenol terminated derivative, ENP. However, copolymers of poly(ethylene oxide) and conducting polymers synthesized by ferric ions were produced in two steps. Firstly, heteroatoms (pyrrole, thiophene etc.) were attached to the poly(ethylene oxide) chains then copolymerization with heterocyclic monomers was carried out. In this work, ethoxylated nonylphenol (ENP) was reacted with 2-thiophenecarbonyl chloride in order to synthesize a macromonomer containing thienyl end-group (ENP-ThC). Then, copolymers of ENP-ThC and pyrrole were synthesized by chemical oxidative polymerization using iron (III) chloride as an oxidant.

Keywords: end capped polymer, ethoxylated nonylphenol, heterophase polymerization, polypyrrole

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Authors: Sukanya Devi Ramachandran, Vaishnavi Muralidharan, Kavya Chandrasekaran

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Polycaprolactone is polymer belonging to the polyester family that has noticeable characteristics of biodegradability and biocompatibility which is essential for medical applications. Polycaprolactone is produced by the ring opening polymerization of the monomer epsilon-Caprolactone (ε-CL) which is a closed ester, comprising of seven-membered ring. This process is normally catalysed by metallic components such as stannous octoate. It is difficult to remove the catalysts after the reaction, and they are also toxic to the human body. An alternate route of using enzymes as catalysts is being employed to reduce the toxicity. Lipase enzyme is a subclass of esterase that can easily attack the ester bonds of ε-CL. This research paper throws light on the extraction of lipase from germinating sunflower seeds and the activity of the biocatalyst in the polymerization of ε-CL. Germinating Sunflower seeds were crushed with fine sand in phosphate buffer of pH 6.5 into a fine paste which was centrifuged at 5000rpm for 10 minutes. The clear solution of the enzyme was tested for activity at various pH ranging from 5 to 7 and temperature ranging from 40oC to 70oC. The enzyme was active at pH6.0 and at 600C temperature. Polymerization of ε-CL was done using toluene as solvent with the catalysis of lipase enzyme, after which chloroform was added to terminate the reaction and was washed in cold methanol to obtain the polymer. The polymerization was done by varying the time from 72 hours to 6 days and tested for the molecular weight and the conversion of the monomer. The molecular weight obtained at 6 days is comparably higher. This method will be very effective, economical and eco-friendly to produce as the enzyme used can be regenerated as such at the end of the reaction and can be reused. The obtained polymers can be used for drug delivery and other medical applications.

Keywords: lipase, monomer, polycaprolactone, polymerization

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Authors: Jorge Prada, Christina Cordes, Carsten Harms, Walter Lang

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The development of microfluidic-based biosensors over the last years has shown an increasing employ of thermoplastic polymers as constitutive material. Their low-cost production, high replication fidelity, biocompatibility and optical-mechanical properties are sought after for the implementation of disposable albeit functional lab-on-chip solutions. Among the range of thermoplastic materials on use, the Cyclo-Olefin Copolymer (COC) stands out due to its optical transparency, which makes it a frequent choice as manufacturing material for fluorescence-based biosensors. Moreover, several processing techniques to complete a closed COC microfluidic biosensor have been discussed in the literature. The reported techniques differ however in their implementation, and therefore potentially add more or less complexity when using it in a mass production process. This work introduces and reports results on the application of a purely thermal bonding process between COC substrates, which were produced by the hot-embossing process, and COC foils containing screen-printed circuits. The proposed procedure takes advantage of the transition temperature difference between two COC grades foils to accomplish the sealing of the microfluidic channels. Patterned heat injection to the COC foil through the COC substrate is applied, resulting in consistent channel geometry uniformity. Measurements on bond strength and bursting pressure are shown, suggesting that this purely thermal bonding process potentially renders a technique which can be easily adapted into the thermoplastic microfluidic chip production workflow, while enables a low-cost as well as high-quality COC biosensor manufacturing process.

Keywords: biosensor, cyclo-olefin copolymer, hot embossing, thermal bonding, thermoplastics

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Authors: Kashan Bashir, Salah Naji Ahmed Sufyan, Mirza Umar Baig

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In this study, n-dodecane, tetralin, decalin, and tetramethybenzene (TMBE) were used as model compounds of alkanes, naphthenic-aromatic, cycloalkanes and alkyl-benzenes presented in hydro-diesel. The catalytic cracking properties of four model compounds over Y zeolite catalyst (Y-Cat.) and ZSM-5 zeolite catalysts (ZSM-5-Cat.) were probed. The experiment results revealed that high conversion of macromolecular paraffin and naphthenic aromatics were achieved over Y-Cat, whereas its low cracking activity of intermediate products micromolecules paraffin and olefin and high activity of hydride transfer reaction goes against the production of value-added products (light olefin and gasoline). In contrast, despite the fact that the hydride transfer reaction was greatly inhabited over ZSM-5-Cat, the low conversion of macromolecules was observed attributed to diffusion limitations. Interestingly, the mixed catalyst compensates for the shortcomings of the two catalysts, and a “relay reaction” between Y-Cat and ZSM-5-Cat was proposed. Specifically, the added Y-Cat acts as a “pre-cracking booster site” and promotes macromolecules conversion. The addition of ZSM-5-Cat not only significantly suppresses the hydride transfer reaction but also contributes to the cracking of immediate products paraffin and olefin into ethylene and propylene, resulting in a high yield of alkyl-benzene (gasoline), ethylene, and propylene with a low yield of naphthalene (LCO) and coke. The catalytic cracking evaluation experiments of mixed hydro-LCO were also performed to further clarify the “relay reaction” above, showing the highest yield of LPG and gasoline over mixed catalyst. The results indicate that the Y-cat and ZSM-5-cat have a synergistic effect on the conversion of hydro-diesel and corresponding value-added product yield and selective coke yield.

Keywords: synergistic effect, hydro-diesel cracking, FCC, zeolite catalyst, ethylene and propylene

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Authors: Vaclav Heral

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Ideas about the mechanism of heterogeneous catalytic hydrogenation are diverse. The Horiuti-Polanyi mechanism is most often referred to, based on the idea of a semi-hydrogenated state. In our opinion, it does not represent a satisfactory explanation of the hydrogenation mechanism, because, for example: (1) It neglects the fact that the bond of atomic hydrogen to the metal surface is strongly polarized, (2) It does not explain why a surface deprived of atomic hydrogen (by thermal desorption or by alkyne) loses isomerization capabilities, but hydrogenation capabilities remain preserved, (3) It was observed that during the hydrogenation of 1-alkenes, the reaction can be of the 0th order to hydrogen and to the alkene at the same time, which is excluded during the competitive adsorption of both reactants on the catalyst surface. We offer an alternative mechanism that satisfactorily explains many of the ambiguities: It is the idea of an independent course of olefin isomerization, catalyzed by acidic atomic hydrogen bonded on the surface of the catalyst, in addition to the hydrogenation itself, in which a two-layer complex appears on the surface of the catalyst: olefin bound to the surface and molecular hydrogen bound to it in the second layer. The rate-determining step of hydrogenation is the conversion of this complex into the final product. We believe that the Horiuti-Polanyi mechanism is flawed and we naturally think that our two-layer theory better describes the experimental findings.

Keywords: acidity of hydrogenation catalyst, Horiuti-Polanyi, hydrogenation, two-layer hydrogenation

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Authors: Xiang Zheng, Zhaoping Zhong

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In this study, Aspen Plus was used to simulate the whole process of biomass conversion to liquid fuel in different ways, and the main results of material and energy flow were obtained. The process optimization and evaluation were carried out on the four routes of cellulosic biomass pyrolysis gasification low-carbon olefin synthesis olefin oligomerization, biomass water pyrolysis and polymerization to jet fuel, biomass fermentation to ethanol, and biomass pyrolysis to liquid fuel. The environmental impacts of three biomass species (poplar wood, corn stover, and rice husk) were compared by the gasification synthesis pathway. The global warming potential, acidification potential, and eutrophication potential of the three biomasses were the same as those of rice husk > poplar wood > corn stover. In terms of human health hazard potential and solid waste potential, the results were poplar > rice husk > corn stover. In the popular pathway, 100 kg of poplar biomass was input to obtain 11.9 kg of aviation coal fraction and 6.3 kg of gasoline fraction. The energy conversion rate of the system was 31.6% when the output product energy included only the aviation coal product. In the basic process of hydrothermal depolymerization process, 14.41 kg aviation kerosene was produced per 100 kg biomass. The energy conversion rate of the basic process was 33.09%, which can be increased to 38.47% after the optimal utilization of lignin gasification and steam reforming for hydrogen production. The total exergy efficiency of the system increased from 30.48% to 34.43% after optimization, and the exergy loss mainly came from the concentration of precursor dilute solution. Global warming potential in environmental impact is mostly affected by the production process. Poplar wood was used as raw material in the process of ethanol production from cellulosic biomass. The simulation results showed that 827.4 kg of pretreatment mixture, 450.6 kg of fermentation broth, and 24.8 kg of ethanol were produced per 100 kg of biomass. The power output of boiler combustion reached 94.1 MJ, the unit power consumption in the process was 174.9 MJ, and the energy conversion rate was 33.5%. The environmental impact was mainly concentrated in the production process and agricultural processes. On the basis of the original biomass pyrolysis to liquid fuel, the enzymatic hydrolysis lignin residue produced by cellulose fermentation to produce ethanol was used as the pyrolysis raw material, and the fermentation and pyrolysis processes were coupled. In the coupled process, 24.8 kg ethanol and 4.78 kg upgraded liquid fuel were produced per 100 kg biomass with an energy conversion rate of 35.13%.

Keywords: biomass conversion, biofuel, process optimization, life cycle assessment

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Authors: Nasrin Bakhshizadeh, Ashkan Forootan

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A major problem that affects the quality control of polymer in the industrial polymerization is the lack of suitable on-line measurement tools to evaluate the properties of the polymer such as melt and density indices. Controlling the polymerization in ordinary method is performed manually by taking samples, measuring the quality of polymer in the lab and registry of results. This method is highly time consuming and leads to producing large number of incompatible products. An online application for estimating melt index and density proposed in this study is a neural network based on the input-output data of the polyethylene production plant. Temperature, the level of reactors' bed, the intensity of ethylene mass flow, hydrogen and butene-1, the molar concentration of ethylene, hydrogen and butene-1 are used for the process to establish the neural model. The neural network is taught based on the actual operational data and back-propagation and Levenberg-Marquart techniques. The simulated results indicate that the neural network process model established with three layers (one hidden layer) for forecasting the density and the four layers for the melt index is able to successfully predict those quality properties.

Keywords: polyethylene, polymerization, density, melt index, neural network

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Authors: Yu Zhang, Il Kim

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Polypeptides with defined peptide sequences illustrate the power of remarkable applications in drug delivery, tissue engineering, sensing and catalysis. Especially the cyclic polypeptides, the distinctive topological architecture imparts many characteristic properties comparing to linear polypeptides. Here, a facile and highly efficient strategy for the synthesis of linear and cyclic polypeptides is reported using N-heterocyclic carbenes (NHCs)-mediated ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCA) in the presence or absence of primary amine initiator. The polymerization proceeds rapidly in a quasi-living manner, allowing access to linear and cyclic polypeptides of well-defined chain length and narrow polydispersity, as evidenced by nuclear magnetic resonance spectrum (1H NMR and 13C NMR spectra) and size exclusion chromatography (SEC) analysis. The cyclic architecture of the polypeptides was further verified by matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectra (MALDI-TOF MS) and electrospray ionization (ESI) mass spectra, as well as viscosity studies. This approach can also simplify workup procedures and make bulk scale synthesis possible, which thereby opens avenues for practical uses in diverse areas, opening up the new generation of polypeptide synthesis.

Keywords: α-amino acid N-carboxyanhydrides, living polymerization, polypeptides, N-heterocyclic carbenes, ring-opening polymerization

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Authors: Wegene Demisie Jima

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Leather is a durable and flexible material used for various purposes including clothing, footwear, upholstery and gloves. However, the use of leather for smart product applications is a challenge since it is electrically insulating material. Here, we report a simple method to produce conducting glove leathers using an in-situ polymerization of pyrrole. The concentrations of pyrrole, ferric chloride and anthraquinone-2-sulfonic acid sodium salt monohydrate were optimized to produce maximum conductivity in the treated leathers. The coating of polypyrrole in the treated leathers was probed using FT-IR, X-ray diffraction and electron microscopic analysis. FTIR confirms that the formation of polypyrrole on the leather surface as well as presence of prominent N-C stretching band. X-ray diffraction analysis suggests para-crystallinity in the PPy-treated leathers.We further demonstrate that the treated leathers, with maximum conductivity of 7.4 S/cm, can be used for making conductive gloves for operating touch-screen devices apart from other smart product applications.

Keywords: electrical conductivity, in-situ polymerization, pyrrole, smart product

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Authors: Krasimira N. Zhilkova, Mariya K. Kyulavska, Roza P. Mateva

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The anionic polymerization of -caprolactam (CL) with bifunctional activators has been extensively studied as an effective and beneficial method of improving chemical and impact resistances, elasticity and other mechanical properties of polyamide (PA6). In presence of activators or macroactivators (MAs) also called polymeric activators (PACs) the anionic polymerization of lactams proceeds rapidly at a temperature range of 130-180C, well below the melting point of PA-6 (220C) permitting thus the direct manufacturing of copolymer product together with desired modifications of polyamide properties. Copolymers of PA6 with an elastic polypropylene glycol (PPG) middle block into main chain were successfully synthesized via activated anionic ring opening polymerization (ROP) of CL. Using novel PACs based on PPG polyols (with differ molecular weight) the anionic ROP of CL was realized and investigated in the presence of a basic initiator sodium salt of CL (NaCL). The PACs were synthesized as N-carbamoyllactam derivatives of hydroxyl terminated PPG functionalized with isophorone diisocyanate [IPh, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane] and blocked then with CL units via an addition reaction. The block copolymers were analyzed and proved with 1H-NMR and FT-IR spectroscopy. The influence of the CL/PACs ratio in feed, the length of the PPG segments and polymerization conditions on the kinetics of anionic ROP, on average molecular weight, and on the structure of the obtained block copolymers were investigated. The structure and phase behaviour of the copolymers were explored with differential scanning calorimetry, wide-angle X-ray diffraction, thermogravimetric analysis and dynamic mechanical thermal analysis. The crystallinity dependence of PPG content incorporated into copolymers main backbone was estimate. Additionally, the mechanical properties of the obtained copolymers were studied by notched impact test. From the performed investigation in this study could be concluded that using PPG based PACs at the chosen ROP conditions leads to obtaining well-defined PA6-b-PPG-b-PA6 copolymers with improved impact resistance.

Keywords: anionic ring opening polymerization, caprolactam, polyamide copolymers, polypropylene glycol

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Authors: Leonnel Mhuka

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Background: The field of photonics has witnessed substantial growth, with an increasing demand for miniaturized and high-performance optical components. Microstructured optical waveguides have gained significant attention due to their ability to confine and manipulate light at the subwavelength scale. Conventional fabrication methods, however, face limitations in achieving intricate and customizable waveguide structures. Two-photon polymerization (TPP) emerges as a promising additive manufacturing technique, enabling the fabrication of complex 3D microstructures with submicron resolution. Objectives: This experiment aimed to utilize two-photon polymerization to fabricate microstructured optical waveguides with precise control over geometry and dimensions. The objective was to demonstrate the feasibility of TPP as an additive manufacturing method for producing functional waveguide devices with enhanced performance. Methods: A femtosecond laser system operating at a wavelength of 800 nm was employed for two-photon polymerization. A custom-designed CAD model of the microstructured waveguide was converted into G-code, which guided the laser focus through a photosensitive polymer material. The waveguide structures were fabricated using a layer-by-layer approach, with each layer formed by localized polymerization induced by non-linear absorption of the laser light. Characterization of the fabricated waveguides included optical microscopy, scanning electron microscopy, and optical transmission measurements. The optical properties, such as mode confinement and propagation losses, were evaluated to assess the performance of the additive manufactured waveguides. Conclusion: The experiment successfully demonstrated the additive manufacturing of microstructured optical waveguides using two-photon polymerization. Optical microscopy and scanning electron microscopy revealed the intricate 3D structures with submicron resolution. The measured optical transmission indicated efficient light propagation through the fabricated waveguides. The waveguides exhibited well-defined mode confinement and relatively low propagation losses, showcasing the potential of TPP-based additive manufacturing for photonics applications. The experiment highlighted the advantages of TPP in achieving high-resolution, customized, and functional microstructured optical waveguides. Conclusion: his experiment substantiates the viability of two-photon polymerization as an innovative additive manufacturing technique for producing complex microstructured optical waveguides. The successful fabrication and characterization of these waveguides open doors to further advancements in the field of photonics, enabling the development of high-performance integrated optical devices for various applications

Keywords: Additive Manufacturing, Microstructured Optical Waveguides, Two-Photon Polymerization, Photonics Applications

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Authors: Mehrji Khosravan, Mostafa Fathali-Sianib, Davood Soudbar, Sasan Talebnezhad, Mohammad-Reza Ebrahimi

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The late transition metal catalyst of the end group of transition metals in the periodic table as Ni, Fe, Co, and Pd was grown up rapidly in polyolefin industries recently. These metals with suitable ligands exhibited special characteristic properties and appropriate activities in the production of polyolefins. The ligand 1,4-bis (2,6-diisopropyl phenyl) acenaphthene was synthesized by reaction of 2,6-diisopropyl aniline and acenaphthenequinone. The ligand was added to nickel (II) dibromide salt for synthesis the 1,4-bis (2,6 diisopropylphenyl) acenaphthene nickel (II) dibromide catalyst. The structure of the ligand characterized by IR technique. The catalyst then deposited on graphene and graphene oxide by vander walss-attachment for use in Ethylene slurry polymerization process in the presence of catalyst activator such as methylaluminoxane (MAO) in hexane solvent. The structure of the catalyst characterized by IR and TEM techniques and some of the polymers were characterized by DSC. The highest activity was achieved at 600 C for catalyst.

Keywords: α-diimine nickel (II) complex, graphene as supported catalyst, late transition metal, ethylene polymerization

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Authors: X. Han, S. Duan, C. Liu, C. Zhou, W. Zhu, L. Kong

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The ionic imprinting technique refers to the three-dimensional rigid structure with the fixed pore sizes, which was formed by the binding interactions of ions and functional monomers and used ions as the template, it has a high level of recognition to the ionic template. The preparation of monolithic column by the in-situ polymerization need to put the compound of template, functional monomers, cross-linking agent and initiating agent into the solution, dissolve it and inject to the column tube, and then the compound will have a polymerization reaction at a certain temperature, after the synthetic reaction, we washed out the unread template and solution. The monolithic columns are easy to prepare, low consumption and cost-effective with fast mass transfer, besides, they have many chemical functions. But the monolithic columns have some problems in the practical application, such as low-efficiency, quantitative analysis cannot be performed accurately because of the peak shape is wide and has tailing phenomena; the choice of polymerization systems is limited and the lack of theoretical foundations. Thus the optimization of components and preparation methods is an important research direction. During the preparation of ionic imprinted monolithic columns, pore-forming agent can make the polymer generate the porous structure, which can influence the physical properties of polymer, what’ s more, it can directly decide the stability and selectivity of polymerization reaction. The compounds generated in the pre-polymerization reaction could directly decide the identification and screening capabilities of imprinted polymer; thus the choice of pore-forming agent is quite critical in the preparation of imprinted monolithic columns. This article mainly focuses on the research that when using different pore-forming agents, the impact of zinc ion imprinted monolithic column on the enrichment performance of zinc ion.

Keywords: high performance liquid chromatography (HPLC), ionic imprinting, monolithic column, pore-forming agent

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Authors: Florin Leon, Silvia Curteanu

Abstract:

Developing complete mechanistic models for polymerization reactors is not easy, because complex reactions occur simultaneously; there is a large number of kinetic parameters involved and sometimes the chemical and physical phenomena for mixtures involving polymers are poorly understood. To overcome these difficulties, empirical models based on sampled data can be used instead, namely regression methods typical of machine learning field. They have the ability to learn the trends of a process without any knowledge about its particular physical and chemical laws. Therefore, they are useful for modeling complex processes, such as the free radical polymerization of methyl methacrylate achieved in a batch bulk process. The goal is to generate accurate predictions of monomer conversion, numerical average molecular weight and gravimetrical average molecular weight. This process is associated with non-linear gel and glass effects. For this purpose, an adaptive sampling technique is presented, which can select more samples around the regions where the values have a higher variation. Several machine learning methods are used for the modeling and their performance is compared: support vector machines, k-nearest neighbor, k-nearest neighbor and random forest, as well as an original algorithm, large margin nearest neighbor regression. The suggested method provides very good results compared to the other well-known regression algorithms.

Keywords: batch bulk methyl methacrylate polymerization, adaptive sampling, machine learning, large margin nearest neighbor regression

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Authors: Tsung-Yen Tsai, Naveen Bunekar, Ming Hsuan Chang, Wen-Kuang Wang, Satoshi Onda

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The structure-property relationship and initiator effect on bulk polymerized poly(methyl methacrylate) (PMMA)–oragnomodified layered silicate nanocomposites was investigated. In this study, we used 2, 2'-azobis (4-methoxy-2,4-dimethyl valeronitrile and benzoyl peroxide initiators for bulk polymerization. The bulk polymerized nanocomposites’ morphology was investigated by X-ray diffraction and transmission electron microscopy. The type of initiator strongly influences the physiochemical properties of the polymer nanocomposite. The thermal degradation of PMMA in the presence of nanofiller was studied. 5 wt% weight loss temperature (T5d) increased as compared to pure PMMA. The peak degradation temperature increased for the nanocomposites. Differential scanning calorimetry and dynamic mechanical analysis were performed to investigate the glass transition temperature and the nature of the constrained region as the reinforcement mechanism respectively. Furthermore, the optical properties such as UV-Vis and Total Luminous Transmission of nanocomposites are examined.

Keywords: initiator, bulk polymerization, layered silicates, methyl methacrylate

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Authors: Fatima Zohra Zeggai, Benjamin Carbonnier, Aïcha Hachemaoui, Ahmed Yahiaoui, Samia Mahouche-Chergui, Zakaria Salmi

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A series of polyaniline (PANI)/modified Montmorillonite (MMT) Clay nanocomposite materials have been successfully prepared by In-Situ polymerization in the presence of modified MMT-Clay or Diazonium-MMT-Clay. The obtained nanocomposites were characterized and compared by various physicochemical techniques. The presence of physicochemical interaction, probably hydrogen bonding, between clay and polyaniline, which was confirmed by FTIR, UV-Vis Spectroscopy. The electrical conductivity of neat PANI and a series of the obtained nanocomposites were also studied by cyclic voltammograms.

Keywords: polyaniline, clay, nanocomposites, in-situ polymerization, polymers conductors, diazonium salt

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Authors: Fatma Zehra Engin Sagirli, Eyup Sabri Kayali, A. Sezai Sarac

Abstract:

In this study, Poly (acrylonitrile-co-methylacrylate)/N-Methyl Pyrrole and Pyrrole ([P(AN-co-MA)]-NMPy and [P(AN-co-MA)]-PPy) core–shell nanoparticles were obtained by in situ emulsion polymerization in the presence of Sodium dodecyl benzene sulfonate and sodium dodecyl sulfate (SDBS and SDS) by using ammonium per sulphate in the aqueous medium. The spectroscopic characterizations during the formation of nanocomposites were studied using Attenuated total reflectance Fourier transform infrared (FTIR-ATR) spectroscopy, ultraviolet–visible spectrophotometer (Uv-Vis). Electrical conductivity of the emulsion solution was measured by Conductivity Meter from aqueous sample solution. Also, yield of the powder nanocomposites was measured. SDBS and SDS used for investigation of surfactant effect on yield, electrical conductivity and polymerization process. Determination of polymerization yield, (FTIR-ATR) and (Uv-Vis) prove that the SDBS surfactant become more incorporated into the conducting polymers and there is strong interaction between the [P(AN-co-MA)]-PPy derivatives which prepared by these surfactants. The similar inclusion of SDS into conducting polymers was not observed, there is a remarkable difference at nanocomposites which prepared with SDS.

Keywords: nanocomposites, core-shell, pyrole, surfactant

Procedia PDF Downloads 377