Search results for: UV-initiated copolymerization.

Authors: Mohammad Najafi, Hossein Roghani-Mamaqani, Mehdi Salami-Kalajahi, Vahid Haddadi-Asl

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A high-performance Monte Carlo simulation, which simultaneously takes diffusion-controlled and chain-length-dependent bimolecular termination reactions into account, is developed to simulate atom transfer radical copolymerization of styrene and nbutyl acrylate. As expected, increasing initial feed fraction of styrene raises the fraction of styrene-styrene dyads (fAA) and reduces that of n-butyl acrylate dyads (fBB). The trend of variation in randomness parameter (fAB) during the copolymerization also varies significantly. Also, there is a drift in copolymer heterogeneity and the highest drift occurs in the initial feeds containing lower percentages of styrene, i.e. 20% and 5%.

Keywords: Atom Transfer Radical Copolymerization, MonteCarlo Simulation, Copolymer Heterogeneity, Styrene n-ButylAcrylate

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Authors: Liliana M. Ştefan, Ana M. Pană, Geza Bandur, Marcel Popa, Lucian M. Rusnac

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Polymers are one of the most widely used materials in our every day life. The subject of renewable resources has attracted great attention in the last period of time. New polymeric materials derived from renewable resources, like carbohydrates draw attention to public eye especially because of their biocompatibility and biodegradability. The aim of our paper was to obtain environmentally compatible polymers from monosaccharides. Novel glycopolymers based on D-glucose have been obtained from copolymerization of a new monomer carrying carbohydrate moiety with methyl methacrylate (MMA) via free radical bulk polymerization. Differential scanning calorimetry (DSC) was performed in order to study the copolymerization process of the monomer into the chosen co-monomer; the activation energy of this process was evaluated using Ozawa method. The copolymers obtained were characterized using ATR-FTIR spectroscopy. The thermal stability of the obtained products was studied by thermogravimetry (TG).

Keywords: DSC, glycopolymer, monosaccarides, TG.

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Authors: M. Wannaborworn, B. Jongsomjit, T. Shiono

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Copolymerization of ethylene with 1-hexene was carried out using two ansa-fluorenyl titanium derivative complexes. The substituent effect on the catalytic activity, monomer reactivity ratio and polymer property was investigated. It was found that the presence of t-Bu groups on fluorenyl ring exhibited remarkable catalytic activity and produced polymer with high molecular weight. However, these catalysts produce polymer with narrow molecular weight distribution, indicating the characteristic of single-site metallocene catalyst. Based on 13C NMR, we can observe that monomer reactivity ratio was affected by catalyst structure. The rH values of complex 2 were lower than that of complex 1 which might be result from the higher steric hindrance leading to a reduction of 1- hexene insertion step.

Keywords: Constrained geometry catalyst, linear low density polyethylene, copolymerization, reactivity ratio

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Authors: Azza. A. Al-Ghamdi, Abir. A. Abdel-Naby

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The construction of Nitro -N-amino phenyl maleimide branches onto Cellulose acetate (CA) substrate by free radical graft copolymerization using benzoyl peroxide as initiator led to formation of highly thermal stable copolymers as shown from the results of gravimetric analysis (TGA). CA-g-2,4-dinitro amino phenyl maleimide exhibited higher thermal stability than the CA-g-4-nitro amino phenyl maleimide as shown from the initial decomposition temperature (T_o). This is due to the ability of nitro group to form hydrogen bonding with hydroxyl group of the glucopyranose ring which increases the crystallinity of polymeric matrix. The crystalline shapes representing the graft part are clearly distinct in the Emission scanning electron microscope (ESEM) morphology of the copolymer. A suggested reaction mechanism for the grafting process was also discussed.

Keywords: Cellulose acetate, crystallinity, graft copolymerization, thermal properties.

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Authors: Li Li, Li-Ru Xia, He-Ye Wang, Xiao-Dong Bi

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In this paper, we presented a highly sensitive immune-affinity monolithic array for detection of α-fetoprotein (AFP) and carcinoembryonic antigen (CEA). Firstly, the epoxy functionalized monolith arrays were fabricated using UV initiated copolymerization method. Scanning electron microscopy (SEM) image showed that the poly(BABEA-co-GMA) monolith exhibited a well-controlled skeletal and well-distributed porous structure. Then, AFP and CEA immune-affinity monolithic arrays were prepared by immobilization of AFP and CEA antibodies on epoxy functionalized monolith arrays. With a non-competitive immune response format, the presented AFP and CEA immune-affinity arrays were demonstrated as an inexpensive, flexible, homogeneous and stable array for detection of AFP and CEA.

Keywords: Chemiluminescent detection, immune-affinity, monolithic copolymer array, UV-initiated copolymerization.

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Authors: B. Tosh, C. R. Routray

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Homogeneous graft copolymerization of methyl methacrylate (MMA) onto cellulose was carried out in N, N – dimethyl acetamide/LiCl (DMAc/LiCl) and dimethyl sulfoxide/ paraformaldehyde (DMSO/PF) solvent system taking ceric ammonium nitrate (CAN), benzoyl peroxide (BPO) and tin (II)-2-ethyl hexanoate [Sn(Oct)2] as initiators. Different grafting parameters like graft yield (GY), grafting efficiency (GE) and total conversion of monomer to polymer (TC) were evaluated at different reaction conditions of temperature, time, and variation of the amount of monomer and initiator. The viscosity average molecular weight of grafted PMMA and number of grafts per cellulose chain were also calculated. The products were characterized by FT-IR and 1H-NMR analyses and possible reaction mechanisms were deduced. Thermal degradation of the grafted products was also studied by thermo-gravimetric analysis (TG) and differential thermo-gravimetry (DTG).

Keywords: Grafting, grafting efficiency, homogeneous medium, methyl methacrylate.

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Authors: Mehdi Salami-Kalajahi, Pejman Ganjeh-Anzabi, Vahid Haddadi-Asl, Mohammad Najafi

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In the following text, we show that by introducing universal kinetic scheme, the origin of rate retardation and inhibition period which observed in dithiobenzoate-mediated RAFT polymerization can be described properly. We develop our model by utilizing the method of moments, then we apply our model to different monomer/RAFT agent systems, both homo- and copolymerization. The modeling results are in an excellent agreement with experiments and imply the validity of universal kinetic scheme, not only for dithiobenzoate-mediated systems, but also for different types of monomer/RAFT agent ones.

Keywords: RAFT Polymerization, Mechanism, Kinetics, Moment Equations, Modeling.

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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 polymeriztion. 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 copolymer, poly(ethylene glycol), polypyrrole.

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Authors: Mohammad Sadeghi, Behrouz Heidari, Korush Montazeri

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In this article, we synthesize a novel chitosan -based superabsorbent hydrogel via graft copolymerization of mixtures acrylic acid (AA) and N-vinyl pyrollidon onto chitosan backbones. The polymerization reaction was carried out in an aqueous medium and in the presence of ammonium persulfate (APS) as an initiator and N,N'-methylene bisacrylamide (MBA) as a crosslinker.The hydrogel structures were confirmed by FTIR spectroscopy. The swelling behavior of these absorbent polymers was also investigated in various salt solutions. Results indicated that the swelling capacity decreased with an increase in the ionic strength of the swelling medium. Furthermore, the swelling of superabsorbing hydrogels was examined in solutions with pH values ranging between 1.0 and 13.0. It showed a reversible pH-responsive behavior at pHs 2.0 and 8.0. This on-off switching behavior makes the synthesized hydrogels as an excellent candidate for controlled delivery of bioactive agents.

Keywords: chitosan, acrylic acid, N-vinyl pyrollidon, hydrogel, Ibuprofen's drug delivery

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Authors: A. Buasri, N. Chaiyut, K. Iamma, K. Kongcharoen, K. Cheunsakulpong

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Biopolymers have gained much attention as ecofriendly alternatives to petrochemical-based plastics because they are biodegradable and can be produced from renewable feedstocks. One class of biopolyester with many potential environmentally friendly applications is polylactic acid (PLA) and polycaprolactone (PCL). The PLA/PCL biodegradable copolyesters were synthesized by bulk ring-opening copolymerization of successively added Llactide (LL) and ε-caprolactone (CL) in the presence of toluene, using 1-hexanol as initiator and stannous octoate (Sn(Oct)2) as catalyst. Reaction temperature, reaction time and amount of catalyst were evaluated to obtain optimum reaction conditions. The results showed that the %conversion increased with increases in reaction temperature and reaction time, but after a critical amount of catalyst was reached the %conversion decreased. The yield of PLA/PCL biopolymer achieved 98.02% at the reaction temperature 160 °C, amount of catalyst 0.3 mol% and reaction time of 48 h. In addition, the thermal properties of the product were determined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

Keywords: Biopolymer, Polylactic Acid (PLA), Polycaprolactone (PCL), L-Lactide (LL), ε-Caprolactone (CL)

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Authors: Azza A. Al-Ghamdi, Abir S. Abdel-Naby

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Cellulose acetate (CA) is a natural biodegradable polymer. It forms transparent films by the casting technique. CA suffers from high degree of water permeability as well as the low thermal stability at high temperatures. To adjust the CA polymeric films to the manufacture of food packaging, its thermal and mechanical properties should be improved. The modification of CA by grafting it with N-Amino phenyl maleimide (N-APhM) led to the construction of hydrophobic branches throughout the polymeric matrix which reduced its wettability as compared to the parent CA. The branches built onto the polymeric chains had been characterized by UV/Vis, ¹³C-NMR and ESEM. The improvement of the thermal properties was investigated and compared to the parent CA using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), differential thermal analysis (DTA), contact angle and mechanical testing measurements. The results revealed that the water-uptake was reduced by increasing the graft percentage. The thermal and mechanical properties were also improved.

Keywords: Cellulose acetate, food packaging, graft copolymerization.

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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, degree of conversion, compressive strength.

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Authors: S. Buchatip, A. Petchsuk

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Polylactic acid-g-polyvinyl acetate (PLLA-g-PVAc) was used as a compatibilizer for 50/50 starch/PLLA blend. PLLA-g- PVAc with different mol% of PVAc contents were prepared by grafting PVAc onto PLLA backbone via free radical polymerization in solution process. Various conditions such as type and the amount of initiator, monomer concentration, polymerization time and temperature were studied. Results showed that the highest mol% of PVAc grafting (16 mol%) was achieved by conducting graft copolymerization in toluene at 110°C for 10 h using DCP as an initiator. Chemical structure of the PVAc grafted PLLA was confirmed by 1H NMR. Blending of modified starch and PLLA in the presence compatibilizer with different amounts and mol% PVAc was acquired using internal mixer at 160°C for 15 min. Effects of PVAc content and the amount of compatibilizer on mechanical properties of polymer blend were studied. Results revealed that tensile strength and tensile modulus of polymer blend with higher PVAc grafting content compatibilizer showed better properties than that of lower PVAc grafting content compatibilizer. The amount of compatibilizer was found optimized in the range of 0.5-1.0 Wt% depending on the mol% PVAc.

Keywords: starch, PLLA, compatibilizer, free radical polymerization, blending

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Authors: M.S. Mazăre, A. M. Pană, L. M. Ştefan, M. Silion, M. Bălan, G. Bandur, L. M. Rusnac

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In the last decade, carbohydrates have attracted great attention as renewable resources for the chemical industry. Carbohydrates are abundantly found in nature in the form of monomers, oligomers and polymers, or as components of biopolymers and other naturally occurring substances. As natural products, they play important roles in conferring certain physical, chemical, and biological properties to their carrier molecules.The synthesis of this particular carbohydrate glycomonomer is part of our work to obtain biodegradable polymers. Our current paper describes the synthesis and characterization of a novel carbohydrate glycomonomer starting from D-glucose, in several synthesis steps, that involve the protection/deprotection of the D-glucose ring via acetylation, tritylation, then selective deprotection of the aromaticaliphatic protective group, in order to obtain 1,2,3,4-tetra-O-acetyl- 6-O-allyl-β-D-glucopyranose. The glycomonomer was then obtained by the allylation in drastic conditions of 1,2,3,4-tetra-O-acetyl-6-Oallyl- β-D-glucopyranose with allylic alcohol in the presence of stannic chloride, in methylene chloride, at room temperature. The proposed structure of the glycomonomer, 2,3,4-tri-O-acetyl-1,6-di- O-allyl-β-D-glucopyranose, was confirmed by FTIR, NMR and HPLC-MS spectrometry. This glycomonomer will be further submitted to copolymerization with certain acrylic or methacrylic monomers in order to obtain competitive plastic materials for applications in the biomedical field.

Keywords: allylation, D-glucose, glycomonomer, trityl chloride

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Authors: T. Moremedi, L. Katata-Seru, S. Sardar, A. Bandyopadhyay, E. Makhado, M. Joseph Hato

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The rapid industrialisation and population growth have led to a steady fall in freshwater supplies worldwide. As a result, water systems are affected by modern methods upon use due to secondary contamination. The application of novel adsorbents derived from natural polymer holds a great promise in addressing challenges in water treatment. In this study, the UV irradiation technique was used to prepare acrylamide (AAm) monomer, and acrylic acid (AA) monomer grafted xanthan gum (XG) copolymer. Furthermore, the factors affecting rhodamine B (RhB) adsorption from aqueous media, such as pH, dosage, concentration, and time were also investigated. The FTIR results confirmed the formation of graft copolymer by the strong vibrational bands at 1709 cm^-1 and 1612 cm^-1 for AA and AAm, respectively. Additionally, more irregular, porous and wrinkled surface observed from SEM of XG-g-AAm/AA indicated copolymerization interaction of monomers. The optimum conditions for removing RhB dye with a maximum adsorption capacity of 313 mg/g at 25 ⁰C from aqueous solution were pH approximately 5, initial dye concentration = 200 ppm, adsorbent dose = 30 mg. Also, the detailed investigation of the isothermal and adsorption kinetics of RhB from aqueous solution showed that the adsorption of the dye followed a Freundlich model (R² = 0.96333) and pseudo-second-order kinetics. The results further indicated that this absorbent based on XG had the universality to remove dye through the mechanism of chemical adsorption. The outstanding adsorption potential of the grafted copolymer could be used to remove cationic dyes from aqueous solution as a low-cost product.

Keywords: Xanthan gum, adsorbents, rhodamine B, Freundlich model.

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Authors: H. Ferfera-Harrar, T. Benhalima, D. Lerari

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Contamination of water, due to the discharge of untreated industrial wastewaters into the ecosystem, has become a serious problem for many countries. In this study, bioadsorbents based on chitosan-g-poly(acrylamide) and montmorillonite (MMt) clay (CTS-g-PAAm/MMt) hydrogel nanocomposites were prepared via free‐radical grafting copolymerization and crosslinking of acrylamide monomer (AAm) onto natural polysaccharide chitosan (CTS) as backbone, in presence of various contents of MMt clay as nanofiller. Then, they were hydrolyzed to obtain highly functionalized pH‐sensitive nanomaterials with uppermost swelling properties. Their structure characterization was conducted by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. The adsorption performances of the developed nanohybrids were examined for removal of methylene blue (MB) cationic dye from aqueous solutions. The factors affecting the removal of MB, such as clay content, pH medium, adsorbent dose, initial dye concentration and temperature were explored. The adsorption process was found to be highly pH dependent. From adsorption kinetic results, the prepared adsorbents showed remarkable adsorption capacity and fast adsorption rate, mainly more than 88% of MB removal efficiency was reached after 50 min in 200 mg L^-1 of dye solution. In addition, the incorporating of various content of clay has enhanced adsorption capacity of CTS-g-PAAm matrix from 1685 to a highest value of 1749 mg g^-1 for the optimized nanocomposite containing 2 wt.% of MMt. The experimental kinetic data were well described by the pseudo-second-order model, while the equilibrium data were represented perfectly by Langmuir isotherm model. The maximum Langmuir equilibrium adsorption capacity (q_m) was found to increase from 2173 mg g⁻¹ until 2221 mg g⁻¹ by adding 2 wt.% of clay nanofiller. Thermodynamic parameters revealed the spontaneous and endothermic nature of the process. In addition, the reusability study revealed that these bioadsorbents could be well regenerated with desorption efficiency overhead 87% and without any obvious decrease of removal efficiency as compared to starting ones even after four consecutive adsorption/desorption cycles, which exceeded 64%. These results suggest that the optimized nanocomposites are promising as low cost bioadsorbents.

Keywords: Chitosan, clay, dye adsorption, hydrogels nanocomposites.

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Authors: D. Berdous, H. Ferfera-Harrar

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Superabsorbent polymers (SAPs) or hydrogels with three-dimensional hydrophilic network structure are high-performance water absorbent and retention materials. The in situ synthesis of metal nanoparticles within polymeric network as antibacterial agents for bio-applications is an approach that takes advantage of the existing free-space into networks, which not only acts as a template for nucleation of nanoparticles, but also provides long term stability and reduces their toxicity by delaying their oxidation and release. In this work, SAP/nanosilver nanocomposites were successfully developed by a unique green process at room temperature, which involves in situ formation of silver nanoparticles (AgNPs) within hydrogels as a template. The aim of this study is to investigate whether these AgNPs-loaded hydrogels are potential candidates for antimicrobial applications. Firstly, the superabsorbents were prepared through radical copolymerization via grafting and crosslinking of acrylamide (AAm) onto chitosan backbone (Cs) using potassium persulfate as initiator and N,N’-methylenebisacrylamide as the crosslinker. Then, they were hydrolyzed to achieve superabsorbents with ampholytic properties and uppermost swelling capacity. Lastly, the AgNPs were biosynthesized and entrapped into hydrogels through a simple, eco-friendly and cost-effective method using aqueous silver nitrate as a silver precursor and curcuma longa tuber-powder extracts as both reducing and stabilizing agent. The formed superabsorbents nanocomposites (Cs-g-PAAm)/AgNPs were characterized by X-ray Diffraction (XRD), UV-visible Spectroscopy, Attenuated Total reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), Inductively Coupled Plasma (ICP), and Thermogravimetric Analysis (TGA). Microscopic surface structure analyzed by Transmission Electron Microscopy (TEM) has showed spherical shapes of AgNPs with size in the range of 3-15 nm. The extent of nanosilver loading was decreased by increasing Cs content into network. The silver-loaded hydrogel was thermally more stable than the unloaded dry hydrogel counterpart. The swelling equilibrium degree (Q) and centrifuge retention capacity (CRC) in deionized water were affected by both contents of Cs and the entrapped AgNPs. The nanosilver-embedded hydrogels exhibited antibacterial activity against Escherichia coli and Staphylococcus aureus bacteria. These comprehensive results suggest that the elaborated AgNPs-loaded nanomaterials could be used to produce valuable wound dressing.

Keywords: Antibacterial activity, nanocomposites, silver nanoparticles, superabsorbent hydrogel.

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