A series of poly(urea-formaldehyde) (PUF) microcapsules filled with dicyclopentadiene (DCPD) was successfully prepared by in situ polymerization. The effect of diverse process parameters and ingredients on the morphology of the microcapsules was observed by SEM, optical microscopy (OM) and digital microscopy. Different techniques for the characterization of the chemical structure and the core content were considered such as FT-IR and 1H-NMR as well as the characterization of thermal properties by DSC. High yields of free flowing powder of spherical microcapsules were produced. The synthesized microcapsules can be incorporated into another polymeric host material. In the event the host material cracks due to excessive stress or strong impact, the microcapsules would rupture to release the DCPD, which could polymerize to repair the crack.
In this paper, the synthesis and characterisation of caffeine-imprinted polymers are described. The polymers were prepared in monolithic form via both reversible addition-fragmentation chain-transfer (RAFT) polymerisation and conventional free radical polymerisation, using methacrylic acid and ethylene glycol dimethacrylate as the functional monomer and crosslinking agent, respectively. The potential benefits in applying RAFT polymerisation techniques towards the synthesis of molecularly imprinted polymers (MIPs) are explored and elucidated. The pore structures of the polymers produced were characterised by nitrogen sorption porosimetry and the molecular recognition properties of representative products were evaluated in high-performance liquid chromatography (HPLC) mode. Molecular imprinting effects were confirmed by analysing the relative retentions of analytes on imprinted and non-imprinted HPLC
stationary phases. It was found that a caffeine-imprinted polymer synthesised by RAFT polymerisation was superior to a polymer prepared using a conventional synthetic approach; the imprinting factor and column efficiency were found to be higher for the former material.
A new crosslinked chitosan grafted with methyl methacrylate (M-CTS) adsorbent was synthesized via free radical polymerization for effective removal of Cu(II) ions from aqueous solution. Crosslinked chitosan (1 g) was grafted with 29.96 × 10-1 M methyl methacrylate in the presence of 2.63 × 10-1 M ammonium persulfate as initiator at 60 °C for 2 h to give grafting and yield percentages of 201% and 67%, respectively. Batch adsorption experiment was performed as a function of solution pH, initial metal ion concentration and contact time. The isotherm data were adequately described by Langmuir model, while kinetic study revealed that the pseudo-second order rate model best fitted for the experimental data. The maximum adsorption capacity for M-CTS at pH 4 was 192.31 mg g-1. Furthermore, the reusability of over six adsorption-desorption cycles suggested that M-CTS is a durable adsorbent and good candidate for metal ions treatment.
50 years ago, Karl Ziegler and Giulio Natta were awarded the Nobel Prize for their discovery of the catalytic polymerization of ethylene and propylene using titanium compounds and aluminum-alkyls as co-catalysts. Polyolefins have grown to become one of the biggest of all produced polymers. New metallocene/methylaluminoxane (MAO) catalysts open the possibility to synthesize polymers with highly defined microstructure, tacticity, and steroregularity, as well as long-chain branched, or blocky copolymers with excellent properties. This improvement in polymerization is possible due to the single active sites available on the metallocene catalysts in contrast to their traditional counterparts. Moreover, these catalysts, half titanocenes/MAO, zirconocenes, and other single site catalysts can control various important parameters, such as co-monomer distribution, molecular weight, molecular weight distribution, molecular architecture, stereo-specificity, degree of linearity, and branching of the polymer. However, in most cases research in this area has reduced academia as olefin polymerization has seen significant advancements in the industries. Therefore, this paper aims to further motivate interest in polyolefin research in academia by highlighting promising and open areas for the future.
A synthesis of acrylonitrile (AN)/butyl acrylate (BA)/fumaronitrile (FN) and AN/EHA (ethyl hexyl acrylate)/FN terpolymers was carried out by redox polymerization using sodium bisulfite (SBS) and potassium persulphate (KPS) as initiator at 40 °C. The effect of comonomers, BA and EHA and termonomer, FN on the glass transition temperature (Tg) and stabilization temperature was studied using Differential Scanning Calorimetry (DSC). The degradation behavior and char yield were obtained by Thermogravimetric Analysis. The conversions of AN, comonomers (BA and EHA) and FN were 55%-71%, 85%-91% and 76%-79%, respectively. It was found that with the same comonomer feed (10%), the Tg of AN/EHA copolymer was lower at 63 °C compared to AN/BA copolymer (70 °C). AN/EHA/FN terpolymer also exhibited a lower Tg at 63 °C when compared to that of the AN/BA/FN terpolymer (67 °C). By incorporating BA and EHA into a PAN system, the char yield was reduced to ~38.0% compared to that of AN (~47.7%). It was found that FN reduced the initial cyclization temperature of AN/BA/FN and AN/EHA/FN terpolymers to 228 and 221 °C, respectively, in comparison to that of AN/BA and AN/EHA copolymers (~260 °C). In addition, FN reduced the heat liberation per unit time during the stabilization process that consequently reduced the emission of volatile group during this process. As a result, the char yields of AN/BA/FN and AN/EHA/FN terpolymers are higher at ~45.1% and ~43.9%, respectively, as compared to those of AN/BA copolymer (37.1%) and AN/EHA copolymer (38.0%).
In this work, poly(MBAAm-co-SBMA) zwitterionic polymer nanoparticles were synthesized in one-step via distillation-precipitation polymerization (DPP) and were characterized. [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) as monomer and N, N'-methylene bis(acrylamide) (MBAAm) as cross-linker are used for the synthesis of nanoparticles. As far as our knowledge, this is the first such report on the synthesis of poly(MBAAm-co-SBMA) nanoparticles via DPP. The newly synthesized nanoparticles were further employed for the surface modification of polysulfone (PSF) hollow fiber membranes for dye removal. The modified hollow fiber membrane exhibited the improved permeability (56 L/ m2 h bar) and dye removal (>98% of Reactive Black 5 and >80.7% of Reactive orange 16) with the high permeation of salts. Therefore, the as-prepared membrane can have potential application in textile and industrial wastewater treatment.
Functional surfaces and polymers with branched structures have a major impact on physicochemical properties and performance of membrane materials. With the aim of greener approach for enhancement of permeation, fouling resistance and detrimental heavy metal ion rejection capacity of polyetherimide membrane, novel grafting of poly (4-styrenesulfonate) brushes on low cost, natural bentonite was carried out via distillation-precipitation polymerisation method and employed as a performance modifier. It has been demonstrated that, modified bentonite clay exhibited significant improvement in the hydrophilicity, porosity, and water uptake capacity with 3 wt. % of additive dosage. SEM and AFM analysis showed the increase in macrovoides and surface roughness with increased additive concentration. Moreover, the inclusion of modified bentonite displayed an increase in permeation rate and high anti-irreversible fouling properties with reversible fouling ratio of 75.6%. The humic acid rejection study revealed that, PEM-3 membrane having rejection efficiency up to 87.6% and foulants can be easily removed by simple hydraulic cleaning. Further, nanocomposite membranes can be significantly employed for the removal of hazardous heavy metal ions with a rejection rate of 80% and its tentative mechanism was discussed. Conspicuously, bentonite clay-bearing poly (4-styrenesulfonate) brushes are having a synergistic effect on physicochemical properties of nanocomposite membrane to enhance the performance in real field applications.
Recent progress on highly tough and stretchable polymer networks has highlighted the potential of wearable electronic devices and structural biomaterials such as cartilage. For some given applications, a combination of desirable mechanical properties including stiffness, strength, toughness, damping, fatigue resistance, and self-healing ability is required. However, integrating such a rigorous set of requirements imposes substantial complexity and difficulty in the design and fabrication of these polymer networks, and has rarely been realized. Here, we describe the construction of supramolecular polymer networks through an in situ copolymerization of acrylamide and functional monomers, which are dynamically complexed with the host molecule cucurbit[8]uril (CB[8]). High molecular weight, thus sufficient chain entanglement, combined with a small-amount dynamic CB[8]-mediated non-covalent crosslinking (2.5 mol%), yields extremely stretchable and tough supramolecular polymer networks, exhibiting remarkable self-healing capability at room temperature. These supramolecular polymer networks can be stretched more than 100× their original length and are able to lift objects 2000× their weight. The reversible association/dissociation of the host-guest complexes bestows the networks with remarkable energy dissipation capability, but also facile complete self-healing at room temperature. In addition to their outstanding mechanical properties, the networks are ionically conductive and transparent. The CB[8]-based supramolecular networks are synthetically accessible in large scale and exhibit outstanding mechanical properties. They could readily lead to the promising use as wearable and self-healable electronic devices, sensors and structural biomaterials.
Compartmentalization was likely essential for primitive chemical systems during the emergence of life, both for preventing leakage of important components, i.e., genetic materials, and for enhancing chemical reactions. Although life as we know it uses lipid bilayer-based compartments, the diversity of prebiotic chemistry may have enabled primitive living systems to start from other types of boundary systems. Here, we demonstrate membraneless compartmentalization based on prebiotically available organic compounds, α-hydroxy acids (αHAs), which are generally coproduced along with α-amino acids in prebiotic settings. Facile polymerization of αHAs provides a model pathway for the assembly of combinatorially diverse primitive compartments on early Earth. We characterized membraneless microdroplets generated from homo- and heteropolyesters synthesized from drying solutions of αHAs endowed with various side chains. These compartments can preferentially and differentially segregate and compartmentalize fluorescent dyes and fluorescently tagged RNA, providing readily available compartments that could have facilitated chemical evolution by protecting, exchanging, and encapsulating primitive components. Protein function within and RNA function in the presence of certain droplets is also preserved, suggesting the potential relevance of such droplets to various origins of life models. As a lipid amphiphile can also assemble around certain droplets, this further shows the droplets' potential compatibility with and scaffolding ability for nascent biomolecular systems that could have coexisted in complex chemical systems. These model compartments could have been more accessible in a "messy" prebiotic environment, enabling the localization of a variety of protometabolic and replication processes that could be subjected to further chemical evolution before the advent of the Last Universal Common Ancestor.
Molecular imprinted polymers (MIP) are considered one of the most promising selective and novel separation methods for removal phenolic compound in wastewater treatment. MIP are crosslinked polymeric materials that exhibit high binding capacity and selectivity towards a target molecule (template), purposely present during the synthesis process. In this work MIP were prepared in a bulk polymerization method in acetonitrile using 2,4-dinitrophenol, acrylamide, ethylene glycol dimethacrylate, and benzoyl peroxide as template, functional monomer, cross-linker and initiator, respectively. An adsorption process for removal of nitrophenol using the fabricated MIP was evaluated under various pH and time conditions. The parameters studied for 2,4-dinitrophenol includes adsorption kinetics, adsorption isotherm, and selectivity. The maximum adsorption of nitrophenol by the fabricated MIP was 3.50 mg/g. The adsorption of 2,4-dinitrophenol by the fabricated MIP was found effective at pH 6.0. A kinetics study showed that nitrophenol adsorption follows a second order adsorption rate and the adsorption isotherm data is explained well by the Langmuir model.
This article demonstrates a novel nanoscale surface modification method to enhance the selectivity of porous poly(dimethylsiloxane) (PDMS) in removing oil from water. The surface modification method is simple and low cost by using sugar as a sacrificial template for temporal adhering of carbon nanotubes (CNT) before addition of PDMS prepolymer to encapsulate the CNT on its surface once polymerized. The PDMS-CNT demonstrated a tremendous increase in absorption capacity up to 3-fold compared to previously reported absorbents composed solely of PDMS. Besides showcasing excellent absorption capacity, the PDMS-CNT also shows a faster absorption rate (25 s) as compared to that of pure PDMS (40 s). The enhanced absorption rate is due to the incorporation of CNT, which roughens the surface of the polymer at the nanoscale and lowers the surface energy of porous PDMS while at the same time increasing the absorbent hydrophobicity and oleophilicity. This property makes the absorbent unique in absorbing only oil but repelling water at the same time. The PDMS-CNT is an excellent absorbent material with outstanding recyclability and selectivity for removing oil from water.
In this study, a novel multiphasic model for the calculation of the polypropylene production in a complicated hydrodynamic and the physiochemical environments has been formulated, confirmed and validated. This is a first research attempt that describes the development of the dual-phasic phenomena, the impact of the optimal process conditions on the production rate of polypropylene and the fluidized bed dynamic details which could be concurrently obtained after solving the model coupled with the CFD (computational fluid dynamics) model, the basic mathematical model and the moment equations. Furthermore, we have established the quantitative relationship between the operational condition and the dynamic gas⁻solid behavior in actual reaction environments. Our results state that the proposed model could be applied for generalizing the production rate of the polymer from a chemical procedure to pilot-scale chemical reaction engineering. However, it was assumed that the solids present in the bubble phase and the reactant gas present in the emulsion phase improved the multiphasic model, thus taking into account that the polymerization took place mutually in the emulsion besides the bubble phase. It was observed that with respect to the experimental extent of the superficial gas velocity and the Ziegler-Natta feed rate, the ratio of the polymer produced as compared to the overall rate of production was approximately in the range of 9%⁻11%. This is a significant amount and it should not be ignored. We also carried out the simulation studies for comparing the data of the CFD-dependent dual-phasic model, the emulsion phase model, the dynamic bubble model and the experimental results. It was noted that the improved dual-phasic model and the CFD model were able to predict more constricted and safer windows at similar conditions as compared to the experimental results. Our work is unique, as the integrated developed model is able to offer clearer ideas related to the dynamic bed parameters for the separate phases and is also capable of computing the chemical reaction rate for every phase in the reaction. Our improved mutiphasic model revealed similar dynamic behaviour as the conventional model in the initial stages of the polymerization reaction; however, it diverged as time progressed.
The composite polymer films of polyvinyl alcohol/polypyrrole/chloral hydrate (PVA-PPy-CH) had been prepared. Effects of γ-rays on the electrical conductivity of the composite polymer films had been investigated by using Inductance Capacitance Resistance meter (LCR) meter at a frequency ranging from 20 Hz to 1 MHz. With the incorporation of chloral hydrate in the polymer sample, the conductivity increased indicates that it is capable to be used as dopant for polymerizing conjugated polymer. The electrical conductivity obtained increased as the dose increased, which is in the order of 10-5 Scm-1 indicates that γ-rays is capable to enhance the electrical conductivity of the composite polymer films. The parameter of s is in the range of 0.31 d s d 0.49 and obeyed simple power law dispersion ωs. The Scanning Electron Microscopy (SEM) micrographs reveal the formation of polypyrrole globules in polyvinyl alcohol matrix which increased as the irradiation dose was increased.
The composite polymer films of polyvinyl alcohol/polypyrrole/chloral hydrate (PVA-PPy-CH) had been prepared. Effects of J-rays on the electrical conductivity of the composite polymer films had
been investigated by using Inductance Capacitance Resistance meter (LCR) meter at a frequency
ranging from 20 Hz to 1 MHz. With the incorporation of chloral hydrate in the polymer sample, the conductivity increased indicates that it is capable to be used as dopant for polymerizing conjugated polymer. The electrical conductivity obtained increased as the dose increased, which is in the order of 10-5Scm-1 indicates that J-rays is capable to enhance the electrical conductivity of the composite polymer films. The parameter of s is in the range of 0.31 d s d 0.49 and obeyed simple power law dispersion Zs. The Scanning Electron Microscopy (SEM) micrographs reveal the formation of polypyrrole globules in polyvinyl alcohol matrix which increased as the irradiation dose was increased.
Graft copolymerisation of methyl methacrylate (MMA) onto Agave angustifolia was conducted with ceric ammonium nitrate (CAN) as the redox initiator. The maximum grafting efficiency was observed at CAN and MMA concentrations of 0.91 × 10(-3) and 5.63 × 10(-2)M, respectively, at 45°C for 3h reaction time. Four characteristic peaks at 2995, 1738, 1440, and 845 cm(-1), attributed to PMMA, were found in the IR spectrum of grafted cellulose. The crystallinity index dropped from 0.74 to 0.46, while the thermal stability improved upon grafting. The water contact angle increased with grafting yield, indicating increased hydrophobicity of cellulose. SEM images showed the grafted cellulose to be enlarged and rougher. The changes in the physical nature of PMMA-grafted cellulose can be attributed to the PMMA grafting in the amorphous regions of cellulose, causing it to expand at the expense of the crystalline component.
Biosynthesis and in vivo depolymerization of intracellular medium-chain-length poly-3-hydroxyalkanoates (mcl-PHA) in Pseudomonas putida Bet001 grown on lauric acid were studied. Highest mcl-PHA fraction (>50 % of total biomass) and cell concentration (8 g L-1 ) were obtained at carbon-to-nitrogen (C/N) ratio 20, starting cell concentration 1 g L-1 , and 48 H fermentation. The mcl-PHA comprised of 3-hydroxyhexanoate (C6 ), 3-hydroxyoctanote (C8 ), 3-hydroxydecanoate (C10 ), and 3-hydroxydodecanoate (C12 ) monomers. In vivo action was studied in a mineral liquid medium without carbon source, and in different buffer solutions with varied pH, molarity, ionic strength, and temperature. The monomer liberation rate reflected the mol percentage distribution of the initial polymer subunit composition. Rate and percentage of in vivo depolymerization were highest in 0.2 M Tris-HCl buffer (pH 9, strength = 0.2 M, 30 °C) at 0.21 g L-1 H-1 and 98.6 ± 1.3 wt%, respectively. There is a congruity vis-à-vis to specific buffer type, molarity, pH, ionic strength, and temperature values for superior in vivo depolymerization activities. Direct products from in vivo depolymerization matched the individual monomeric composition of native mcl-PHA. It points to exo-type reaction for the in vivo process, and potential biological route to chiral molecules.
In this paper, we review various novel/modified interfacial polymerization (IP) techniques for the fabrication of polyamide (PA) thin film composite (TFC)/thin film nanocomposite (TFN) membranes in both pressure-driven and osmotically driven separation processes. Although conventional IP technique is the dominant technology for the fabrication of commercial nanofiltration (NF) and reverse osmosis (RO) membranes, it is plagued with issues of low membrane permeability, relatively thick PA layer and susceptibility to fouling, which limit the performance. Over the past decade, we have seen a significant growth in scientific publications related to the novel/modified IP techniques used in fabricating advanced PA-TFC/TFN membranes for various water applications. Novel/modified IP lab-scale studies have consistently, so far, yielded promising results compared to membranes made by conventional IP technique, in terms of better filtration efficiency (increased permeability without compensating solute rejection), improved chemical properties (crosslinking degree), reduced surface roughness and the perfect embedment of nanomaterials within selective layers. Furthermore, several new IP techniques can precisely control the thickness of the PA layer at sub-10 nm and significantly reduce the usage of chemicals. Despite the substantial improvements, these novel IP approaches have downsides that hinder their extensive implementation both at the lab-scale and in manufacturing environments. Herein, this review offers valuable insights into the development of effective IP techniques in the fabrication of TFC/TFN membrane for enhanced water separation.
The effect of filler content and storage conditions such as drying, storing in water and thermal cycling on linear dimensional changes were investigated and evaluated. The dimensional accuracy studies were performed using a specific designed mould and a coordinate measuring machine. The findings gave support to the view that tiller content is an important factor influencing the physical and mechanical properties of the composite inlay material. The higher tiller content gave less polymerization shrinkage. The greatest linear shrinkage recorded was 0.79 %. The average linear shrinkage (in air, water and thermal cycling) for 79 % filler Prisma AP.H was 0.33 %, for 65 % tiller Prisma AP.H was 0.35 % and for 50 % filler Prisma AP.H was 0.42 %. Generally, dimensional changes was greatest when stored dry. This was followed by materials which were thermal cycled. The least dimensional change recorded was when the materials were stored in water.
The aim of the study was to evaluate post-polymerization of resin composite by measuring NanoHardness (H), Young’s Modulus (E) and Degree of Conversion (DC) using nanoindentation and Micro-Raman spectroscopy. For this purpose a computer-controlled NanoIndenter™ and a Renishaw 1000 Raman Spectrometer fitted with an Olympus microscope attachment, operated at 638 nm, were used. A light-activated resin composite was used in this study, (Z250, 3MESPE). Sub-groups (n=3) of specimens were irradiated for 20, 30, 40 s. All samples for nanoindentation were polished metallographically and typically 50 nanoindentations were performed per specimen. After curing and polishing, half of the samples were tested immediately (Group 1); the others after being stored dry at 37 °C for 7 days (Group 2) to allow scope for postpolymerization. H values ranged from 1.08 to 1.40 GPa for Group 1, and from 1.64 to1.71 GPa for Group 2. E values in Group 1 ranged from 19.60 to 19.94 GPa and for Group 2, from 21.42 to 22.05 GPa. DC values ranged from 55 to 66.39%, and 60.90 to 66.47% for Group 1 and Group 2 respectively. All values obtained shown significant different between Groups 1 and 2 (p
A molecularly imprinted polymer (MIP), with the ability to bind Pb(II) ion, was prepared using the non-covalent molecular imprinting methods and evaluated as a sorbent for the Pb(II) ion uptake. 4-vinylbenzoic acid was chosen as the complexing monomer. The imprinted polymer was synthesized by radical polymerization. The template (Pb(II) ions) was removed using 0.1 M HCl. As a result, the efficient adsorption was found to occur at pH 7. The result also showed the applicability of the Langmuir model for the sorption, with the maximum sorption capacity of 204.08 μg/mg.