Side-chain type benzoxazine-functional cellulose via click chemistry

A side-chain type benzoxazine-functional cellulose has been developed using click chemistry via the reaction of ethynyl-monofunctional benzoxazine monomer and azide-functional cellulose. The synthesis, crosslinking, and thermal properties of the benzoxazine-functional cellulose are studied by NMR, FTIR, DSC, and TGA. The crosslinking reaction of the benzoxazine side-chain unusually takes place at low-temperatures in comparison to an ordinary benzoxazine resins. Upon crosslinking, the polymer shows high char yield of 40%, which is a marked improvement from a mere 4% of the unfunctionalized cellulose. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of chain microstructure on the conformational behavior of ethylene-1-olefin copolymers. Impact of the comonomeric mole content and the catalytic inversion ratio

The rotational isomeric state model was employed to provide a better understanding of the role of chain microstructure on the conformational behavior of homogeneous ethylene-1-olefin copolymers. The chain microstructure was assembled in accordance with the copolymerization theory using a set of conditional probabilities in direct relation to the reactivity ratios and the feed compositions of the comonomers. The catalytic inversion influence on the tacticity of the polymeric microstructure was also taken into account by considering the replication probability during the Monte Carlo simulation. Statistical weight factors of the rotational isomeric states were evaluated using molecular dynamics runs of the various homopolymers according to the earlier work of Mattice et al. Probability distribution surfaces constructed by the integration of the molecular dynamics trajectories of sufficient length to sample all of the conformational space indicated the increase of the probability of g^±t joint states at the expense of g^±g^± pairs with the increase in the side chain length of the 1-olefin comonomers. It was also indicated that this behavior had a maximum around poly(1-butene)/poly(1-hexene) with an apparent reversal in case of poly(1-octene) due to the side chain crowding, which forces the chain to favor more of the g^±g^± joint states. The characteristic ratios calculated for the copolymers on the basis of the rotational isomeric state model also indicated the increased extension of the polymer backbone with the increase in the side chain length. The lower characteristic ratio calculated for the octene polymers may, in fact, explain the experimental observation that poly(1-octene) has a lower melting point than those of other poly(1-olefin)s of shorter side chains. A complete account of the role of tacticity on the characteristic ratio and the radial distribution function is also given.     

Organoiron Polyelectrolytes: Synthesis and Characterization of Cationic Cyclopentadienyliron Complexes of Polyarylether-Imines

The synthesis of an aromatic ether complex of cyclopentadienyliron containing two terminal aldehyde groups was achieved via metal-mediated nucleophilic aromatic substitution reactions. This dialdehyde monomer was subsequently reacted with a variety of aliphatic and aromatic diamines to produce the corresponding soluble cationic organoiron polyether-imines. These cationic organometallic polymers were characterized using IR, ¹H, and ¹³C NMR, viscosity and thermogravimetric analysis. Viscosity measurements showed that these polymers exhibited polyelectrolyte effects in DMSO solutions. Thermogravimetric analysis showed that decoordination of the iron moieties occurred at about 300°C for polymers with aliphatic spacers in their backbones, while the cyclopentadienyliron moieties were cleaved from the polymers with aromatic spacers in their backbones at about 200°C. Photolytic demetallation of the organoiron polymers resulted in the removal of the pendent cyclopentadienyliron moieties and allowed for the isolation of their organic analogs. While the organoiron polymers were soluble in polar organic solvents, the corresponding organic polymers exhibited very limited solubilities or were insoluble. The organic polymers had glass transition temperatures between 101 and 120°C     

Novel organic-inorganic hybrids prepared from polybenzoxazine and titania using sol-gel process

Novel organic-inorganic hybrids were prepared from polybenzoxazine and titania using sol-gel process by blending titanium isopropoxide as a precursor for titania with a typical benzoxazine monomer, bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane (Ba). Deep red brown and transparent hybrid materials were obtained after thermal cure at 200 °C. DSC indicated that, in the presence of titania precursor, the onset and maximum temperature of the exothermic peak due to the ring opening polymerization of Ba decreased by ca. 30 and 70 °C, respectively. Viscoelastic analyses revealed that the glass transition temperatures (T_g) of the polybenzoxazine-titania hybrids shifted to higher temperature than the neat polybenzoxazine. The storage moduli below T_g for the hybrids increased with the increase of the titania content, and the storage moduli were maintained constant up to higher temperature than the neat resin. TGA results confirmed that the thermal stability and char yield of polybenzoxazine increased by hybridization with titania.     

Optimizations and heat integrations on the separation of toluene and 1-butanol azeotropic mixture by pressure swing distillation

In this study, optimizations on separation of Toluene and 1-Butanol mixture is carried out by pressure swing distillation process. New heat integration methods are applied and compared to conventional PSD process by using vapor recompression technique combined with pressure swing distillation process. New heat integration methods show positive results to decrease the utilities used in the process. A simulator Aspen HYSYS V8.4 is used for simulating all processes. Cost analysis is also performed and Aspen HYSYS V8.4 optimizer program is used for optimizing profit for the process. Pressure is also optimized for minimum heat duty requirements in the process and the ultimate concern is to minimize the total reboiler heat duties and overall operating cost for the system which results into increasing profit.     

Synthesis and characterization of Ag nanoparticles embedded in PVA via UV-photoreduction technique for synthesis of Prussian blue pigment

Silver nanoparticles doped in polyvinyl alcohol (AgNps/PVA) were synthesized via polymer-promoted reductive reaction of AgNO₃ and PVA under time-dependent exposure to UV radiation. The AgNps/PVA composites were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction, UV–Vis spectroscopy, and transmission electron microscopy to describe the structure, nuclearity, and distribution of Ag Nps within the PVA matrix. The UV–Vis spectrum of AgNps/PVA exhibited a broad surface plasmon absorption around 425–443 nm which originated from the formation of Ag NPs. Surface analysis by XPS indicated that the Ag NPs were grown solely on the PVA surface at UV exposure time of 2 h (2.0AgNPs/PVA). Increasing the UV exposure time to 4 h will cause the transformation of metallic nanosilver to oxidized nanosilver. UV–Vis absorption spectra were in situ recorded to follow the synthesis of Prussian blue (PB) on 2.0AgNPs/PVA (PB@2.0AgNPs/PVA). The colloidal dispersion of 2.0AgNPs/PVA in an acidic medium containing free Fe(III) ions and potassium hexacyanoferrate(III) revealed an additional band centered at 720 nm due to the intermetal charge-transfer absorbance of the polymeric Fe(II)-C-N-Fe(III) of the PB@2.0AgNPs/PVA nanocomposite. Control experiments were shown to involve a spontaneous electron transfer reaction between 2.0AgNPs/PVA and Fe(III) ions, with a concomitant decomposition of hexacyanoferrate(III) and formation of PB was observed. Moreover, IR gave clear cut evidence for the synthesis of PB@2.0AgNPs/PVA from the appearance of a band for the cyano group at 2090 cm^?1.     

Tuned interactions of silver nanoparticles with ZSM-5 zeolite by adhesion-promoting poly(acrylic acid) deposited by electrospray ionization (ESI)

The electrospray ionization (ESI) method was used for deposition of thin films of poly(acrylic acid) (PAA) on Cu/ZSM-5 (5 wt.% Cu) and Ag–Cu/ZSM-5 (1 wt.% Ag and 4 wt.% Cu) composites. For comparative purposes, the ZSM-5 zeolite was synthesized under hydrothermal conditions and loaded with PAA under the same treating conditions as the composites. This method allowed the formation of uniform polymer films of controlled thickness on conductive substrates. The structural characteristics were characterized by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, atomic force microscopy and X-ray diffraction (XRD). The deposited PAA layer over ZSM-5 acts as a common dispersing and stabilizing agent through coordination-driven guest-templated polymer via interaction of Ag⁺ and Cu²⁺ with carboxylic acid groups, thus increasing and controlling the adhesion and the release of metallic species. A short exposure to light and temperature has reduced the metal ions to Cu⁰ and Ag⁰ metallic nanoparticles. The results of XRD analysis let suggest that the interaction of Cu and Ag with carboxylic groups of PAA inhibits the formation of large metallic silver particles. These samples were being studied for their potential as antibacterial agents toward the bacterial strains such as Staphylococcus pneumonia, Bacillus subtilis, Escherichia coli and Pseudomonas aeruginosa as Gram positive and Gram negative bacteria, respectively. Aspergillus fumigatus and Candida albicans as Fungi were also evaluated. The Cu/ZSM-5 and Ag–Cu/ZSM-5 nanocomposites coated with a 10 nm thick PAA layer exhibit significant antibacterial activity.     

Ameliorating Effects of Exogenously Applied Proline on Seed Composition,Seed Oil Quality and Oil Antioxidant Activity of Maize (Zea mays L.) under Drought Stress

This study was carried out to appraise whether or not the exogenous application of a potential osmoprotectant, proline, could ameliorate the adverse effects of drought stress on maize seed and seed oil composition, as well as oil antioxidant activity. Water stress reduced the kernel sugar, oil, protein and moisture contents and most of the seed macro- and micro-elements analyzed in both maize cultivars but it increased the contents of seed fiber and ash. Water stress increased the oil oleic acid content with a subsequent decrease in the amount of linoleic acid, resulting in an increased oil oleic/linoleic ratio for both maize cultivars. However, no variation was observed in oil stearic and palmitic acids content due to water stress. A considerable drought induced an increase in seed oil α-, γ-, δ- and total tocopherols and flavonoids were observed in both maize cultivars. However, oil phenolic and carotenoid content as well as 1,1-diphenyl-2-picryl-hydrazyl (DPPH) free radical scavenging activity decreased. Foliar-applied proline significantly increased the content of seed sugar, oil, protein, moisture, fiber and ash in both maize cultivars under well irrigated and water deficit conditions. Furthermore, exogenous application of proline increased the oil oleic and linoleic acid contents. The concentrations of antioxidant compounds namely phenolics, carotenoids, flavonoids and tocopherols estimated in the seed oil increased due to foliar-applied proline under water deficit conditions that was positively correlated with the enhanced oil DPPH free radical scavenging activity. Moreover, the increase in the contents of these antioxidant compounds and oil antioxidant activity due to the foliar application of proline was noted to be more pronounced under water deficit conditions.     

Polymerization behavior of methylol-functional benzoxazine monomer

This study focuses on methylol functional benzoxazines as precursors to build a network structure utilizing both benzoxazine and resole chemistry. The first part is a review of systems that contain methylol groups which play a role on their crosslinking formation. The polymerization mechanism and properties of resoles will be highlighted as the most abundant polymers that are characterized by polymerization through condensation reaction of methylol group. In the second part, the effect of incorporating methylol group into benzoxazine monomers is studied. Differential scanning calorimetry (DSC) is used to study the effect of methylol group on the rate of polymerization. Kissinger and Ozawa methods using non-isothermal DSC at different heating rates show that methylol monomer exhibits lower average activation energy compared to the un-functionalized monomer. The effect of adding catalysts into the monomers is also studied. p-Toluene sulfonic acid (PTSA) is found to be more efficient than 1-methyl-imidazole (IMD) and lithium iodide (LiI) in the case of methylol monomer due to its ability of accelerating both the methylol condensation and ring-opening polymerization. Additionally, thermal behavior of the monomers is studied using thermogravimetric analysis (TGA).