Urethane‐forming reaction kinetics and catalysis of model palm olein polyols: Quantified impact of primary and secondary hydroxyls

Model palm olein natural oil polyols (NOPs) with varying ratios of primary to secondary hydroxyls were synthesized, characterized, and evaluated in reaction kinetics study with isocyanate in formation of polyurethanes. Reaction rate constants and activation energies associated with primary and secondary hydroxyls of NOPs were quantified. The kinetic study in toluene shows that the NOP containing primary hydroxyls have three times higher reaction rate constants in noncatalyzed reaction with 4,4′‐diphenylmethane diisocyanate (4,4′‐MDI) compared to the model NOP containing only secondary hydroxyls, which is associated with higher activation energy of secondary hydroxyls. However, the difference in reaction rate constants of primary and secondary hydroxyls in NOPs diminished in the reactions catalyzed with dibutyltin dilaurate. Bulk polymerization reaction confirms the kinetics results in toluene, showing that the model NOP containing primary hydroxyls reached gel time at a faster rate. Evaluation of elastomers from bulk polymerization shows low degree of phase separation of hard and soft segments for elastomers based on the model NOPs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42955.     

The morphology and gas‐separation performance of membranes comprising multiwalled carbon nanotubes/polysulfone–Kapton

The development of desirable chemical structures and properties in nanocomposite membranes involve steps that need to be carefully designed and controlled. This study investigates the effect of adding multiwalled nanotubes (MWNT) on a Kapton–polysulfone composite membrane on the separation of various gas pairs. Data from Fourier transform infrared spectroscopy and scanning electron microscopy confirm that some studies on the Kapton–polysulfone blends are miscible on the molecular level. In fact, the results indicate that the chemical structure of the blend components, the Kapton–polysulfone blend compositions, and the carbon nanotubes play important roles in the transport properties of the resulting membranes. The results of gas permeability tests for the synthesized membranes specify that using a higher percentage of polysulfone (PSF) in blends resulted in membranes with higher ideal selectivity and permeability. Although the addition of nanotubes can increase the permeability of gases, it decreases gas pair selectivity. Furthermore, these outcomes suggest that Kapton–PSF membranes with higher PSF are special candidates for CO₂/CH₄ separation compared to CO₂/N₂ and O₂/N₂ separation. High CH₄, CO₂, N₂, and O₂ permeabilities of 0.35, 6.2, 0.34, and 1.15 bar, respectively, are obtained for the developed Kapton–PSF membranes (25/75%) with the highest percentage of carbon nanotubes (8%), whose values are the highest among all the resultant membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43839.     

Synthesis and characterization of exfoliated poly(styrene‐co‐methyl methacrylate) nanocomposite via miniemulsion atom transfer radical polymerization: an activators generated by electron transfer approach

Exfoliated poly(styrene‐co‐methyl methacrylate) nanocomposites were synthesized using activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP). Miniemulsion polymerization was used for its abundant advantages to encapsulate inorganic materials and eliminate organic solvents from products for environmentally friendly purposes. Cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, which is an effective surfactant at higher temperatures, was used to stabilize the miniemulsion system. Successful miniemulsion AGET ATRP was carried out by using 4,4'‐dinonyl‐2,2'‐bipyridine (dNbPy) as a hydrophobic ligand. Formation of monodispersed droplets and particles with sizes in the range of 200nm was examined by dynamic light scattering (DLS). Conversion and molecular weight study were also carried out using gravimetry and gel permeation chromatography, respectively. By adding clay content, a decrease in the conversion and molecular weight of the nanocomposites are observed. However, an increase in the PDI values of nanocomposites was observed by the addition of nanoclay content. Thermogravimetric analysis results demonstrate that thermal stability of all the nanocomposites in comparison with the neat copolymer increases. Differential scanning calorimetry results show that T_g decreases by increasing clay content. Monodisperse distribution of spherical shape particles with sizes in the range of ∼ 200 nm was demonstrated by using scanning electron microscopy images of nanocomposite containing 1 wt% of nanoclay, which is more compiled with DLS results. Transmission electron microscopy results shows well‐dispersed exfoliated clay layers in the polymer matrix of PSMNM 1, which is coincidence with X‐ray diffraction data. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Preparation of tailor‐made polystyrene nanocomposite with mixed clay‐anchored and free chains via atom transfer radical polymerization

Tailor‐made polystyrene nanocomposite with mixed free and clay‐attached polystyrene chains was synthesized using atom transfer radical polymerization. Vinylbenzyl trimethylammonium chloride having a double bond, which could be incorporated into polystyrene chains by a grafting through process, was used as a nanoclay modifier. Conversion and molecular weight evaluation was carried out using gas chromatography and gel permeation chromatography, respectively. The thermogravimetric analysis results confirmed the elevated thermal stability of the nanocomposites in comparison with the neat polystyrene sample. Additionally, the T_g increases by clay loading was confirmed by differential scanning calorimetry (DSC). The difference in the degradation temperature of C? Br bond in attached and free polystyrene chains was well revealed in DSC thermograms. Finally, a lower clay loading resulted in an exfoliated structure as proved by X‐ray diffraction and transmission electron microscopy results. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Synthesis and Characterization of ZnO Nanoparticles via Thermal Decomposition of Two Zinc(II) Supramolecular Compounds

A new nano-sized Zn(II) complex, [Zn(5,5′-dtbu-2,2′-bipy)Cl₂] _n (1) was synthesized and its structure determined by X-ray crystallography. The new nano-sized complex was prepared at oleic acid as a surfactant at 280 °C and characterized by scanning electron microscopy, elemental analyses and IR spectroscopy. The ZnO nano-particles were synthesized from thermolysis of nano-compound 1 at 600 °C and similar compound, [Zn(5,5′-dimethyl-2,2′-bipy)Cl₂] _n (2), at two different methods. SEM images show the average size of ZnO nano-particles are 78 and 50 nm for the compounds 1 and 2, respectively.     

Theoretical and practical investigations of copper ion selective electrode with polymeric membrane based on N,N′-(2,2-dimethylpropane-1,3-diyl)-bis(dihydroxyacetophenone)

A novel ion-selective poly(vinyl chloride) (PVC) membrane sensor for Cu²⁺ ions based on N,N′-(2,2-dimethylpropane-1,3-diyl)-bis(dihydroxyacetophenone) (NDHA) as a new ionophore was prepared and studied. The best performance was observed for the membrane composition, including 30:65:1:4 (wt%) = PVC:DBP:KTpClPB:NDHA. The electrode showed a good Nernstian slope of 30.0 ± 0.5 mV/decade in a wide linear range activity of 3.0 × 10⁻⁷ to 1.0 × 10⁻² mol dm⁻³ Cu(NO₃)₂ with limit of detection 2.5 × 10⁻⁷. Sensor exhibited a fast response time (t_95% < 10 s) and could be used for about 4 months in the pH range of 3.0–7.4. The proposed potentiometric sensor was found to work satisfactorily in partially non-aqueous media up to 30 (vol%) content of methanol, ethanol and acetone. Applications of this electrode for the determination of copper in real samples, and as an indicator electrode for potentiometric titration of Cu²⁺ ion using EDTA, were reported. In order to predict the extraction ability of NDHA for different metallic ions, the complexes [M(NDHA)] and [M(H₂O)₆] (where M = Cu²⁺, Co²⁺, Hg²⁺, Pb²⁺, Ag⁺, Mg²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Cd²⁺, K⁺ and Al³⁺) were investigated using ab initio theoretical calculations. The metal binding capability was evaluated using the binding energy. Results of our study could be useful for prediction of the extraction power of this Schiff base and could play a guiding role in planning experiments.     

Using weighted pseudo‐inverse method for reconstruction of reflectance spectra and analyzing the dataset in terms of normality

Most of spectral estimation methods are based on improving the learning‐based procedures which mainly modify the training sets used by the basic methods. In this article, a new method is developed for analyzing of superiority of these modified processes to the basic methods in terms of normality of datasets. Hence, two qualitative terms, named generality and similarity are introduced to interpret the recovery achievements of different databases and their roles as training and testing sets. Also, a simple technique based on dataset modification of pseudo‐inverse method is introduced for the recovery of reflectance spectra of samples from their corresponding colorimetric data. The method modifies the training dataset according to the color specifications of test sample. In fact, different weighting matrices are employed as dynamic modifiers to improve the pseudo‐inverse estimation as a simple recovery method. The employed datasets are examined in the self as well as cross test conditions and the results are spectrally and colorimetrically evaluated. The root mean square errors between the reconstructed and actual spectra along with the corresponding color difference values under different illuminants decrease by employing the suggested modification method in comparison to classical pseudo‐inverse technique as well as the recently improved version named optimized adaptive Wiener method. © 2010 Wiley Periodicals, Inc. Col Res Appl, 2010     

First-principles DFT study of SO2 and SO3 adsorption on 2PANI: a model for polyaniline response

Interaction of SO_x (x?=?2,3) molecules on active sites of dianiline (as a model for polyaniline, denoted here as 2PANI) was studied using density functional theory at the BLYP-D/6-31+G(d) level of theory. Natural population analysis was used to find out the charge distribution as well as the net transferred charge of SO_x upon adsorption on 2PANI and the result has been compared with Mulliken charge analysis to evaluate the sensing ability of 2PANI. The computed density of states point to the remarkable orbital hybridization between SO_x and 2PANI during the adsorption process. As a consequence, the results of UV–VIS confirm the sensing ability of 2PANI toward SO₂ and SO₃. Based on our results, it can be found that at proper configuration the SO₂ and SO₃ molecules can be adsorbed on 2PANI with adsorption energies (E_ads) of ?18.2 and ?62.9?kJ/mol (BSSE), respectively.