Efficient Copper‐Catalyzed Synthesis of N‐Alkylanthranilic Acids via an ortho‐Substituent Effect of the Carboxyl Group of 2‐Halobenzoic Acids at Room Temperature

We have developed an efficient copper‐catalyzed method for the synthesis of N‐alkylanthranilic acids. The protocol uses inexpensive copper(I) iodide/racemic 1,1′‐binaphthyl‐2,2′‐diol (rac‐BINOL) as the catalyst/ligand system, readily available 2‐halobenzoic acids and aliphatic amines as the starting materials, the coupling reactions were performed at room temperature, and various functionalities in the substrates were tolerated.     

Miscibility and thermal behavior of poly(vinyl chloride)/feather keratin blends

Various poly(vinyl chloride) (PVC)/feather keratin (FK) blends were prepared via a solution blending method in the presence of N,N‐dimethylformamide as a solvent. The miscibility of the blends was studied with different analytical methods, such as dilute solution viscometry, differential scanning calorimetry, refractometry, and atomic force microscopy. According to the results obtained from these techniques, it was concluded that the PVC/FK blend was miscible in all the studied compositions. Specific interactions between carbonyl groups of the FK structure and hydrogen from the chlorine‐containing carbon of the PVC were found to be responsible for the observed miscibility on the basis of Fourier transform infrared spectroscopy. Furthermore, increasing the FK content in the blends resulted in their miscibility enhancement. The thermal stability of the samples, as an important characteristic of biobased polymer blends, was finally examined in terms of their FK weight percentage and application temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polyacrylonitrile‐grafted Cassia pudibunda seed gum: A potential commercial gum from renewable source

Cassia pudibunda (CP) seed gum was grafted with poly(acrylonitrile) using persulphate/ascorbic acid redox initiator. Optimal grafting Conditions were determined and maximum % grafting and % efficiency observed were 294 and 85.3%, respectively. Grafted CP gum (gum‐g‐polyacrylonitrile; CP‐g‐PAN) was characterized using FTIR, XRD, and TGA analysis. The CP‐g‐PAN sample with maximum %G was observed to be water insoluble, however, 1% solution of the base‐hydrolyzed CP‐g‐PAN had a viscosity of 114.7 centipoises, which was observed to increase continuously for first 5 days and there upon became fixed and was shown to be stable even after 20 days when left at room temperature. Water and saline retention for CP‐g‐PAN after 10 min soaking were observed to be 47 and 30.15 g/g, respectively. Thus, base‐hydrolyzed CP‐g‐PAN samples may find use as water sorbents and their aqueous solutions may be used commercially where medium to low viscosity solutions with high shelf life is the requirement. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 619–627, 2006     

Blend modification of feather keratin‐based films using sodium alginate

Feather keratin (FK), which can be extracted from waste feathers, is a kind of biodegradable and renewable protein resource and it has a great potential in the field of materials such as keratin sponges, films, and microcapsules. The aim of the current study was to investigate the blend modification of FK‐based films using sodium alginate (SA). A series of FK‐based films blended with different ratios of SA were prepared by the casting process. The cross‐section of blend films had a compact and homogeneous structure and no distinct phase separation was observed, indicating the favorable compatibility between FK and SA. The result of DSC analysis, in which there was a change in crystal structure, confirmed the interaction between FK and SA in the blend films. The FTIR spectra pointed out that the main interaction between the two components would be through the formation of hydrogen bonds. The incorporation of SA to FK significantly enhanced the strength and maintained the extensibility of the resultant films. The water vapor permeability reached its lowest level when the ratio of FK to SA was 7:3. Moreover, the blend films exhibited a relatively high level of transparency with SA content below 30%. These improvements by incorporation of SA provided the potential to expand the application of FK‐based films in packing and bio‐medical industries. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44680.     

Capacitance properties of unipolar pulsed electro‐polymerized PEDOT films

Poly(3,4‐ethylenedioxythiophene) (PEDOT) film has been prepared on conductive carbon paper (CP) substrates by unipolar pulse electrochemical deposition. The effects of different polymerization parameters, including pulse potential and width, deposition frequency, and duty cycle on the capacitance of PEDOT films, were studied by cyclic voltammetry in 0.5 M sulfuric acid solution. The PEDOT‐coated CP electrode was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy to confirm the three‐dimensional porous structure and the presence of dopant ion conjugation during the electro‐polymerization. The results of cyclic voltammetry and galvanostatic charge‐discharge show that the PEDOT electrodes exhibit good specific capacitance of 151.31 F/g, rate performance and stability with a retention rate of 80.25% after 5000 cycles. The thin, lightweight electrode materials show considerable potential for low‐cost, high‐performance energy storage applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46729.     

Water Solvent Method for Esterification and Amide Formation between Acid Chlorides and Alcohols Promoted by Combined Catalytic Amines: Synergy between N‐Methylimidazole and N,N,N′,N′‐Tetramethylethylenediamine (TMEDA)

An efficient method for esterification between acid chlorides and alcohols in water as solvent has been developed by combining the catalytic amines, N‐methylimidazole and N,N,N′,N′‐tetramethylethylenediamine (TMEDA). The present Schotten–Baumann‐type reaction was performed by maintaining the pH at around 11.5 using a pH controller to prevent the decomposition of acid chlorides and/or esters and to facilitate the condensation. The choice of catalysts (0.1 equiv.) was crucial: the combined use of N‐methylimidazole and TMEDA exhibited a dramatic synergistic effect. The catalytic amines have two different roles: (i) N‐methylimidazole forms highly reactive ammonium intermediates with acid chlorides and (ii) TMEDA acts as an effective HCl binder. The production of these intermediates was rationally supported by a careful ¹H NMR monitoring study. Related amide formation was also achieved between acid chlorides and primary or secondary amines, including less nucleophilic or water‐soluble amines such as 2‐(or 4‐)chloroaniline, the Weinreb N‐methoxyamine, and 2,2‐dimethoxyethanamine.     

In‐process ultrasonic measurements of orientation and disorientation relaxation of high‐density polyethylene/polyamide‐6 composites with compatibilizer

The relaxation processes of orientation and disorientation of melts of high‐density polyethylene (HDPE) and polyamide‐6 (PA6) blends compatibilized with a compatibilizer precursor (CP) of HDPE‐grafted maleic anhydride (HDPE‐g‐MAH) were investigated in a restricted channel using real‐time ultrasonic technique. The experimental results showed that the evolution of ultrasonic velocity of HDPE/PA6 blends during the orientation or disorientation processes could be described by the exponential equation from which the maximum orientation degree and relaxation time could be obtained. Subsequently, the effects of CP on the relaxation processes of orientation and disorientation were studied. In addition, the relations of the CP content and the morphology and viscosity were investigated by scanning electron microscope analysis and rheological tests. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Conversion of Canola Meal into a High-Protein Feed Additive via Solid-State Fungal Incubation Process

The study goal was to determine the optimal fungal culture to reduce glucosinolates (GLS), fiber, and residual sugars while increasing the protein content and nutritional value of canola meal. Solid‐state incubation conditions were used to enhance filamentous growth of the fungi. Flask trials were performed using 50 % moisture content hexane‐extracted (HE) or cold‐pressed (CP) canola meal with incubation for 168 h at 30 °C. Incubation on HE canola meal Trichoderma reesei (NRRL‐3653) achieved the greatest increase in protein content (23 %), while having the lowest residual levels of sugar (8 % w/w) and GLS (0.4 μM/g). Incubation on CP canola meal Trichoderma reesei (NRRL‐3653), A. pullulans (NRRL‐58522), and A. pullulans (NRRL‐Y‐2311‐1) resulted in the greatest improvement in protein content (22.9, 16.9 and 15.4 %, respectively), while reducing total GLS content from 60.6 to 1.0, 3.2 and 10.7 μM/g, respectively. HE and CP canola meal GLS levels were reduced to 65.5 and 50.7 % by thermal treatments while solid‐state microbial conversion further reduced GLS up to 99 and 98 %, respectively. Fiber levels increased due to the concentration effect of removing oligosaccharides and GLS.     

Schiff base‐substituted polyphenol: synthesis,characterisation and non‐isothermal degradation kinetics

BACKGROUND: Polymers of phenols and aromatic amines have emerged as new materials in fields such as superconductors, coatings, laminates, photoresists and high‐temperature environments. The stability, kinetics and associated pollution of the thermal decomposition of oligophenols are of interest for the aforementioned fields. RESULTS: A new Schiff base polymer, derived from N,N′‐bis(2‐hydroxy‐3‐methoxyphenylmethylidene)‐2,6‐pyridinediamine, was prepared by oxidative polycondensation. Characterisations using Fourier transform infrared, UV‐visible, ¹H NMR and ¹³C NMR spectroscopy, thermogravimetric/differential thermal analysis, gel permeation chromatography, cyclic voltammetry and conductivity measurements were performed. The number‐average (M_n) and weight‐average molecular weight (M_w) and dispersity (D = M_w/M_n) of the polymer were found to be 61 000 and 94 200 g mol^?1 and 1.54, respectively. Apparent activation energies of the thermal decomposition of the polymer were determined using the Tang, Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose and Coats–Redfern methods. The most likely decomposition process was a D_n deceleration type in terms of the Coats–Redfern and master plot results. CONCLUSION: The mechanism of the degradation process can be understood through the use of kinetic parameters obtained from various non‐isothermal methods. Copyright © 2009 Society of Chemical Industry     

Determination of Ni and Zn in an Oil Matrix using Schiff Base‐Assisted Extraction Followed by a Flame Atomic Absorption Spectrometer: A Simple Strategy to Determine Ni and Zn

In the present work, a new and simple Schiff base‐assisted extraction strategy for Ni and Zn from an edible oil matrix with subsequent determination using a flame atomic absorption spectrometer was suggested. According to the green approach, laborious sample‐pretreatment procedures were eliminated via complexation of the analytes with N,N′‐bis(4‐methoxysalycylidene)‐2‐hydroxy‐1,3‐propanediamine (4MSHP) and transferred from the oil phase to the aqueous phase. The complexation properties of 4MSHP, Ni, and Zn were investigated using UV–vis spectrophotometry. The experimental conditions that affect the extraction efficiency were optimized using central composite design. The optimum conditions for the extraction of Ni and Zn were as follows: a volume to oil mass ratio of 0.83 to 1.31 mL g^?1 of 4MSHP solution; 62.3‐ and 50.6‐min, stirring time; 27.3 and 31.1 °C, temperature, respectively. The detection limits (3s_bm^?1) were 0.41 μg g^?1 for Ni and 0.16 μg g^?1 for Zn. Validation of the suggested work was performed by the analysis of organometallic standard‐doped n‐hexane solutions as certified reference materials under the optimum experimental conditions. The recovery percentages were warranted the accuracy and found as 98.2 ± 1.8% for Ni and 99.8 ± 1.2% for Zn. In addition, relative SD values were below 5% for both the analytes. The Student's t‐test showed that there was no significant difference between the found and doped amount of analytes at 95% confidence level. The features such as the detection technique, cheapness, eco‐friendly solvent usage, and practicality were better compared to the literature.     

Temperature and pH effects on the stability and rheological behavior of the aqueous suspensions of smart polymers based on N‐isopropylacrylamide,chitosan, and acrylic acid

This study describes the stability and rheological behavior of suspensions of poly(N‐isopropylacrylamide) (PNIPAM), poly(N‐isopropylacrylamide)‐chitosan (PNIPAM‐CS), and poly(N‐isopropylacrylamide)‐chitosan‐poly(acrylic acid) (PNIPAM‐CS‐PAA) crosslinked particles sensitive to pH and temperature. These dual‐sensitive materials were simply obtained by one‐pot method, via free‐radical precipitation copolymerization with potassium persulfate, using N,N′‐methylenebisacrylamide as a crosslinking agent. Incorporation of the precursor materials into the chemical networks was confirmed by elementary analysis and infrared spectroscopy. The influence of external stimuli such as pH and temperature, or both, on particle behavior was investigated through rheological measurements, visual stability tests, and analytical centrifugation. The PNIPAM‐CS particles showed higher stability in acid and neutral media, whereas PNIPAM‐CS‐PAA particles were more stable in neutral and alkaline media, both below and above the lower critical solution temperature of PNIPAM (stability data). This is due to different interparticle interactions as well as those between the particles and the medium (also evidenced by rheological data), which were also influenced by the pH and temperature of the medium. Based on the results obtained, we found that the introduction of pH‐sensitive polymers to crosslinked PNIPAM particles not only produced dual‐sensitive materials but also allowed particle stability to be adjusted, making phase separation faster or slower, depending on the desired application. Thus, it is possible to adapt the material to different media. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nickel(0)/Imidazolium Carbene Catalyst System for Efficient Cross‐Coupling of Aryl Bromides and Chlorides with Organomanganese Reagents

N,N′‐Bis(2,6‐diisopropylphenyl)imidazolium chloride associated with nickel(II) acetylacetonate (3–5 mol %) was used as catalyst to efficiently cross‐couple functionalized aryl bromides with organomanganese reagents. The reactions were performed between 0 °C and room temperature, giving unsymmetrical biaryls in 0.25 to 24 h with 52 to 100 % yields for isolated materials. Aryl chlorides showed slightly diminished reactivity in Ni/2 IPr‐catalyzed cross‐couplings and good yields could only be attained with activated or neutral substrates.     

Novel polyion complex films from chitosan and quarternized poly(4‐vinyl‐N‐carboxymethylpyridine) containing zwitterion structure units

Novel polyion complexes films of chitosan and quarternized poly(4‐vinyl‐N‐carboxymethylpyridine) containing zwitterion structure units were prepared by casting method. The aim of this work was to produce a hydrophilic film with the potential use as a hydrophilic membranes of the types used in membranes distillation and osmotic distillation for separating azeotropic, close‐boiling, and aqueous organic mixtures. Their structure and properties were studied by infrared, wide‐angle X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, tensile tester, and swelling measurements. The results indicated that polyion complexes occurred between chitosan and quarternized poly (4‐vinyl‐N‐carboxymethylpyridine) containing zwitterion structure units. The thermostability of these blends decreased with the increase of quarternized poly(4‐vinyl‐N‐carboxymethylpyridine) content. Initially, appreciable improvement in tensile strength and breaking elongation were achieved with increase of quarternized poly(4‐vinyl‐N‐carboxymethyl‐pyridine) content to 30%, the maximum value of 46.65 MPa tensile strength and 25.67% breaking elongation were achieved, respectively. The maximum degree of swelling was achieved when the weight ratio of chitosan versus poly(4‐vinyl‐N‐carboxymethylpyridine) was 50 : 50. Meanwhile, the relationship between their structure and properties was also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and evaluation of a molecularly imprinted polymer for tolazoline

A uniformly sized molecularly imprinted polymer for the peripheral vasodilator drug tolazoline (T‐MIP) was prepared, and a nonimprinted polymer (NIP) was also synthesized in the same way but in the absence of the template. The T‐MIP was prepared with methylacrylic acid as functional monomer and ethylene glycol dimethacrylate as crosslinker by a multistep swelling and polymerization method. These imprinted materials were characterized by scanning electron microscopy, nitrogen adsorption, and static adsorption experiments. Binding studies were also performed to evaluate the uptake of T‐MIP and NIP with the results that T‐MIP had a significantly higher binding capacity for tolazoline (T) than did NIP. The maximum static adsorption capacities of T‐MIP and NIP for T were 78.9 and 38.8 μmol/g, respectively. The T‐MIPs and NIPs were used as stationary phases of solid‐phase extraction (SPE), and a relative selectivity coefficient (k′) value of 5.21 was obtained, which showed that the T‐MIP sorbent had higher selectivity than the NIP sorbent. The method was applied to the determination of T in urine samples. The prepared polymer sorbent showed promise for SPE for gas chromatography determination of T in urine samples. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of triple polymer‐coated controlled‐release urea with water‐retention property and enhanced durability

Triple polymer coated with controlled‐release water retention fertilizer (TCWF) and enhanced mechanical property was developed by coating polyethylene (first layer), poly (acrylic acid‐co‐acrylamide) superabsorbent (second layer), and poly (butyl methacrylate) (third layer) consecutively on the granule core urea in the fluidized‐bed coater. The inner layer possessed controlled‐release property, the middle layer had water absorbent characteristic, and the thin outer layer aimed to protect the fragile layer of the superabsorbent. The relationship between the thickness of coating layer and the nutrient releasing properties was established. The effects of polymerization parameters on the water absorbency of the superabsorbent were studied and optimized as well. The nutrients release behaviors of this triple‐coated urea in both water and soil were investigated and compared. The results showed that TCWF not only performed as a good controlled‐release fertilizer but also had excellent water retention capacity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adsorption removal of Cu2+ and Ni2+ from waste water using nano‐cellulose hybrids containing reactive polyhedral oligomeric silsesquioxanes

Cellulose is an important biomass in natural material fields. Reactive polyhedral oligomeric silsesquioxane (R‐POSS) bearing multi‐N‐methylol groups is novel high reactive POSS monomer. The nano‐cellulose hybrids containing R‐POSS were synthesized by crosslinking reaction. It was interesting to investigate properties and applications of hybrids containing R‐POSS. In this work, nano‐cellulose hybrids as novel biosorbent were used for adsorpting copper and nickel ions in aqueous solution. Adsorption kinetics and equilibrium isotherm of Cu²⁺ and Ni²⁺ on the nano‐cellulose hybrids were investigated. The results showed that R‐POSS had been grafted to cellulose macromolecule. The nano‐cellulose hybrids could form new adsorptive position for heavy metal ions. The adsorption capacities of hybrid materials were obviously higher than that of control cellulose. The adsorption of heavy metal ions on nano‐cellulose hybrids followed the second‐order model. The equilibrium isotherms for adsorpting copper and nickel ions on the hybrids followed Langmuir isotherm model. Nano‐cellulose materials containing POSS as biosorbents or ultrafiltration membranes would be used in separation of toxic heavy metal ions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Elemental sulfur‐based polymeric materials: Synthesis and characterization

New elemental sulfur‐based polymeric materials called poly(sulfur‐random‐divinylbenzene) [poly(S‐r‐DVB)] were synthesized by ring opening polymerization via inverse vulcanization technique in the presence of a mixture of o‐, m‐, and p‐diviniylbenzene (DVB) as a cross‐linker. A clear yellow/orange colored liquid was obtained from the elemental sulfur melted at 160 °C and then by adding various amounts of DVB to this liquid directly via a syringe at 200 °C viscous reddish brown polymeric materials were obtained. The copolymers are soluble in common solvents like tetrahydrofuran, dichloromethane, and chloroform, and they can be coated on any surface as a thin film by a spray coating technique. The characterization of the materials was performed by using nuclear magnetic resonance, fourier transform infrared, and Raman spectroscopies. The morphological properties were monitored via scanning electron microscope technique. Thermal analysis showed that an increase in the amount of DVB in the copolymers resulted in an increase in the thermal decomposition temperature. On the other hand, poly(S‐r‐DVB) copolymers exhibited good percent transmittance as 50% T between 1500 and 13,000 nm in electromagnetic radiation spectrum, which makes them good candidates to be amenable use in military and surveillance cameras. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43655.     

Synthesis and characterization of polyacrylamide‐grafted coconut coir pith having carboxylate functional group and adsorption ability for heavy metal ions

The present investigation was undertaken to evaluate the effectiveness of a new adsorbent prepared from coconut coir pith (CP), a coir industry‐based lignocellulosic residue in removing metal ions from aqueous solutions. The adsorbent (PGCP‐COOH) having a carboxylate functional group at the chain end was prepared by grafting polyacrylamide onto CP using potassium peroxydisulphate as an initiator and in the presence of N,N′‐methylenebisacrylamide as a crosslinking agent. The adsorbent was characterized by infrared (IR) spectroscopy, thermogravimetry (TG), X‐ray diffraction (XRD) patterns, scanning electron microscopy (SEM), and potentiometric titration. The adsorbent exhibits very high adsorption potential for the removal of Pb(II), Hg(II), and Cd(II) ions from aqueous solutions. The optimum pH range for metal ion removal was found to be 6.0–8.0. The adsorption process follows a pseudo‐second‐order kinetic model. The adsorption capacities for Hg(II), Pb(II), and Cd(II) calculated using the Langmuir isotherm equation were 254.52, 189.49, and 63.72 mg g^?1, respectively. Adsorption isotherm experiments were also conducted for comparison with a commercial carboxylate form cation exchanger. Different industry wastewater samples were treated by the PGCP‐COOH to demonstrate its efficiency in removing heavy metals from wastewater. The reusability of the PGCP‐COOH was also demonstrated using 0.2M HCl. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3670–3681, 2007     

Covalent approach for in situ enhancement of interaction between pristine graphene and styrene‐butadiene‐p‐(2,2,2‐triphenylethyl)styrene rubber

A facile method for enhancing the interaction between pristine graphene and nonpolar rubber matrices was developed by preparing a new solution‐polymerized styrene‐butadiene‐p‐(2,2,2‐triphenylethyl)styrene (TPES) rubber (SBTR). SBTR macroradicals were formed by the thermal decomposition of a 1,1,1,2‐tetraphenylethane pendant. The macroradicals were successfully trapped by graphene through the formation of covalent bonds. This was confirmed by rotorless rheometer and X‐ray photoelectron spectroscopy measurements. The dispersion of graphene and interfacial interaction between graphene and the SBTR was significantly increased by increasing the TPES content in SBTR composites, as demonstrated by differential scanning calorimetry, scanning electron microscopy, rubber process analysis, and dynamic mechanical thermal analysis. The mechanical properties of the SBTR/GNS composites were significantly improved by the improved dispersion and the increased surface affinity of SBTR for graphene. The developed approach can be generally applied to the functionalization of other polymer matrices by copolymerizing TPES with other vinyl monomers for pristine graphene‐based composite materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44923.     

Synthesis and characterization of poly(methyl methacrylate)‐grafted silica microparticles

A procedure to synthesize poly(methyl methacrylate)‐grafted silica microparticles was developed by using radical photopolymerization of methyl methacrylate (MMA) initiated from N,N‐diethyldithiocarbamate (DEDT) groups previously bound to the silica surface (grafting “from”). The functionalization of silica microparticles with DEDT groups was performed in two steps: introduction of chlorinated functions onto the surface of silica particles, and then nucleophilic substitution of chlorines by DEDT functions via a S_N2 mechanism. The study was performed with a Kieselgel® S silica which was initially chlorinated in surface, either by direct chlorination of silanols with thionyl chloride, or by using a condensation reaction between silanols and a chlorofunctional trialkoxysilane reagent, 4‐(chloromethyl)phenyltrimethoxysilane and chloromethyltriethoxysilane, respectively. Three types of DEDT‐functionalized silica microparticles were prepared with a good control of the reactions, and then characterized by solid‐state ¹³C and ²⁹Si CP/MAS NMR. Their ability to initiate MMA photopolymerization was studied. The kinetics of MMA photopolymerization was followed by HPLC and ¹H‐NMR. Whatever the silica used the grafting progresses very slowly. On the other hand, the conversion of MMA in PMMA grafts is depending on the structure of the DEDT‐functionalized Kieselgel® S used. Poly(methyl methacrylate)‐grafted silica microparticles bearing high length grafts ( about 100) were synthesized. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008