The effect of crosslinking on the adsorption behavior of copper (II) onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone)

The adsorption behavior of Cu(II) ions onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone), polymer I, and onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone) crosslinked with different amounts of divinylbenzene (DVB), polymers II, III, and IV, in aqueous solutions was investigated using batch adsorption experiments as a function of contact time, pH, and temperature. The amount of metal ion uptake of the polymers was determined by using atomic absorption spectrometry (AAS) and the highest uptake was achieved at pH 7.0 and by using perchlorate as an ionic strength adjuster for polymers I, II, III, and IV. Results revealed that the adsorption capacity (q_e and Q_m) of Cu(II) ions decreases with increasing crosslinking due to the decrease of chelation sites. In addition, the rate of adsorption (k₂) of Cu(II) ions decreases with the increase of crosslinking because it becomes more difficult for Cu(II) ions to diffuse into the chelation sites. The isothermal behavior and the kinetics of adsorption of Cu(II) ions on these polymers with respect to the initial mass of the polymer and temperature were also investigated. The experimental data of the adsorption process was found to correlate well with the Langmuir isotherm model. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of a surface imprinting silica gel polymer functionalized with phosphonic acid groups for selective adsorption of Fe(III) from aqueous solution

A Fe(III) ion‐imprinted silica gel polymer functionalized with phosphonic acid groups (IIP‐PA/SiO₂) was prepared with surface imprinting technique by using Fe(III) ion as template ion, grafted silica gel as support, and vinylphosphonic acid as functional monomer. The polymer was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–Teller, and thermogravimetric analysis. The synthesized imprinted silica gel polymer was used as a sorbent for Fe(III) adsorption. The adsorption properties, such as the effect of solution pH, adsorption kinetic, adsorption isotherm, adsorption selectivity as well as the regeneration of sorbent were studied. The results showd that the prepared sorbent (IIP‐PA/SiO₂) had a short adsorption equilibrium time (12 min) and high adsorption capacity (29.92 mg g^?1) for Fe(III) at the optimal pH of 2.0. The selectivity coefficients of the sorbent for Fe(III) in presence of Cr(III), M_n (II), and Zn(II) were 51.76, 27.86, and 207. 76, respectively. Moreover, the adsorption capacity of the prepared sorbent did not decrease significantly after six repeated use. Thus, the prepared ion‐imprinted silica gel polymer was a promising candidate sorbent for the selective adsorption of Fe(III) from aqueous solutions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45165.     

Preparation and characterization of selective phenyl thiosemicarbazide modified Au(III) ion‐imprinted cellulosic cotton fibers

In this study, a novel selective Au(III) chelating surface ion imprinted fibers based on phenyl thiosemicarbazide modified natural cotton (Au‐C‐PTS) has been synthesized, and applied for selective removal of Au(III) from aqueous solutions. Batch adsorption experiments were performed with various parameters, such as contact time, pH, initial Au(III) concentration, and temperature. The kinetic studies revealed that the adsorption process could be described by pseudo‐second‐order kinetic model, while the adsorption data correlated well with the Langmuir and Freundlich models. The maximum adsorption capacities calculated from the Langmuir equation are 140 ± 1 mg g^?1 and 72 ± 1 mg g^?1 at pH 5 for both Au‐C‐PTS and NI‐C‐PTS, respectively. The estimated thermodynamic parameters (Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy change (ΔS°)) indicated the spontaneity and exothermic nature of the adsorption process. Furthermore, the selectivity study revealed that the ion imprinted fibers was highly selective to Au(III) compared with Cu(II), Cd(II), Hg(II), and Fe(III). The adsorbent was successfully regenerated with a 0.1M HNO₃ solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40769.     

Selective separation and concentration of Pd(II) from Fe(III), Co(II), Ni(II), and Cu(II) ions using thiourea‐formaldehyde resin

Thiourea‐formaldehyde (TUF), a well‐known chelating resin, has been synthesized and it was used in the adsorption, selective separation, and concentration of Pd(II) ions from Fe(III), Co(II) Ni(II), and Cu(II) base metal ions. The composition of the synthesized resin was determined by elemental analysis. The effect of initial acidity/pH and the adsorption capacity for Pd(II) ions were studied by batch technique. The adsorption and separation of Pd(II) were then examined by column technique. FTIR spectra and SEM/EDS analysis were also recorded before and after the adsorption of Pd(II). The optimum pH was found to be 4 for the adsorption. The adsorption data fitted well to the Langmuir isotherm. The maximum adsorption capacity of the TUF resin for Pd(II) ions was found to be 31.85 mg g⁻¹ (0.300 mmol g⁻¹). Chelating mechanism was effective in the adsorption. Pd(II) ions could be separated efficiently from Fe(III), Cu(II), Ni(II), and Co(II) ions using TUF resin. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dithieno[2,3‐d:2′,3′‐d′]naphtho[2,1‐b:3,4‐b′]dithiophene based medium bandgap conjugated polymers for photovoltaic applications

Three novel medium band gap (MBG) conjugated polymers (CPs) (named as P1, P2, and P3, respectively) were developed by copolymerizing 2,7‐dibromo‐10,11‐di(2‐hexyldecyloxy)dithieno[2,3‐d:2′,3′‐d′]naphtho[2,1‐b:3,4‐b′]dithiophene (NDT‐Br) with three different units: 2,5‐bis(tributylstannyl)thiophene, 2,5‐bis(trimethylstannyl)thieno[3,2‐b]thiophene and trans?1,2‐bis(tributylstannyl)ethene, respectively. The thermal, optical, and electrochemical properties of the polymers were investigated. All of the polymers have good thermal stability and medium band gap (～ 1.9 eV). Prototype bulk heterojunction photovoltaic cells based on the blend P1/P2/P3 and [6, 6] phenyl‐C61 butyric acid methyl ester (PC₆₁BM) were assembled and the photovoltaic properties were assessed. Power conversion efficiencies (PCEs) of 1.61% ～ 2.43% have been obtained under 100 mW cm^?2 illumination (AM1.5). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43288.     

Molecularly imprinted polymer for solid phase extraction of nicotinamide in pork liver samples

Aromatic polyamides and polythioamides with pendent chlorobenzylidine rings were synthesized through direct polycondenzation of 2‐(p‐chlorobenzalimino) terephthalic acid with the diamines 4,4′‐oxidianiline (1a), 4,4′‐methylenediamide (1b), 4,4′‐diaminodiphenyl sulfone (1c), and thioamines 4,4′‐(bisthiourea) diphenyl ether (3a), 4,4′‐(bisthiourea) diphenyl methane (3b), 4,4′‐(bisthiourea) diphenyl sulfone (3c), respectively, in DMF using P(OPh)₃/pyridine. The polymers were precipitated using water as nonsolvent. FTIR and ¹H‐NMR spectroscopic analysis was used to characterize the monomers and polymers. Representative polyamides and polythioamides were used for the removal of heavy metal ions such as Pb(II), Cd(II), Cu(II), and Cr(III) from aqueous solutions. The effects of pH, contact time, and initial concentration on the uptake of metal ions have been investigated. The adsorption capacities under competitive conditions were in the order Pb (II) > Cu (II) > Cr (III) > Cd (II). The adsorbed ions were eluted by treatment with 2N HCl, and the activities of the polymers are retained after fourth regeneration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adsorption of bismuth(III) by bayberry tannin immobilized on collagen fiber

The adsorption behavior of collagen fiber‐immobilized bayberry tannin towards Bi(III) at acidic pH values was investigated. The adsorption capacity of the adsorbent towards Bi(III) was 0.348 mmol g^?1 at 303 K, and increased with the rise in temperature. The adsorption isotherms of Bi(III) were in the shape of so‐called type II isotherms and could be described by an empirical equation, ln q_e = k + (1/n)C_e, which implies that chemical adsorption is predominant at lower concentrations of Bi(III) and that physical adsorption is involved at higher concentrations. The adsorption kinetics of Bi(III) on the immobilized bayberry tannin could be well described by the pseudo‐second‐order rate model, and the adsorption capacities calculated by the model were almost the same as those determined by actual measurements. The adsorbent could be regenerated by using 0.02 mol dm^?3 ethylenediaminetetraacetic acid (EDTA) solution after adsorption of Bi(III). The adsorption selectivity of the immobilized bayberry tannin towards Bi(III) in a Cu(II)–Bi(III) binary solution in acidic medium was remarkable. Therefore, it is strongly suggested that the immobilized bayberry tannin could be applied to the removal of Bi(III) from crude Cu(II) samples under proper conditions. Copyright © 2006 Society of Chemical Industry     

Tuning the photovoltaic performances of the terpolymers based on thiophene‐benzene‐thiophene via the modification of alkyl side chains

Three new random conjugated terpolymers based on thiophene‐2,5‐bis((2‐ ethylhexyl)oxy)benzene‐thiophene or thiophene‐2,5‐bis((2‐octyl)oxy)benzene‐ thiophene as electron‐donating units, diketopyrrolopyrrole (DPP) and 4,7‐dithien‐5‐yl‐2,1,3‐benzothiadiazole (DTBT) side group as electron‐withdrawing units have been designed and synthesized by Stille‐coupling reaction. All the terpolymers exhibit good thermal stability, broad absorption in the range of 300 to 800 nm. By tuning the alkyl side chains of the terpolymers, the absorption spectra, HOMO energy levels and photovoltaic properties of the terpolymers changed dramatically. A bulk heterojunction polymer solar cell fabricated from terpolymer GP2 and PC₆₁BM exhibited a promising power conversion efficiency of 3.31% without any processing additives. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42982.     

Synthesis and characterization of copolythiophene

Copolythiophenes (Co‐PTs), poly(3‐hexylthiophene‐co‐3‐thiophene carboxylic acid) (P3HT‐TCa), poly(3‐hexyloxylthiophene‐co‐3‐thiophene carboxylic acid) (P3HOT‐TCa), and poly(3‐phenylthiophene‐co‐3‐thiophene carboxylic acid) (P3PhT‐TCa), were synthesized by chemical oxidized polymerization to investigate the effect of copolymerization on the properties of polythiophenes (PTs). Gel permeation chromatography showed that the molecular weight (MW) of Co‐PT was lower than that of homopolythiophene. Fourier transform infrared (FTIR) spectra indicated that the copolymerization was successful between the monomers. The λ_max of Co‐PTs gave a “blue shift” in ultraviolet‐visible (UV‐VIS) spectra. Photoluminescence (PL) spectra showed that the PL intensity of Co‐PT became weaker than that of homopolythiophene and the disappearance of PL had been observed in P3HOT‐TCa. The thermal stability of Co‐PT was influenced by the carboxyl for its low decomposition temperature. Furthermore, the copolymerization between multi‐wall carbon nanotube containing thiophene ring (MWNT‐Th) and 3‐hexyloxylthiphene could also take place successfully. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Thiophene π‐bridge effect on photovoltaic performances of dithienosilole and bithiazole backboned polymers

In this article, two dithienosilole (DTS) and bithiazole (BTz) backboned donor–acceptor (D‐A) copolymers with (poly{5‐(5‐(4,4‐bis(2‐ethylhexyl)‐4H‐silolo[3,2‐b:4,5‐b']dithiophen‐2‐yl)thiophen‐2‐yl)‐4,4'‐dinonyl‐5'‐(thiophen‐2‐yl)‐2,2'‐bithiazole} (PDTS‐DTBTz)) and without (poly{5‐(4,4‐bis(2‐ethylhexyl)‐4H‐silolo[3,2‐b:4,5‐b']dithiophen‐2‐yl)‐4,4'‐dinonyl‐2,2'‐bithiazole} (PDTS‐BTz)) thiophene π‐bridge were synthesized to study the influence of thiophene π‐bridge on their photovoltaic performances. Both polymers show similar band gap, but polymer with thiophene π‐bridge (PDTS‐DTBTz) has a higher molecular weight, narrower polydispersity index (PDI), more planar geometry, higher crystallinity, higher hole mobility, and better miscibility with fullerene (polymer solar cells (PSCs) acceptor). Although PDTS‐BTz polymer based PSCs devices show higher open circuit voltage (V_oc), PDTS‐DTBTz polymer does show higher power conversion efficiency (PCE) with improved short circuit current density (J_sc) and fill factor (FF). The present results indicate that thiophene π‐bridge does contribute to the PSCs performances of dithienosilole and bithiazole backboned copolymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42798.     

Structure characterization and adsorption properties of tetraethylenepentamine ion exchange fiber

A novel tetraethylenepentamine ion exchange fiber (TAIEF) was prepared using polypropylene grafted styrene (PP‐g‐ST) fiber as raw material. The chemical structure of TAIEF was characterized using infrared spectrum (IR) method. TAIEF had good appearance and shape after reaction in SEM images, the TGA curves revealed that both PP‐g‐ST fiber and acetyl PP‐g‐ST fiber had good thermal stability below 250 °C, and the weight loss rate of TAIEF is 9% from 50 °C to 200 °C obtained by TGA. TAIEF adsorption capacity to Fe(III) is larger than that of In(III) in the pH value 1.00 to 3.00, while the pH value is at 2.50 to 3.00, TAIEF adsorption capacity to Fe(II) and Zn(II) are smaller than that of In(III). The selective adsorption ability to Fe(III) is higher than In(III), and the selective absorptivity to In(III) is better than Fe(II) and Zn(II). The mechanism was explained of TAIEF favorable selective adsorption to In(III) and Fe(III) ions in mixed solutions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44513.     

Synthesis of N‐polyethereal polypyrroles and their application for the preconcentration of rare earth ions

Conducting polymers containing polyether pseudocages (P I , P II , P III ) have been synthesized via chemical oxidation of 1,5‐bis(1,1‐pyrrole)‐3‐oxabutane (M I ), 1,8‐bis(1,1‐pyrrole)‐3,6‐dioxahexane (M II ), and 1,11‐bis(1,1‐pyrrole)‐3,6,9‐trioxaundecane (M III ) using anhydrous FeCl₃ in CHCl₃. Because as obtained polymer resins did not give any response toward any cations, they were reduced (undoped) using chemical reducing agents. Tetrabutylammonium hydroxide was found to be more effective in undoping to obtain more reproducible and reusable polymer resins. The undoped polymer resins were tried in the extraction of rare earth metal ions from the aqueous medium. Among them, only P III resin removes La(III), Eu(III) and Yb(III) and can be employed for the preconcentration of these metal ions. For batch extraction of La(III), Eu(III) and Yb(III) at neutral pH values, percent recoveries of 98.0 ± 1.0, 90.7 ± 1.4, 87.3 ± 4.0, respectively, has been obtained. The sorption capacity is found as 1.3 mg of La(III) per gram of P III resin. The P III resin could be reused at least five times without significant change in its sorption capacity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Palladium Isolation and Purification from Nitrate Media: Efficient Process Based on Malonamides

ABSTRACT

Solvents based on malonamides have been described to be very efficient and selective for liquid-liquid extraction of Pd(II) from nitrate media. The present study details the possibility to selectively extract Pd(II) over common metallic cations, Cu(II), Ni(II), Co(II), Zn(II), Nd(III), Fe(III) and Al(III) using N,N’-dimethyl,N,N’-dibutyltetradecylmalonamide (DMDBTDMA) in toluene. The lowest selectivity was obtained considering Fe(III) and Nd(III), the extraction of all other cations being negligible. Pd(II) distribution and selectivity regarding Fe(III) have been fine-tuned using the aqueous HNO₃ concentration as the sole parameter, so that extraction, scrubbing and stripping steps can be simply designed without the need for other specific metal chelating reagents and/or aqueous media and without the extensive generation of aqueous effluents. DMDBTDMA was also benchmarked with other classical Pd(II) extractants such as tributylphosphate (TBP), dihexylsulfide (DHS), tetraoctyl diglycolamide (TODGA) and bis(2-ethylhexyl)sulfoxide (BESO) in toluene and in n-heptane. Overall, this study reveals that malonamides are very well positioned and should be considered for further processing of aqueous nitrate wastes containing Pd contaminated with common base metals.     

Synthesis,extraction, and anti‐bacterial studies of some new bis‐1,2,4‐triazole derivatives part I

A series of new bis triazole Schiff base derivatives (4) were prepared in good yields by treatment of 4‐amino‐3,5‐diphenyl‐4H‐1,2,4‐triazole (3) with bisaldehydes (1). Schiff bases (4) were reduced with NaBH₄ to afford the corresponding bisaminotriazoles (5). All the new compounds were characterized by IR, ¹H NMR and ¹³C NMR spectral data. Their overall extraction (log K_ex) constants for 1 : 1 (M : L) complexes and CHCl₃/H₂O systems were determined at 25 ± 0.1°C to investigate the relationship between structure and selectivity toward various metal cations. The extraction equilibrium constants were estimated using CHCl₃/H₂O membrane transfer with inductively coupled plasma‐atomic emission spectroscopy spectroscopy. The stability sequence of the triazole derivatives in CHCl₃ for the metal cations was exhibited a characteristic preference order of extractability to metal ions [Fe(III) > Cu(II) > Pb(II) > Co(II) > Ni(II) > Mn(II) > Zn(II) > Mg(II) > Ca(II)]. The compounds were tested for anti‐microbial activity applying agar diffusion technique for 11 bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel aromatic and aromatic–aliphatic poly(thiourea‐amide)s for the extraction of toxic heavy metal ions

A series of novel aromatic and aromatic–aliphatic diamines [isophthaloyl bis(3‐(3‐aminophenyl)thiourea), terephthaloyl bis(3‐(3‐aminophenyl)thiourea), adipoyl bis(3‐(3‐aminophenyl)thiourea), sebacoyl bis(3‐(3‐aminophenyl)thiourea)] were synthesized starting from the dinitro compounds. Spectroscopic and elemental analyses were carried out for the structure elucidation of the monomers. Three series of poly(thiourea‐amide)s (PTAMs) bearing C?S groups were prepared through the condensation of new diamines with the diacid chlorides such as isophthaloyl, terephthaloyl and adipoyl chloride. The ensuing PTAMs were characterized using FTIR, ¹H‐NMR and ¹³C‐NMR techniques. Physical properties of the polymers such as solution miscibility, crystallinity, solution viscosity, molecular weight, and thermal properties were measured. Consequently, good organosolubility of these polymers was experiential in amide solvents as DMAc, DMF, DMSO and NMP. Moreover, PTAMs exhibited η_inh in the range of 0.92–1.56 dL/g and GPC measurements revealed M_w around 607 × 10²‐851 × 10². DSC served to envisage the glass transition temperatures (T_g) of poly(thiourea‐amide)s located between 232 and 258°C and the initial decomposition temperatures (T₀) probed by thermogravimetry were in the range of 305–419°C. Structure‐property relationship of these polymers was also studied. Eventually, solid?liquid extraction tests of the selected poly(thiourea‐amide)s systems revealed excellent results because these polymers show nearly 100% elimination of lead and mercury cations from water media. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Poly(styrene–divinyl benzene)‐immobilized Fe(III) complex of 1,3‐bis(benzimidazolyl)benzene: Efficient catalyst for the photocatalytic degradation of xylenol orange

A polymer‐supported Fe(III) complex of 1,3‐bis(benzimidazolyl)benzene [PS–Fe(III)BBZNH] was used in the photodegradation of xylenol orange (XO) dye with H₂O₂ under UV irradiation. The catalyst was synthesized and characterized by elemental analysis, and Fourier transform infrared, far‐infrared, and UV–visible–diffuse reflectance spectroscopy, Scanning electron microscopy, Brunauer–Emmett–Teller surface area measurements, thermogravimetric analysis, and magnetic measurements. An octahedral coordination around Fe(III) was confirmed by electronic spectral data, and a decrease in the intensity of the ν_CH2Cl peak in PS–Fe(III)BBZNH was observed compared to the polymer support; this indicated the binding of the ligand to the support. An array of experiments were carried out to assess the influence of various reaction parameters on its photocatalytic performance to ensure maximum dye degradation. The maximum photocatalytic activity was observed at pH 8 with 125 mg of catalyst, 300 ppm of XO, and 200 ppm of H₂O₂ with complete mineralization after 90 min, as confirmed by chemical oxygen demand measurements. Furthermore, the reactions were repeated under sunlight and under dark conditions to check the photocatalytic efficiency of PS–Fe(III)BBZNH. It displayed better catalytic performance compared than the unsupported complex, PS–Cu(II)BBZNH [Cu(II) complex of 1,3‐bis(benzimidazolyl)benzene], and PS–VO(IV)BBZNH [VO(IV) complex of 1,3‐bis(benzimidazolyl)benzene]. PS–Fe(III)BBZNH could be recycled for up to seven runs. A tentative mechanism involving ·OH radical was proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46480.     

Adsorption Behaviors of Platinum Group Metals in Simulated High Level Liquid Waste Using Macroporous (MOTDGA-TOA)/SiO2-P Silica-based Absorbent

As fundamental research for separation of platinum group metals (PGMs) from high level liquid waste (HLLW) by macroporous silica-based adsorbent, (MOTDGA-TOA)/SiO₂-P adsorbent was prepared by impregnation of N,N′-dimethyl-N,N′-di-n-octyl-thiodiglycolamide (MOTDGA) and Tri-n-octylamine (TOA) into silica/polymer composite support (SiO₂-P). The adsorption behavior of Ru(III), Rh(III), and Pd(II) in simulated HLLW onto the adsorbent were investigated by the batch method to obtain their corresponding equilibrium and kinetic data. The adsorbent showed strong adsorption for Pd(II) and the adsorption reached equilibrium within 2 hr. High distribution coefficient (K _d) values for Pd(II) were obtained in 0.1–1 M HNO₃ concentration. In addition, the use of both MOTDGA and TOA improved adsorption of Ru(III) and Rh(III) better than individual use of them. Especially, the K _d value for Ru(III) towards (MOTDGA-TOA)/SiO₂-P adsorbent was three times larger than that in the adsorption using only with MOTDGA or TOA as extractant. The adsorptions of Ru(III), Rh(III), and Pd(II) followed the Langmuir adsorption model, and were found to be controlled by the chemisorption mechanism.     

Synthetic and spectroscopic studies of chelate polymers involving azelaoyl bis‐N‐phenyl hydroxamic acid with transition metal ions

Chelate polymers of azelaoyl bis‐N‐phenyl hydroxamic acid with Mn(II), Co(II), Ni(II), and Zn(II) were synthesized for the first time in a dimethylformamide (DMF) medium. These newly synthesized chelate polymers were characterized on the basis of several analytical techniques, namely, elemental analyses, infrared and reflectance spectral studies, magnetic moment, and thermal analyses. On the basis of data obtained with these techniques, the composition of the polymeric units, the structure, and the geometry were ascertained. It was found that the Mn(II) and Zn(II) chelate polymers had a tetrahedral geometry, whereas the Co(II) and Ni(II) chelate polymers were octahedral. Thermal analytical data clearly indicated that the Ni(II) chelate polymer was highly thermally stable relative to the Mn(II), Co(II), and Zn(II) chelate polymers. Since these chelate polymers are highly insoluble in almost all the organic solvents, including alcohol, acetone, chloroform, carbon tetrachloride, DMF, and DMSO, and have high thermal stability, they may be used as surface‐coating materials and as thermally stable materials. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 273–278, 2006     

Synthesis,structures, and density functional theory computational study of thiophene‐containing and fluorodecorated imine‐linked polymers

A new series of extended–conjugated and thermally stable thiophene‐containing imine‐linked polymers were synthesized via a Schiff‐base condensation reaction between aryl aldehydes and 2,6‐diaminopyridine building blocks. The backbones of the polymers were functionalized with phenyl, fluorosubstituted phenyl, thienyl, and pyridyl aromatic rings. The successful synthesis was confirmed with spectrochemical characterization techniques, including IR, ¹H‐NMR, ¹³C‐NMR, and elemental analyses. The electronic properties of the polymers were investigated with ultraviolet–visible (UV–vis) absorption spectroscopy; the properties were collected experimentally and calculated with density functional theory (DFT) in the gas phase. The maximum absorption calculated from DFT was higher than the experimental values by about 60 nm; this was attributed to the absence of the solvent effect in the DFT case. The frontier molecular orbital ((HOMO) highest occupied molecular orbital and (LUMO) lowest unoccupied molecular orbital), optical band gap (E_g), and total energy (E_T) values of the optimized structures were calculated. Apparently, there was a significant relation between the number of thiophene rings and the resulting E_g and E_T values. As the number of thiophene rings in the polymer chain increased, E_g and E_T decreased, and the thermal stability of the polymers increased. E_g and the absorption band edges were determined experimentally from the UV–vis and transmittance spectra, respectively. Poly(terthienyl–azomethine–pyridine–azomethine), with the highest thiophene content, had the lowest experimental and calculated E_g values (2.10 and 2.63 eV, respectively). In contrast, upon fluorination, poly[(2,5‐dithienyl–1,4‐difluorobenzene)–azomethine–pyridine–azomethine] exhibited the highest E_g (2.81 eV) and absorption band edges (2.94 eV), whereas the thermal stability decreased to 250 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44331.