Synthesis and photovoltaic properties of dithienyl benzotriazole based poly(phenylene vinylene)s

Two new alternating copolymers based on dithienyl benzotriazole segment and phenylene vinyl unit were synthesized by Heck cross coupling method. The polymers exhibited broad absorption bands (from 300 nm to 752 nm for P1 , and from 300 nm to 654 nm for P2 ) in the UV‐visible region with optical bandgap ranging between 1.6 and 1.9 eV and proper electronic energy levels measured by cyclic voltammetry. The photovoltaic properties of the polymers as electron donors with 6.6‐phenyl C61‐butyric acid methyl ester as the electron acceptor in a bulk heterojunction structures were reported. Preliminary results showed moderate power conversion efficiency of 0.36% and 0.4%, respectively, under the illumination of AM 1.5, 100 mW/cm² with a device structure of ITO/PEDOT : PSS/polymer : PC₆₀BM (1 : 3)/Ca/Al. Furthermore, the side chain effect on properties has also been investigated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synergism effect between modified carbon black and organic ultraviolet absorber in polymer matrix for ultraviolet protection

Modified carbon black (MCB) was obtained by oxidization and hydroxymethylation reactions with conductive carbon black (CB); in the MCB, some hydroxyl groups were introduced on the surface of the CB particles. CB, MCB, and a kind of organic ultraviolet absorber (UA) were used as UV antidotes, and binary composites and ternary composites were prepared by solvent casting with polystyrene, styrene–butadiene–styrene triblock copolymer, and poly(methyl methacrylate) as the matrix, respectively. In the binary composites, only one kind of UV antidote was used, whereas in the ternary composites, the organic and inorganic UAs were combined. The ultraviolet–visible absorption spectra of the composites were investigated extensively, and it was found that no synergism occurred when CB was combined with the organic absorber; on the other hand, an obvious synergism effect emerged when MCB was combined with the organic absorber in the same matrix, which was attributed to the formation of hydrogen bonds between MCB and UA. The interaction between MCB and UA was studied by Fourier transform infrared spectroscopy, differential scanning calorimetry, and transmission electron microscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of PS‐PMMA/ZnO nanocomposite films with novel properties of high transparency and UV‐shielding capacity

High transparent and UV‐shielding poly (styrene)‐co‐poly(methyl methacrylate) (PS‐PMMA)/zinc oxide (ZnO) optical nanocomposite films were prepared by solution mixing using methyl ethyl ketone (MEK) as a cosolvent. The films were characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible (UV–vis) spectra, high‐resolution transmission electron microscopy (HR‐TEM), and atomic force microscope (AFM). Cross‐section HR‐TEM and AFM images showed that the ZnO nanoparticles were uniformly dispersed in the polymer matrix at the nanoscale level. The XRD and FTIR studies indicate that there is no chemical bond or interaction between PS‐PMMA and ZnO nanoparticles in the nanocomposite films. The UV–vis spectra in the wavelength range of 200–800 nm showed that nanocomposite films with ZnO particle contents from 1 to 20 wt % had strong absorption in UV spectrum region and the same transparency as pure PMMA‐PS film in the visible region. The optical properties of polymer are greatly improved by the incorporation of ZnO nanoparticles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and optical performance of chiral polymers having azobenzene segments

A series of monomeric azobenzene derivatives of 6‐(4‐nitro‐4′‐oxy‐azobenzene acrylate with carbon numbers of 6 and 11, and the chiral monomer of bornyl 4‐(6‐acryloyloxyhexyloxy)‐phenyl‐4′‐benzoate were synthesized. Chiral polymers having bornyl group end‐capped pendants with azobenzene‐derived segments were prepared. Molecular structures and polymer compositions were confirmed by using ¹H‐NMR, elemental analysis, FTIR, and UV–vis analyzers. Thermodynamic properties of both monomers and polymers were investigated. Specific rotations of chiral monomers and polymers were estimated by using an automatic digital polarimeter. Liquid crystalline textures of monomers and polymers were analyzed by using a polarizing optical microscope and confirmed by a small‐angle X‐ray analyzer. The optical reflection characteristics of composite cells with chiral nematic liquid crystal and various amounts of azobenzene derivatives were evaluated by using a UV–vis spectrophotometer. The reliability and stability of the composite cells with E48/S811 and azobenzene derivatives were studied. The photoisomerization of the chiral polymer film was investigated by using SEM and AFM analyzers. It was found that the UV irradiation of a laser spot caused the shrinkage of polymer film due to the photoisomerization of azobenzene segments. The contraction of the polymer film can be recovered by heat treatment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3693–3704, 2004     

Synthesis and characterization of tanninsulfonic acid doped polyaniline–metal oxide nanocomposites

Composites of conducting polymers and metal oxides have a potential role in electronic devices because of their enhanced physical and electronic properties. An in situ synthesis of metal oxide nanocomposites of polyaniline (PANI) and tanninsulfonic acid doped PANI was carried out at ?10°C with two different ratios of aniline to sodium persulfate (oxidant) and the simultaneous incorporation of TiO₂, Al₂O₃, and ZnO nanopowders. The products were characterized by X‐ray diffraction (XRD), thermal analysis, spectroscopy, and electrical conductivity measurements. XRD and thermogravimetric analysis confirmed the presence of the metal oxide in the final product, whereas the spectroscopic characterization revealed interactions among the tannin, metal oxides, and PANI. The electrical properties were determined by four‐point‐probe bulk conductivity measurements. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Online monitoring of the influence of the chemical structure of hindered amines on the hydrolysis of polycarbonate in a polycarbonate/poly(acrylonitrile–butadiene–styrene) blend by ultraviolet–visible spectroscopy

Without stabilization, polycarbonate (PC)/poly(acrylonitrile–butadiene–styrene) (ABS) blends are susceptible to a loss of mechanical properties after a few days of exposure to weathering conditions. ABS can be stabilized against terrestrial light by the use of hindered amines in combination with a UV absorber; such hindered amines cannot be used when PC is present in the polymer blend. The hydrolysis of PC is accelerated when a small amount of a hindered amine light stabilizer (HALS) is incorporated into the resin and is exposed to elevated temperatures. In this study, three different HALSs (Tinuvin 123, Tinuvin 770, and Tinuvin 765, Ciba, Basel, Switzerland) were used as UV stabilizers for PC/ABS blends, and their effects on the PC phase were observed with online ultraviolet–visible spectroscopy on extruded flat films. These stabilizers were compounded with the blends in a corotating twin‐screw extruder at 240°C. The molecular weight of the compounded samples was determined by gel permeation chromatography. The extent of degradation induced by the HALSs on the PC phase was found to be a function of its chemical structure. Tinuvin 123 with an amino ether functional group enhanced degradation in comparison with Tinuvin 770 and Tinuvin 765. Tinuvin 770, a secondary amine, was apt to be more reactive than Tinuvin 765, a tertiary amine, because less steric hindrance was experienced by the former. Accelerated aging of the compounded samples was performed. Decreased degradation was observed for the samples containing hindered amines; however, the HALSs alone were not effective in protecting the PC/ABS blends against harmful UV light. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Interaction of dis‐azo dyes with quaternized poly(dimethylaminoethyl methacrylate) as a function of the dye structure and polycation charge density

Interactions between some dis‐azo dyes, different by either the position of their sulfonic groups or their number (Ponceau SS, Crocein Scarlet MOO, Congo Red, and Direct Blue 1), and some strong polycations (PCs), with cationic centers in their side chains and dye removal from artificial wastewaters were systematically investigated in this study. PCs with variable charge densities (CDs) were prepared from poly(dimethylaminoethyl methacrylate) by controlled quaternization with benzyl chloride. Even when the main process in the dye removal was charge neutralization (coagulation) for all of the dyes, significant effects of the CD and dis‐azo dye structure on the metachromatic behavior of the dyes in dilute aqueous solutions and on the dye removal efficiency were observed. The stability of the PC/azo dye complex and, connected with this, the flocculation window were higher when the PC with the highest CD was used. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of waterborne polyurethane/polyaniline codoped with dodecyl benzene sulfonic acid and hydrochloric acid blends

A conductive poly(aniline codoped with dodecyl benzene sulfonic acid and hydrochloric acid) [PANI‐D/H, yield: 32.2%, intrinsic viscosity ([η]): 1.39 dL/g, electrical conductivity: 7.3 S/cm] was synthesized by chemical oxidative polymerization from aniline‐dodecylbenzene sulfonic acid salt (A‐DS)/aniline‐hydrochloric acid salt (A‐HS) (6/4M ratio) in an aqueous system. Waterborne polyurethane (WBPU) dispersion obtained from isophorone diisocyanate/poly(tetramethylene oxide)glycol/dimethylol propionic acid/ethylene diamine/triethylene amine/water was used as a matrix polymer. The blend films of WBPU/PANI‐D/H with various weight ratios (99.9/0.1–25/75) were prepared by solution blending/casting. Effect of PANI‐D/H content on the mechanical property, dynamic mechanical property, hardness, electrical conductivity, and antistaticity of WBPU/PANI‐D/H blend films was investigated. The dynamic storage modulus and initial tensile modulus increased with increasing PANI‐D/H content up to 1 wt %, and then it was significantly decreased about the content. With increasing PANI‐D/H content, the glass transition temperature of soft segment (T_gs) and hard segment (T_gh) of WBPU/PANI‐D/H blend films were shifted a bit to lower the temperature. The tensile strength and hardness of WBPU/PANI‐D/H blend films increased a little with increasing PANI‐D/H content up to 0.5 wt %, and then it was dramatically decreased over the content. The elongation at break of WBPU/PANI‐D/H decreased with an increase in PANI‐D/H content. From these results, it was concluded that 0.5–1 wt % of PANI‐D/H was the critical concentration to reinforce those various properties of WBPU/PANI‐D/H blend films prepared in this study. The electrical conductivity of WBPU/ultrasonic treated PANI‐D/H (particle size: 0.7 μm) blend films prepared here increased from 4.0 × 10^?7 to 0.33 S/cm with increasing PANI‐D/H content from 0.1 to 75 wt %. The antistatic half‐life time (τ_1/2) of pure WBPU film was about 110 s. However, those of WBPU/ultrasonic treated PANI‐D/H blend films (τ_1/2: 8.2–0.1 s, and almost 0 s) were found to decrease exponentially with increasing PANI‐D/H content (0.1–9 wt %, and above 9 wt %). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 700–710, 2004     

Surface phase separations of PMMA/SAN blends investigated by atomic force microscopy

The thin films of poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN) and their blends were prepared by means of spin-coating their corresponding solutions onto silicon wafers, followed by being annealed at different temperatures. The surface phase separations of PMMA/SAN blends were characterized by virtue of atomic force microscopy (AFM). By comparing the tapping mode AFM (TM-AFM) phase images of the pure components and their blends, surface phase separation mechanisms of the blends could be identified as the nucleation and growth mechanism or the spinodal decomposition mechanism. Therefore, the phase diagram of the PMMA/SAN system could be obtained by means of TM-AFM. Contact mode AFM was also used to study the surface morphologies of all the samples and the phase separations of the blends occurred by the spinodal decomposition mechanism could be ascertained. Moreover, X-ray photoelectron spectroscopy was used to characterize the chemical compositions on the surfaces of the samples and the miscibility principle of the PMMA/SAN system was discussed.     

Preparation and surface activity of biodegradable polymeric surfactants II: Dyeing properties of biodegradable dextrin derivatives in cotton dyeing

The biodegradability and dyeing properties of a series of dextrin‐derivative surfactants in direct‐dye cotton‐dyeing systems have been studied. It was found that these surfactants have good biodegradability, which is lacking in traditional dyeing auxiliaries. In dye‐surfactant systems, the degree of aggregation of direct dyes with surfactants was found to influence the rate of cotton dyeing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2620–2624, 2007     

Spectroscopic behavior of poly(vinyl alcohol) films with different molecular weights after UV irradiation,thermal annealing,and double treatment with UV irradiation and thermal annealing

Pure poly(vinyl alcohol) (PVA) films with molecular weights 5,000, 72,000, and 125,000 g/mole were prepared by casting technique. The thickness of prepared samples was 0.21 mm. Xenon arc lamp was used to irradiate two samples from each molecular weight at 400 W for 5 min. One from each irradiated PVA samples was heated at 423 K for 2 h. An additional PVA sample unirradiated from each molecular weight was heated at 423 K for 2 h. Optical absorption measurements have been carried out in the wavelength range of 190–900 nm for untreated, UV‐irradiated, heated, and double‐treated samples by UV irradiation and heat. The double‐treated PVA samples with molecular weights 5,000 and 72,000 g/mole showed approximately zero transmission in comparison with untreated PVA sample in the wavelength range of 190–320 nm. PVA sample with 125,000 g/mole was irradiated with 600 W for 5 min to obtain the zero transmission in the same wavelength range. Identification of the structure and assignments of energy bands were studied also by using FTIR. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 589–594, 2003     

Synthesis and characterization of novel two‐component conjugated polythiophenes with 3‐octyl and 3‐isooctylthiophene side chains

With copolymerization functionalization, a novel solution‐processable polymer, poly{(3‐octylthiophene)‐co‐[3‐(2‐ethyl‐1‐hexyl)thiophene]} (P3OTIOT), combining the electrochemical properties of poly(3‐octylthiophene) (P3OT) and poly[3‐(2‐ethyl‐1‐hexyl)thiophene] (P3IOT) was synthesized by the FeCl₃‐oxidative approach. The characterization of the polymers included Fourier transform infrared, ¹H‐NMR, gel permeation chromatography, thermogravimetric analysis (TGA), ultraviolet–visible spectroscopy, and photoluminescence (PL). P3OTIOT had excellent solubility in common organic solvents. Investigations of the optical properties showed that the optical band‐gap energy of P3OTIOT was similar to that of P3OT (2.43 eV) at 2.45 eV and 6% lower than that of P3IOT in CHCl₃ solutions. The bandwidth of the P3OTIOT absorption approached that of P3OT, ranging from 370 to 570 nm, and the emission maximum of P3OTIOT was only 50 nm blueshifted with respect to that of P3OT. However, the PL intensity of P3OTIOT was 7 times higher than that of P3OT. TGA studies showed that P3OTIOT had very good thermal stability, losing 5% of its weight on heating to 300°C. It is suggested that P3OTIOT has low band‐gap energy, a high PL quantum yield, and processability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1169–1175, 2007     

Humidity and wetting effects in spin‐cast blends of insulating polymers and conducting polyaniline doped with DBSA

In this article, morphological structures are presented that are formed during spin coating of thin composite polymer films, containing a conjugated polymer. The system under study is a mixture of electrically conductive polyaniline doped with dodecylbenzenesulfonic acid and a conventional, nonconducting polymer—polystyrene or poly(methyl methacrylate). The dopant strongly influences film morphology, acting as a surfactant at a polymer/polymer interface. The effect of solution composition, spin‐coating atmosphere, and solvent on final morphology is analyzed. Experimental data were collected by means of several techniques: dynamic Secondary Ion Mass Spectrometry, Atomic Force Microscopy, UV–Vis spectroscopy, and optical microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Spectroscopic study of the modification of cellulose with polyethylenimines

The reaction of cellulose with polyethylenimines (PEIs) was studied using diffuse reflectance ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance FTIR spectroscopy, and standard colorimetry. PEIs were applied from aqueous solutions at the natural pH (pH ～ 11) and at pH = 6. The obtained materials were exposed to different thermal treatments in air. Celluloses treated at pH = 11 suffer the reversible formation of amine bicarbonate salts. This reaction was not observed in celluloses treated at pH = 6 because of the protonation of the amine groups. In all treated celluloses, the PEI amine groups reacted with cellulose carbonyl groups at moderate temperatures to form Schiff bases, which were responsible for the yellowing of the material. At higher temperatures other oxidation products were detected in the UV–vis and infrared spectra. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2196–2202, 2004     

Synthesis and characterization of carboxymethyl chitosan containing functional ultraviolet absorber substituent

A series of carboxymethyl chitosan (CMC) with 2.4‐dihydoxybenzophenone (UV‐0) substituent were synthesized by the Mannich reaction of CMC hydrochloride and UV‐0 in the solvent of methanol and water. The different molar degree of substitution (MS) was achieved by changing the UV‐0 content. The effects of MS on ultraviolet absorbability, crystallinity, moisture‐absorption and ‐retention property, and photostability were investigated respectively. The obtained products were characterized by means of Fourier transform infrared spectra (FTIR), proton nuclear magnetic resonance spectroscopy (¹H NMR), X‐ray diffraction, and UV spectrophotometer. It was found that the grafted products were water‐soluble, and the increased MS values could enhance the moisture‐retention property and photostability, while decreased the crystallinity and moisture‐absorption property. The ultraviolet absorption peaks became stronger by introducing UV‐0 into the CMC backbones. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis,characterization, and photochemical properties of chromophores containing photoresponsive azobenzene and stilbene

In this article, we describe the synthesis of two azobenzene and two stilbene‐based diacetylene chromophores containing terminal electron‐donating (? OCH₃) and electron‐withdrawing (? NO₂) terminal groups with esterification reactions. The target compounds were characterized by NMR, X‐ray diffraction (XRD), absorption, and photoluminescence spectroscopies. We investigated the structural effects of these photochromic compounds on the E–Z photoisomerization and 1,4‐addition under UV irradiation. 4‐[(4‐Nitrophenyl)‐diazenyl]phenyl pentacosa‐10,12‐diynoate, incorporating the electron‐withdrawing nitro group (? NO₂), underwent the fastest rate of Z‐to‐E isomerization in darkness via a rotation mechanism. Our results demonstrate that self‐assembled azobenzene Z isomers exhibited enhanced fluorescence under UV irradiation. XRD spectroscopy identified bilayer packing by the polydiacetylene films after 1,4‐addition. Chromophores comprising the diacetylene group presented moderate photochromic stability upon 1,4‐addition, changing from their original yellowish color to form a blue phase. These synthesized compounds may be useful in the development of new and unique functional materials that exhibit bistable photochromism. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of processable polyaniline doped with novel dopant NaSIPA

Aniline has been polymerized in the presence of a novel dopant sodio‐5‐sulfo‐isophthallic acid (NaSIPA), via the chemical oxidative polymerization route. The thermal stability and processability of polyaniline prepared by indirect method (PD1) have been improved significantly (290°C) as compared to polyaniline doped with conventional inorganic dopants like HCl or H₂SO₄, without much loss of electronic conductivity (5.07 S/cm in PD1). This suggests its use for melt blending with engineering thermoplastics. However, polyaniline prepared by direct method (PD2) can be melt‐blended only with conventional thermoplastics like polyethylene, polypropylene, polystyrene, etc. Low‐temperature studies reveal the 1‐D variable range hopping as a conduction mechanism for direct polymer (PD2), with parameters T_o and σ_o as 4112 K and 15.1 S/cm, respectively. However, for indirectly doped polymer (PD1) Arrhenius‐type model, having parameters |(E_F ? E_C)| and σ_C as 0.04 eV and 28.4 S/cm, respectively, it suited well. The coherence length as found from XRD data was around 28.8 nm for PD1 and 25.2 nm for PD2. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

New antimicrobial agents: The synthesis of Schiff base polymers containing transition metals and their characterization and applications

A new polymeric Schiff base containing formaldehyde and 2‐thiobarbituric acid moieties was synthesized by the condensation of a monomeric Schiff base derived from 2‐hydroxyacetophenone and hydrazine. Polymer–metal complexes were also synthesized by the reaction of the polymeric Schiff base with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) acetate. The polymeric Schiff base and its polymer–metal complexes were characterized with magnetic moment measurements, elemental analyses, and spectral techniques (infrared, ¹H‐NMR, and ultraviolet–visible). The thermal behaviors of these coordination polymers were studied by thermogravimetric analysis in a nitrogen atmosphere up to 800°C. The thermal data revealed that all of the polymer–metal complexes showed higher thermal stabilities than the polymeric Schiff base and also ascribed that the Cu(II) polymer–metal complex showed better heat resistant properties than the other polymer–metal complexes. The antimicrobial activity was screened with the agar well diffusion method against various selected microorganisms, and all of the polymer–metal complexes showed good antimicrobial activity. Among all of the complexes, the antimicrobial activity of the Cu(II) polymer–metal complex showed the highest zone of inhibition because of its higher stability constant and may be used in biomedical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and optical properties of transparent epoxy composites containing ZnO nanoparticles

Polymer nanocomposites are usually made by incorporating dried nanoparticles into polymer matrices. This way not only leads to easy aggregation of nanoparticles but also readily brings about opaqueness for nanocomposites based on functionally transparent polymers. In this letter, transparent ZnO/epoxy nanocomposites with high‐UV shielding efficiency were prepared via two simple steps: first, in situ preparation of zinc hydroxide (Zn(OH)₂)/epoxy from the reaction of aqueous zinc acetate (Zn(Ac)₂·2H₂O) and sodium hydroxide (NaOH) at 30°C in the presence of high‐viscosity epoxy resin; second, thermal treatment of the as‐prepared Zn(OH)₂/epoxy hybrid into ZnO/epoxy composites. Optical properties of the resultant ZnO/epoxy nanocomposites were studied using an ultraviolet–visible (UV–vis) spectrophotometer. The nanocomposites containing a very low content of ZnO nanoparticles (0.06 wt %) possessed the optimal optical properties, namely high‐visible light transparency and high‐UV light shielding efficiency. Consequently, the as‐prepared ZnO/epoxy nanocomposites are promising for use as novel packaging materials in lighting emitting diodes technology. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012