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     

Synthesis of amine‐functionalized block copolymers for nanopollutant removal from water

Polyamines are rare in literature owing to increased reactivity, sensitivity to air and moisture, low stability, and processing difficulties. Here, we report the synthesis and characterization of highly processable polyamines and use them for the removal of dissolved metallic nanoparticles from water. Three amphiphilic block polyamines such as poly(N‐aminoethyl acrylamide‐b‐styrene), poly(N‐aminopropyl acrylamide‐b‐styrene), and poly(N‐aminoxylyl acrylamide‐b‐styrene) have been synthesized using atom transfer radical polymerization of ethyl acrylate and styrene followed by aminolysis of the acrylic block. The polymerization and properties of the polymers are studied using different physicochemical techniques. Surface morphology of films prepared from these block copolymers by dissolving in different solvents such as chloroform, tetrahydrofuran and N,N‐dimethylformamide, and drop‐casting polymers on a glass substrate show interesting porous films and spherical nanostructures. In addition, the amine‐functionalized block copolymers have been used for the removal of nanoparticles from water and show high extraction efficiency toward silver (Ag) and gold (Au) nanoparticles. All three amine‐functionalized block copolymers show higher extraction capacities (Q_e) toward Au NPs (50–109 mg g^?1) and Ag NPs (99–117 mg g^?1). Our approach allows us to make amine‐functionalized block copolymers which are stable in air and can be easily processed in nonpolar solvents. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40943.     

Emission properties of composite semiconducting polymer nanoparticles

A series of composite polymer nanoparticles was prepared from poly(N‐vinylcarbazole) (PVK) and poly(2,5‐bistriethoxy‐p‐phenylene vinylene‐alt‐phenylene vinylene) (BTEO–PPV‐alt‐PPV). The nanoparticle sizes were measured to be in the range of 50–80 nm with transmission electron microscopy. The photoluminescence intensity of PVK decreased with the content of BTEO–PPV‐alt‐PPV increasing in the composite polymer nanoparticles because the excited states in PVK were quenched by BTEO–PPV‐alt‐PPV. The emission from BTEO–PPV‐alt‐PPV was enhanced in the composite polymer nanoparticles because of energy transfer from PVK to BTEO–PPV‐alt‐PPV for excitation at the absorption maximum of PVK. The energy‐transfer efficiency was markedly improved in the composite polymer nanoparticles versus the composite polymer films according to emission spectral analyses. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Optical‐limiting properties of poly(arylene ethynylenes) containing thiophene ring

Poly(arylene ethynylenes) containing thiophene ring were synthesized in good yield. In synthesis, pyridine was added to accelerate reaction owing to its phase transfer effect on CuI. The optical‐limiting properties of the prepared polymers were investigated with a Q‐switched Nd : YAG laser at 532 nm with 10‐ns pulse width. The experiments showed that the order of the optical‐limiting response of the polymers is poly(3‐hexyl‐2,5‐thienyleneethylene) (P3) > poly(2,5‐dihexyloxy‐1,4‐benzyleneethylene‐3‐hexyl‐2,5‐thienyleneethylene) (P2) > poly(9‐hexyl‐3,6‐carbazoleethylene‐3‐hexyl‐2,5‐thienyleneethylene) (P1). It can be understood well by the comparison of their conjugation length and D‐A structure. In addition, the results indicated that introducing the electron‐rich aromatic ring into the polymer backbone to enhance the D‐A structure would be an effective way to improve its optical‐limiting property. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 131–135, 2004     

Controlled dispersion of a porphyrin/fullerene donor‐acceptor complex in semiconducting polymer thin films: Intermolecular interactions of polymers with porphyrin and fullerene

Thin films composed of semiconducting polymers [poly(2‐vinyl naphthalene), poly(4‐diphenyl aminostyrene), poly(1‐vinyl pyrene), and poly(3‐hexyl thiophene‐2,5‐diyl)], zinc(II)?5,10,15,20‐tetra‐(2‐naphthyl)porphyrin, and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester blends were prepared to investigate the controlled dispersion of porphyrin molecules in semiconducting polymer thin films. Tailoring the intermolecular interactions between the polymer/fullerene, polymer/porphyrin, and porphyrin/fullerene systems was found to be an effective method of controlling the dispersion. When the polymer/porphyrin interactions were enhanced, intermixed porphyrin/fullerene donor–acceptor complex domains were formed, whereas under conditions where the polymer/porphyrin interactions were weakened, the complex assembled at the borders between the polymer and fullerene phases. This concept could potentially be applied to various combinations of porphyrin/fullerene systems in semiconducting polymer thin films to develop polymer solar cells with excellent performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41629.     

Semiconductive poly[N1,N4‐bis(thiophen‐2‐ylmethylene)benzene‐1,4‐diamine]‐nickel oxide nanocomposite based ethanol sensor

This study aims to use the conductivity of a synthetic polymer as the sensing probe for ethanol. In order to enhance the sensitivity of the sensor, a composite of the polymer and nickel oxide (NiO) nanoparticles was formed as it improved the conductivity. This composite exhibited 100 times more conductivity than the neat polymer. The semiconductive nanocomposite of poly [N¹,N⁴‐bis(thiophen‐2‐ylmethylene)benzene‐1,4‐diamine]‐nickel oxide (PBTMBDA‐NiO) was prepared by in situ chemical oxidative polymerization. The monomer was N¹,N⁴‐bis(thiophen‐2‐ylmethylene)benzene‐1,4‐diamine (BTMBDA). The monomer (BTMBDA), polymer (PBTMBDA), and NiO nanoparticles used in this study were synthesized. The monomer was prepared by refluxing together 2‐thiophene carboxaldehyde, benzene‐1,4‐diamine, and few drops of glacial acetic acid in ethanol medium for 3 h. The polymer, PBTMBDA, was formed by the chemical oxidative polymerization of BTMBDA in chloroform by FeCl₃. NiO nanoparticles were prepared by slow addition of aqueous ammonia to anhydrous nickel chloride at room temperature (28 ± 2 °C), and at a pH of 8 under constant stirring condition. The composite was formed by in situ chemical oxidative polymerization of BTMBDA in chloroform by FeCl₃ in the presence of the dispersed NiO nanoparticles. The molecular structure of BTMBDA and PBTMBDA were confirmed by nuclear magnetic resonance (NMR) (¹H, ¹³C, and Dept‐90°), Fourier transform infrared spectroscopy, and ultraviolet (UV)–visible spectroscopy. The PBTMBDA and PBTMBDA‐NiO nanocomposite were characterized by X‐ray diffraction, thermogravimetric analysis, field emission scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy analysis. The results of characterization studies indicate the strong interaction between PBTMBDA and NiO in the nanocomposite. The broadness of ¹H NMR peaks in PBTMBDA was due to the increased number of monomer units. The disappearance of the peak of α‐hydrogens on thiophene confirms the polymerization involving the fifth position of thiophene part of BTMBDA. The Fourier transform infrared spectroscopy spectra revealed that position of the characteristic peaks of the functional groups in the monomer shifted toward lower wave numbers in PBTMBDA and PBTMBDA‐NiO nanocomposite. This shifting confirms the presence of extended conjugation along the polymer backbone. Electronic spectra of these compounds showed three absorption bands corresponding to π→π*, n→π* and n→π* transitions of π electron of carbon, lone pair electrons of S, and lone pair electrons of N (imine) groups, respectively. From the Tafel plot, the exchange current density evaluated for the BTMBDA and PBTMBDA are 0.2815 × 10⁻⁸ and 1.1508 × 10⁻⁸ A cm⁻², respectively. PBTMBDA is evaluated to be a better electrode material than the BTMBDA. The X‐ray diffraction plots showed that the characteristic peak of NiO in PBTMBDA‐NiO nanocomposite suggested successful incorporation of NiO in PBTMBDA‐NiO nanocomposite. The thermogravimetric analysis revealed the improved thermal stability of the composite. Field emission scanning electron microscopy and energy‐dispersive X‐ray spectroscopy analysis confirmed the presence of the NiO in the composite. Incorporation of nickel oxide nanoparticles improved the electrical conductivity and stability of PBTMBDA. The conductivity of the polymer was found to be of the order of 10⁻⁵ S cm⁻¹ while that of the composite was of the order of 10⁻³ S cm⁻¹. The nanocomposite was found to be thermally more stable than PBTMBDA and exhibited better direct‐current electrical conductivity and isothermal stability than the PBTMBDA as revealed by the four‐probe study. The electrical conductivity as inferred from the four‐probe method was used as the parameter to study the isothermal stability of the composite. The PBTMBDA‐NiO nanocomposite based vapor sensor was constructed for the sensing of ethanol vapor in commercial ethanol and real samples (alcoholic drinks: Beer, Wine, Brandy, Vodka, Whisky, and Rum) It was observed that on exposure to ethanol vapor at ambient temperature, the electrical resistivity of the nanocomposite increased indicating suppression of charge carriers. The interaction of ethanol vapor with PBTMBDA in PBTMBDA‐NiO nanocomposite was confirmed by IR spectral technique. The change in the structure of the PBTMBDA on interaction with ethanol was highlighted by the changes in the infrared spectrum. The conductivity of the polymer was explained using the structure‐activity relationship of the monomer evaluated using Gaussian 09 software. This study also analyzed the total electron density with electrostatic potential of the monomer and its correlation with chemical reactivity in order to explain the ethanol vapor sensing‐property of the nanocomposite. A new method of ethanol vapor sensing by a conducting polymer composite is hereby reported. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45918.     

Imidazolium‐functionalized norbornene ionic liquid block copolymer and silica composite electrolyte membranes for lithium‐ion batteries

Imidazolium‐functionalized norbornene and benzene‐functionalized norbornene were synthesized and copolymerized via ring‐opening metathesis polymerization to afford a polymeric ionic liquid (PIL) block copolymers {5‐norbornene‐2‐methyl benzoate‐block ‐5‐norbornene‐2‐carboxylate‐1‐hexyl‐3‐methyl imidazolium bis[(trifluoromethyl)sulfonyl]amide [P(NPh‐b ‐NIm‐TFSI)]} with good thermal stability. On this basis, the solid electrolyte, P(NPh‐b ‐NIm‐TFSI)–lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), through blending with LiTFSI, and the nanosilica composite electrolyte, P(NPh‐b ‐NIm‐TFSI)–LiTFSI–SiO₂, through blending with LiTFSI and nanosilica, were prepared. The effects of the PILs and silica compositions on the properties, morphology, and ionic conductivity were investigated. The ionic conductivity was enhanced by an order of magnitude compared to that of polyelectrolytes with lower PIL compositions. In addition, the ionic conductivity of the nanosilica composite polyelectrolyte was obviously improved compared with that of the P(NPh‐b ‐NIm‐TFSI)–LiTFSI polyelectrolyte and increased progressively up to a maximum with increasing silica content when SiO₂ was 10 wt % or lower. The best conductivity of the P(NPh‐b ‐NIm‐TFSI)–20 wt % LiTFSI–10 wt % SiO₂ composite electrolyte with 7.7 × 10^?5 S/cm at 25 °C and 1.3 × 10^?3 S/cm at 100 °C were obtained, respectively. All of the polyelectrolytes exhibited suitable electrochemical stability windows. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44884.     

Conductive polyaniline–polythiophene/poly(ethylene terephthalate) composite fiber: Effects of pH and washing processes on surface resistivity

A conductive polyaniline (PAn)–polythiophene (PTh)/poly(ethylene terephthalate) (PET) composite fiber was prepared by polymerization of aniline and thiophene in the presence of PET fibers in an organic medium with FeCl₃. The effects of polymerization conditions, such as polymerization medium, mol ratios of aniline/thiophene and FeCl₃/aniline‐thiophene as well as polymerization temperature and time, were investigated on PAn–PTh content (%) and surface resistivity of the composite. The composite with the lowest surface resistivity (1.30 MΩ/cm²) was obtained by polymerization of aniline and thiophene (1/3 mol ratio) in acetonitrile/chloroform (1/5 volume ratio) at 20°C. The surface resistivity of the PAn–PTh/PET composite containing 4.8% PAn–PTh was increased from 1.9 MΩ/cm² to 270 MΩ/cm² at pH 11. The washing durability of the composites was determined with domestic and commercial laundering processes by monitoring the surface resistivity and morphology. The composite was also characterized with FTIR, TGA, elemental analysis, optic microscope and SEM techniques. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41979.     

Effects of molecular weight on electroluminescence of nanogold‐bonded poly(9,9‐dioctylfluorene‐alt‐thiophene) at a constant polymer‐to‐gold weight ratio

The effects of molecular weight on electroluminescent properties of the light emitting polymeric nanocomposite, poly(9,9‐dioctylfluorene‐alt‐thiophene) with chemically bonded gold nanoparticles (PDOFT‐Au), have been studied under a condition of constant polymer‐to‐gold weight ratio. The polymer, PDOFT, was first synthesized via the Suzuki cross‐coupling reaction and then bonded to in situ‐formed gold nanoparticles (AuNPs) via terminal thiol functional groups which had been generated during the quenching of polymerization. A series of PDOFT‐Au's of various molecular weights have thus been synthesized. At a constant polymer‐to‐gold weight ratio, the average size of gold nanoparticles (AuNPs) increased with an increase in the molecular weight of PDOFT. Although an increased molecular weight led to a red shift in UV‐absorption and PL spectra as well as an increased PL quantum efficiencies (?_PL) for all samples (both PDOFT and PDOFT‐Au), the effect of AuNPs bonding became more noticeable when the molecular weight was higher. As for light emitting diode (LED) device fabrication, an increase in the molecular weight of PDOFT also led to a red shift in the EL spectra of the fabricated LED devices. Nevertheless, PDOFT‐Au, compared with PDOFT, had a lower threshold voltage, an increased brightness and current density, and an improved photometric efficiency. Moreover, the photometric efficiency increased with an increase in the molecular weight of the polymer, from 0.298 cd/A for PDOFT‐Au3 up to 0.645 cd/A for PDOFT‐Au1. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermosensitive polymeric micelles based on the triblock copolymer poly(d,l‐lactide)‐b‐poly(N‐isopropyl acrylamide)‐b‐poly(d,l‐lactide) for controllable drug delivery

A thermosensitive amphiphilic triblock copolymer, poly(d,l ‐lactide) (PLA)‐b‐poly(N‐isopropyl acrylamide) (PNIPAAM)‐b‐PLA, was synthesized by the ring‐opening polymerization of d,l ‐lactide; the reaction was initiated from a dihydroxy‐terminated poly(N‐isopropyl acrylamide) homopolymer (HO‐PNIPAAM‐OH) created by radical polymerization. The molecular structure, thermosensitive characteristics, and micellization behavior of the obtained triblock copolymer were characterized with Fourier transform infrared spectroscopy, ¹H‐NMR, gel permeation chromatography, dynamic light scattering, and transmission electron microscopy. The obtained results indicate that the composition of PLA‐b‐PNIPAAM‐b‐PLA was in good agreement with what was preconceived. This copolymer could self‐assemble into spherical core–shell micelles (ca. 75–80 nm) in aqueous solution and exhibited a phase‐transition temperature around 26 °C. Furthermore, the drug‐delivery properties of the PLA‐b‐PNIPAAM‐b‐PLA micelles were investigated. The drug‐release test indicated that the synthesized PLA‐b‐PNIPAAM‐b‐PLA micelles could be used as nanocarriers of the anticancer drug adriamycin (ADR) to effectively control the release of the drug. The drug‐delivery properties of PLA‐b‐PNIPAAM‐b‐PLA showed obvious thermosensitive characteristics, and the release time of ADR could be extended to 50 h. This represents a significant improvement from previous PNIPAAM‐based drug‐delivery systems. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45304.     

Modification of bitumen emulsion via heterocoagulation with SIS triblock copolymer latex

Bitumen emulsions have often been modified by styrene–butadiene rubber latex. The modified bitumen can have excellent low‐temperature cracking resistance, but rutting resistance at high temperature still remains poor. In the current work, for the first time, a stable poly(styrene‐b‐isoprene‐b‐styrene) (SIS) triblock copolymer latex is synthesized by reversible addition–fragmentation transfer (RAFT) emulsion polymerization. Based on this, a simple heterocoagulation process is developed to prepare the bitumen emulsions modified by SIS. The heterocoagulation results in hybrid particles of SIS shell and bitumen core. With addition of 5 wt % SIS, a continuous polymer‐rich phase could be formed in the modified bitumen once the modified emulsion was broken down. The bitumen modified by 5 wt % SIS shows a significant increase in complex modulus at high temperature and a significant decrease in loss tangent, suggesting excellent resistance to rutting at high temperature, which is consistent with the significant increase in softening point from 41 °C for the base bitumen up to 64 °C. Meanwhile, the ductility at 5 °C of the modified bitumen is also dramatically increased from 1.4 cm for the base bitumen to 40 cm, indicating the low‐temperature cracking resistance should also be much enhanced. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45510.     

Synthesis and characterization of a kind of poly(3‐butylthiophene methine) with azo side groups

To enhance the third nonlinear optical properties of poly(thiophene methine), we synthesized a new kind of poly(3‐butylthiophene methine) with azo side groups: poly[(3‐butylthiophene‐2,5‐diyl)‐p‐(N,N‐dimethylamino)azobenzylidenequinomethane] (PBTDMABQ). PBTDMABQ and its intermediate product were characterized with IR, ultraviolet–visible, and ¹H‐NMR spectroscopy. The band gaps of PBTDMABQ were calculated to be 1.94 and 2.06 eV with two different models. The thermal stability, determined by thermogravimetric analysis, indicated that PBTDMABQ decomposed above 345°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1261–1265, 2005     

Influence of alkyl chain length on the gelation mechanism of thermoreversible gels of regioregular poly(3‐alkyl thiophenes) in xylene

The gelation rates of poly(3‐alkyl thiophenes) (P3AT) are strongly dependent on the pendent alkyl chain length. Poly(3‐hexyl thiophene (P3HT) gels at higher isothermal temperatures than that of poly(3‐dodecyl thiophene), (P3DDT). Gelation rate has been expressed as a combination of a temperature dependent function f(T) and a concentration dependent function (φⁿ); φ being the reduced overlapping concentration of P3AT. From the slope of double logarithmic plot of gelation rate and φ, n values are calculated to be 0.52 and 0.60 for P3HT and P3DDT, respectively. These values are close to the value of percolation exponent β (0.45) for three‐dimensional lattice; so both the gels may approximately obey three dimensional percolation model. The f(T) of gelation rate consists of two steps (i) coil‐to‐rod transformation followed by (ii) fibrillar crystallization. The coil‐to‐rod transition is accompanied by a red shift in the π–π* transition band in UV–vis spectra. Flory and Weaver theory is used to understand the coil‐to‐rod transformation process. The theory of fibrillar crystallization extended to dilute solution has been employed to understand the crystallization process. The results clearly indicate that the activation energy of conformational change (ΔF) is higher for P3DDT than that of P3HT. But the free energy change for the formation of critical size nucleus (Δ G) is lower for P3DDT than that of P3HT. A comparison of ΔF and Δ G values indicate conformational ordering is the rate‐determining step for P3AT with dodecyl substituent whereas crystallization is the rate‐determining step for P3AT with hexyl substituent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2528–2537, 2007     

Study of the processing pathway for cosolvent addition in active layer preparation of inverted organic solar cell

Investigation on processing pathway for co‐solvent addition in active layer preparation of an inverted organic solar cell indicated that the composite films cast out of simple marginal solvent (like cyclohexanone) addition in poly(3‐hexyl thiophene)‐[6,6]‐phenyl C₆₁‐butyric acid methyl ester (P3HT‐PCBM) solution were not effectively crystallized. A comparison of one step direct marginal solvent addition to the P3HT‐PCBM solution with the modified two step process consisting of primary P3HT crystallization in first step by marginal solvent addition to a solution of only P3HT in good solvent (like ortho‐dichloro benzene) followed by mixing of PCBM solution revealed improvement in P3HT crystallization in the latter method. Grazing incidence X‐ray diffraction measurements supported favorable vertical concentration gradient in the P3HT‐PCBM composite film. This modification of active layer morphology with the two step individually mixed cyclohexanone addition into the active layer spin coating solution results in an improved power conversion efficiency of 3.39%, an improvement of more than 10% compared to the conventional one step blended co‐solvent addition method. POLYM. ENG. SCI., 55:1758–1766, 2015. © 2014 Society of Plastics Engineers     

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     

Highly efficient adsorbent for organic dyes based on a temperature‐ and pH‐responsive multiblock polymer

The self‐assembly behavior of amphiphilic block copolymers in selective solutions has many applications in environmentally responsive polymer materials. In this article, we report on a new amphiphilic, temperature and pH dual‐responsive poly[2‐dimethylaminoethyl methacrylate‐co‐(methyl methacrylate)]‐b‐poly[poly(ethylene glycol) methacrylate] [P(DMAEMA‐co‐MMA)‐b‐PPEGMA], which was synthesized via reversible addition–fragmentation chain‐transfer polymerization. The structure, self‐assembly behaviors, and process of organic dye adsorption were characterized by ¹H‐NMR, ultraviolet–visible absorbance spectroscopy, and DLS measurements. P(DMAEMA‐co‐MMA)‐b‐PPEGMA was proven to be an outstanding adsorbent with excellent reversibility. Methyl red was released from the micelles as the pH value of the solution was adjusted to 4, and it could also be encapsulated again when the pH value was adjusted to 7.4 because of the sensitive pH‐responsive ability. It is promising that the triblock polymer had a positive effect on dye adsorption for environmental protection. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46626.     

Synthesis and spectroelectrochemistry of dithieno(3,2‐b:2′,3′‐d)pyrrole derivatives

New π‐conjugated polymers containing dithieno(3,2‐b:2′,3′‐d)pyrrole (DTP) were successfully synthesized via electropolymerization. The effect of structural differences on the electrochemical and optoelectronic properties of the 4‐[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl]aniline (DTP–aryl–NH₂), 10‐[4H‐dithiyeno(3,2‐b:2′,3′‐d)pirol‐4‐il]dekan‐1‐amine (DTP–alkyl–NH₂), and 1,10‐bis[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl] decane (DTP–alkyl–DTP) were investigated. The corresponding polymers were characterized by cyclic voltammetry, NMR (¹H‐NMR and ¹³C‐NMR), and ultraviolet–visible spectroscopy. Changes in the electronic nature of the functional groups led to variations in the electrochemical properties of the π‐conjugated systems. The electroactive polymer films revealed redox couples and exhibited electrochromic behavior. The replacement of the DTP–alkyl–DTP unit with DTP–aryl–NH₂ and DTP–alkyl–NH₂ resulted in a lower oxidation potential. Both the poly(10‐(4H‐Dithiyeno[3,2‐b:2′,3′‐d]pirol‐4‐il)dekan‐1‐amin) (poly(DTP–alkyl–NH₂)) and poly(1,10‐bis(4H‐dithieno[3,2‐b:2′,3′‐d]pyrrol‐4‐yl) decane) (poly(DTP–alkyl–DTP)) films showed multicolor electrochromism and also fast switching times (<1 s) in the visible and near infrared regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40701.     

The tough microcapsules of acrylic acid–styrene–isoprene–styrene quadrablock copolymer shell via Pickering emulsion technique

Pickering emulsion technique has been demonstrated a simple method to fabricate the microcapsules. However, the resulted microcapsules are often fragile. This limits their applications. Here, we report that the microcapsules with the nanostructured shell of poly(acrylic acid‐b‐styrene‐b‐isoprene‐b‐styrene) (ASIS), which is of high toughness and elasticity, could be fabricated via Pickering emulsions using ASIS nanoparticles as stabilizing particles. The surfactant‐free ASIS latex (with theoretical molecular weight for each block: 1.5k–15k–55k–10k) was synthesized by reversible additional fragmentation transfer (RAFT) emulsion polymerization using amphiphilic macro‐RAFT agent [poly(acrylic acid)₂₀‐b‐polystyrene₅ trithiocarbonate] as both reactive surfactant and polymerization mediator. It was found that the ASIS nanoparticles were able to self‐assemble on oil/water interface to stabilize Pickering emulsion of hexadecane in the pH range from 8 to 12. The droplet diameter was finely tuned from 17 to 5 µm by increasing the ASIS particle levels from 0.13 to 12 wt % based on the mass of the ASIS aqueous dispersions. With toluene as a coalescing aid, the capsules with a coherent and nonporous shell were obtained with the dispersed phase volume percentage as high as 50%. The toluene treated capsules were so mechanically strong to survive the utrasonic treatment. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46700.     

Hydrophobic and tribological behaviors of a poly(p‐phenylene benzobisoxazole) fabric composite reinforced with nano‐TiO2

1H,1H,2H,2H‐Perfluorooctyl trichlorosilane (PFTS) was used to modify TiO₂ nanoparticles, and hydrophobic PFTS–TiO₂ nanoparticles were obtained by an ultrasonic reaction method. The PFTS–TiO₂ surface morphological and hydrophobic properties were analyzed with scanning electron microscopy (SEM), Fourier transform infrared spectrometry, and contact angle (CA) testing. Then, the poly(p‐phenylene benzobisoxazole) fabric–phenolic composite filled with PFTS–TiO₂ as a lubricant additive was fabricated by a dip‐coating process. The tribological properties of the composite were investigated, and the wear surface morphology was observed by SEM. The experimental results show that the water CA of the composite filled with PFTS–TiO₂ was 158°, and the composite containing 4 wt % PFTS–TiO₂ exhibited excellent antifriction and abrasion resistance. The hydrophobic surface of the composite showed excellent durable performance with a static water CA of 126.7° after abrasion. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45077.     

Visualization of PVDF nanofibers coated on filter paper using fluorescein silica nanoparticles

Fluorescein silica nanoparticles (NPs) were prepared using a silane compound bound between fluorescein‐N‐hydroxysuccinimide (NHS‐Fluorescein) and 3‐aminopropylorthosilicate by a sol–gel method. The fluorescein‐silica NPs were mixed with a poly(vinylidene fluoride) (PVDF) solution, and the solution loaded with the NPs was electrospun on a filter paper. Scanning electron microscopy and transmission electron microscopy images confirmed the encapsulation of the fluorescein silica NPs in the PVDF nanofibers. Laser scanning confocal microscopy (LSCM) images showed fluorescein silica NPs as dots, and photoluminescence (PL) images obtained using a fluoroanalyzer indicated the emission of uniform PL from filter papers coated with fluorescein‐silica‐NP‐encapsulated PVDF nanofibers. It was demonstrated that the fluorescein silica NPs enabled PVDF nanofibers coated on a filter paper to be easily visualized. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45125.