Electrochemical behaviour and electrochemical polymerization of fluoro‐substituted anilines

The electrochemical behaviour of three fluoro‐substituted aniline monomers, 2‐fluoroaniline (2FAN), 3‐fluoroaniline (3FAN) and 4‐fluoroaniline (4FAN), was investigated in aqueous acidic and organic media by means of cyclic voltammetry (CV) studies. Constant potential electrolysis (CPE) of the monomers in acetonitrile–water mixture (1:1 by volume) using NaClO₄ as supporting electrolyte yielded soluble polymers. The mechanism of electrochemical polymerization was investigated using in situ electron spin resonance (ESR) and in situ UV–VIS spectroscopic techniques for one of the monomers (4FAN). Both CV and in situ UV–VIS measurements indicated that the polymers obtained are in the emeraldine base form. In situ ESR studies indicated that electrochemical polymerization involves a radical‐cation as an intermediate. Characterization of polymer products have been carried out using FTIR and NMR spectroscopic techniques, and thermal behaviour was studied using differential scanning calorimetry (DSC). It was found that conductivity can be imparted to as‐synthesized polyfluoroanilines via iodine doping. © 2002 Society of Chemical Industry     

Vinyl ester/clay based nanocomposites: a complementary study of vinyl ester polymerization by hyphenated rheo‐Fourier transform infrared and separate rheology/Fourier transform infrared measurements

This work is focused on the complementary information obtained from advanced in situ Fourier transform infrared (FTIR) spectroscopy and rheological measurements to correlate the structural changes with rheological properties upon polymerization of different organically modified montmorillonite clay/vinyl ester composites prepared by in situ polymerization. The microstructure and morphology of the nanocomposites were examined by X‐ray diffraction and transmission electron microscopy. The effect exerted by the presence of organic clay on the polymerization reaction of a vinyl ester based polymer matrix was evaluated. In situ and ex situ rheo‐FTIR measurements were compared to demonstrate the accuracy of this technique. © 2013 Society of Chemical Industry     

Polyaniline nanofibers for In situ MAO‐catalyzed polymerization of ethylene

In this work electro‐conductive polyaniline nanofibers (PAni‐nanofibers) were prepared via interfacial methodology. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations revealed that the synthesized PAni‐nanofibers present high aspect ratio with an average diameter of 80 nm, while they exhibit high conductivity (DC conductivity values: 4.19 ± 0.21 S cm^?1). After specific treatment to remove moisture and remaining trapped HCl from PAni‐nanofibers, it was possible to prepare promising polyethylene (PE)/PAni composites by in situ polymerization of ethylene using bis(cyclopentadienyl) zirconium(IV) dichloride (Cp₂ZrCl₂) and methylaluminoxane (MAO) as catalytic system. More precisely, various contents of PAni‐nanofibers (from 0.2 to 7 wt %) were successfully incorporated in the in situ produced PE/PAni nanocomposites. PAni‐nanofibers were found to affect significantly the crystallization of the polyolefinic matrix while preserving its thermal stability. Preliminary measurements of electric properties showed PAni‐nanofibres are able to bring electro‐conductive properties to the in situ polymerized PE/PAni composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41197.     

Efficient Synthesis of 9‐Tosylaminofluorene Derivatives by Boron Trifluoride Etherate‐Catalyzed Aza‐Friedel–Crafts Reaction of in situ Generated N‐Tosylbenzaldimines

An efficient and expeditious boron trifluoride etherate (BF₃⋅Et₂O) catalyzed one‐pot reaction for the synthesis of N‐tosyl‐9‐aminofluorenes and anthracene derivatives from in situ generated N‐tosylbenzaldimines via an aza‐Friedal–Crafts reaction has been developed. The catalytic reaction shows high substrate tolerance with excellent yields.     

Conducting properties of iodine‐doped low‐density polyethylene–poly(4‐vinylpyridine) blends

The conductivities of blends of low‐density polyethylene and poly(4‐vinyl pyridine) (P4VP) were studied. The blends were synthesized by in situ sorption and thermal polymerization of 4‐vinylpyridine in low‐density polyethylene. They showed, after iodine doping, conductivities of 1.7 to 5.0 × 10^?7 S cm^?1 at 298 K, depending on the P4VP mass increment into the matrix. Their conductivities were one order of magnitude higher for measurements at 338 K. The optimum ratio of iodine to pyridine (n) which gave the highest conductivity was 0.21. The thermal stability of doped blends was acceptable for their uses as electrochemical devices. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 939–944, 2003     

Effects of preparation method on microstructure and properties of UV‐curable nanocomposite coatings containing silica

UV‐curable nanocomposites were prepared by the blending method or the in situ method with nanosilica obtained from a sol–gel process. The microstructure and properties of the nanocomposite coatings were investigated using ²⁹Si‐NMR cross‐polarization/magic‐angle spinning, transmission electron microscopy (TEM), Fourier transform IR (FTIR), differential scanning calorimetry (DSC), and UV–visible (UV–vis) spectra, respectively. The NMR and TEM showed that during the blending method, tetraethyl orthosilicate (TEOS) completely hydrolyzed to form nanosilica particles, which were evenly dispersed in the polymer matrix. However, for the in situ method, TEOS partially hydrolyzed to form some kind of microstructure and morphology of inorganic phases intertwisted with organic molecules. FTIR analysis indicated that the nanocomposites prepared from the in situ method had much higher curing rates than those from the blending method. DSC and UV–vis measurements showed that the blending method caused higher glass‐transition temperatures and UV absorbance than the in situ method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1119–1124, 2005     

Infrared study on in situ polymerization of zinc dimethacrylate in poly(α‐octylene‐co‐ethylene) elastomer

An infrared spectroscopic method was used to follow the course of in situ polymerization of zinc dimethacrylate (ZDMA) in poly(α‐octylene‐co‐ethylene) elastomer (POE). The integral intensity of the 831 cm^?1 band, ie the out‐of‐plane deformation mode of ?CH, was used to determine the residual amount of ZDMA in composites cured at 165°C for different times, through which the course of in situ polymerization of ZDMA in POE was traced and the dynamic curve determined. The curing course of the ZDMA/POE/peroxide system at 165°C was examined with a rheometer and compared with the course of in situ polymerization. The results surprisingly show that the in situ polymerization of ZDMA is almost complete at the beginning stage of curing, and that substantial crosslinking starts subsequently. Scanning electron microscopy and transmission electron microscopy observations on morphologies of ZDMA/POE composites cured at 165°C for different times were carried out and confirmed the results of infrared experiments. Combining all the investigations, it was deduced that a competition exists between in situ polymerization and crosslinking in the composites. Covalent crosslinking rather than ionic bond crosslinks are the major types of crosslinks structures in ZDMA/POE composites, and its total density is lower than that of carbon‐ black‐reinforced POE. Copyright © 2004 Society of Chemical Industry     

Asymmetric,Regioselective Bromohydroxylation of 2‐Aryl‐2‐propen‐1‐ols Catalyzed by Quinine‐Derived Catalysts

The asymmetric bromohydroxylation of 2‐aryl‐2‐propen‐1‐ols catalyzed by quinine‐derived bifunctional catalyst has been developed. The regioselectivity was controlled by employing a boronate ester as tether which was formed in situ and enantioselectivity was introduced by taking advantage of a quinine‐derived bifunctional catalyst which activated the boronate ester and N‐bromosuccinimide (NBS) at the same time. Chiral bromohydrin, which is a useful feedstock in organic synthesis, was produced in moderate to excellent enantioselectivity in a two‐step reaction sequence.     

Polar polystyrene‐isoprene‐styrene copolymers with long polybutadiene branches

Polar polystyrene‐isoprene‐styrene (SIS) copolymers having epoxide groups and long polybutadiene (PB) branches were synthesized via the combination of in situ epoxidation, anionic polymerization and graft‐onto reaction. They were characterized with ¹H NMR, GPC, FT‐IR, DSC, and contact angle test. Their polarity was determined by the epoxidation degree and graft efficiency. The epoxidation degree linearly increased with the epoxidation time. The graft efficiency decreased with the branch length, but increased with the epoxidation degrees. Although their glass transition temperature (T_g) of diene blocks and flexibility properties had been negatively affected by in situ epoxidation, they could be modulated by the epoxidation degree, branch length, and branch density. Their T_g could be tailored by the branch length and branch density since they fitted the Fox equation very well, especially as the longer branches were grafted. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40303.     

Aerobic Oxidation of Benzylic Alcohols in Water by 2,2,6,6‐Tetramethylpiperidine‐1‐oxyl (TEMPO)/Copper(II) 2‐N‐Arylpyrrolecarbaldimino Complexes

Novel copper(II) 2‐N‐arylpyrrolecarbaldimine‐based catalysts for the aerobic oxidation of benzylic alcohols mediated by the 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) radical are reported. The catalytic activity for both synthesized and in situ made complexes in alkaline water solutions was studied revealing high efficiency and selectivity (according to GC selectivity always >99%) for both of these catalytic systems. For example, quantitative conversion of benzyl alcohol to benzaldehyde can be achieved with the in situ prepared bis[2‐N‐(4‐fluorophenyl)‐pyrrolylcarbaldimide]copper(II) catalysts in 2 h with atmospheric pressure of O₂ at 80 °C. Interestingly, these catalysts can utilize dioxygen as well as air or hydrogen peroxide as the end oxidants, producing water as the only by‐product.     

In situ thermal polymerization of an ionic liquid monomer for quasi‐solid‐state dye‐sensitized solar cells

In situ thermal polymerization of a model ionic liquid monomer and ionic liquids mixture to form gel electrolytes is developed for quasi‐solid‐state dye‐sensitized solar cells (Q‐DSSCs). The chemical structures and thermal property of the monomers and polymer are investigated in detail. The effect of iodine concentration on the conductivity and triiodide diffusion of the gel electrolytes is also investigated in detail. The conductivity and triiodide diffusion of the gel electrolytes increase with the increasing I₂ concentration, while excessive I₂ contents will decrease the electrical performances. Based on the in situ thermal polymeric gel electrolytes for Q‐DSSCs, highest power conversion efficiency of 5.01% has been obtained. The superior long‐term stability of fabricated DSSCs indicates that the cells based on in situ thermal polymeric gel electrolytes can overcome the drawbacks of the volatile liquid electrolyte. These results offer us a feasible method to explore new gel electrolytes for high‐performance Q‐DSSCs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42802.     

Doubly Stereocontrolled Asymmetric Aza‐Henry Reaction with in situ Generation of N‐Boc‐Imines Catalyzed by Novel Rosin‐Derived Amine Thiourea Catalysts

The doubly stereocontrolled organocatalytic aza‐Henry reaction of nitroalkanes to N‐Boc‐imines generated in situ from a variety of substituted α‐amido sulfones was investigated for the first time, in general, affording the corresponding products with high to excellent yields (up to 93% yield) and enantioselectivities (up to 98% ee), and satisfactory diastereoselectivies (anti/syn up to 98:2). Furthermore, these organocatalysts based on rosin have been proved to be the very effective promoters for this catalytic asymmetric process along side the Cinchona alkaloid‐derived catalysts.     

In‐Situ Raman Spectroscopy Study of Photoinduced Structural Changes in Ge‐rich Chalcogenide Films

Very few studies have been directed at the compositional dependence of the intrinsic photostability of the Ge_xSe_1?x binary ChG films especially for the Ge‐rich films with the mean coordination number (MCN) larger than 2.67. Here, by measuring the in‐situ transmission changes, it shows that the photosensitivity (e.g., photobleaching, PB) of the Ge‐rich films (as compared to the GeSe₂ film) is attenuated, in fact almost completely eliminated in the film with the largest MCN. A straightforward technique, in‐situ Raman spectroscopy, is used to record the time‐resolved intrinsic structural changes during the irradiation of the films. The result indicates a transition from PB towards photostability occurs at the critical composition of GeSe₂ corresponding to the structural phase transition. The stressed rigid structures of the Ge‐rich films inhibit any significant photo‐structural changes.     

Synthetic Applications of Synergism using Catalytic Binuclear Elimination Reactions. Further Examples of Rhodium‐Manganese and Rhodium‐Rhenium‐Catalyzed Hydroformylations

Synergism has been previously observed in both rhodium‐manganese‐ and rhodium‐rhenium‐catalyzed hydroformylation. Furthermore, detailed in situ spectroscopic investigations have conclusively shown that the phenomenological origin of this synergistic effect is catalytic binuclear elimination (J. Am. Chem. Soc. 2003 , 125, 5540–5548; 2007 , 129, 13327–13334). In the present contribution, further substrates are used in the hydroformylation reaction with both rhodium‐manganese and rhodium‐rhenium. In situ spectroscopic studies show that (i) significant rate enhancements occur in the mixed metal systems with the new substrates and (ii) the organometallics present in the active systems, and their concentration profiles are consistent with those present in the previously studied catalytic binuclear elimination reactions (CBER). It is therefore concluded that catalytic binuclear elimination is a rather general mechanism in mixed metal hydroformylations and is rather independent of the substrates used. Further discussion is given to mechanistic aspects, synthetic efficiency, and the possibility that such synergistic effects might be useful to other classes of organic syntheses.     

Suzuki–Miyaura Reactions of Aryl Chloride Derivatives with Arylboronic Acids using Mesoporous Silica‐Supported Aryldicyclohexylphosphine

The Suzuki–Miyaura reactions using mesoporous‐supported aryldicyclohexylphosphine as ligand have been investigated. The catalysts were based on SBA‐15 type mesoporous silica which was transformed in a four‐step synthesis leading to a phosphine‐containing hybrid material The most productive catalytic system studied was generated in situ from this material and the homogeneous palladium complex, Pd(OAc)₂. Other catalytic systems were studied for comparison [homogeneous cataysts, a “preformed” catalyst obtained by reaction of PdCl₂(PhCN)₂ and the phosphine‐containing material]. Variations involving the solvent system, the substrate aryl chloride and the arylboronic acid reactant were also studied. For both in situ and preformed catalyst systems, high conversions and yields are obtained for activated aryl chlorides. Success of the reaction for unactivated aryl chlorides was limited to the catalyst formed in situ. The catalyst formed in situ was also shown to be reactive under aqueous reaction conditions in the cross‐coupling of 1‐(4‐chlorophenyl)ethanone with phenylboronic acid.     

Field emission of MWCNTs/PANi nanocomposites prepared by ex‐situ and in‐situ polymerization methods

The present work describes the field‐emission properties of multiwalled carbon nanotubes (MWCNTs) coated with conducting polymer polyaniline (PANi). MWCNTs/PANi nanocomposites have been prepared by ex‐ situ polymerization methods and inex‐ situ chemical polymerization and are analyzed by SEM and Raman spectroscopy. It is fairly clear from SEM images that PANi is coated on the surface of MWCNT. SEM image of PANi powder also shows that the powder obtained is PANi nanofibers. It is also observed from SEM images that the shell diameter of MWCNTs depends on PANi content in thenanocomposites. The average outer diameter of MWCNTs increases from 7–15 to 50–80 nm upon PANi coating. Field‐emission study shows that although there is decrease in the value of turnex‐on field E_to and increase in the value field enhancement factor β of the nanocomposites as we go from direct solid‐state mixing method to inex‐ situ chemical polymerization method, the parameters obtained by inex‐ situ polymerization chemical method shows superior field emission. The turn‐on field of the nanocomposites are between 2.5 and 4.5 V/μm and the field enhancement factors are significantly high, between 1.2 × 10³ and 9.2 × 10³ while. PANi nanofibers does not show any field emission. POLYM. COMPOS. 34:1298–1305, 2013. © 2013 Society of Plastics Engineers     

Electrochemical synthesis and In situ spectroelectrochemistry of conducting NMPy‐TiO2 and ZnO polymer nanocomposites for Li secondary battery applications

Poly(N‐methylpyrrole) (PNMPy), poly(N‐methylpyrrole‐TiO₂) (PNMPy‐TiO₂), and poly (N‐methylpyrrole‐ZnO) (PNMPy‐ZnO) nanocomposites were synthesized by in situ electropolymerization for cathode active material of lithium secondary batteries. The charge–discharging behavior of a Li/LiClO₄/PNMPy battery was studied and compared with Li/LiClO₄/PNMPy‐nanocomposite batteries. The nanocomposites and PNMPy films were characterized by cyclic voltammetry, in situ resistivity measurements, in situ UV–visible, and Fourier transform infra‐red (FTIR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The differences between redox couples (ΔE) were obtained for polymer nanocomposites and PNMPy films. During redox scan, a negative shift of potential was observed for polymer nanocomposite films. Significant differences from in situ resistivity of nanocomposites and PNMPy films were obtained. The in situ UV–visible spectra for PNMPy and polymer nanocomposite films show the intermediate spectroscopic behavior between polymer nanocomposites and PNMPy films. The FTIR peaks of polymer nanocomposite films were found to shift to higher wavelengths in PNMPy films. The SEM and TEM micrographs of nanocomposite films show the presence of nanoparticle in PNMPy backbone clearly. The result suggests that the inorganic semiconductor particles were incorporated in organic conducting PNMPy, which consequently modifies the properties and morphology of the film significantly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41526.     

Synthesis and characterization of nylon‐6/mesoporous silica nanocomposites via in situ synchronous hydrolytic polymerization of tetraethylorthosilicate and ε‐caprolactam

Nylon 6 (N6)/mesoporous silica (MS) nanocomposites (NMSNs) were synthesized via in situ synchronous hydrolytic polymerization of tetraethylorthosilicate (TEOS) and ε‐caprolactam. The novelty of this technique lies in that the nanosilica generated in situ has unique mesoporous structure and ultrahigh‐specific surface area (SSA). Mechanical test showed that, compared to conventional precipitated silica (PS) nanofillers, the MS generated in situ shows better reinforcing efficiency on N6. At a loading of only 3.0 wt % MS, the tensile modulus, flexural modulus, and the heat distortion temperature of NMSNs exhibit increase of 54.8%, 77.9%, and 55.9°C, respectively. The effects of MS on the crystallization behaviors of N6 have been studied by differential scanning calorimetry (DSC), which shows that the incorporation of MS influences the crystallization behaviors of N6 obviously: (1) increases crystallization temperature (T_c) by serving as heterogonous nucleating agent; (2) favors the formation of γ‐phase by hindering the mobility of N6 chains. Dynamic mechanical analysis confirmed that, compared ti that of neat N6, the temperature of the main α‐relaxation (T_α) and the secondary β‐relaxation (T_β) of NMSNs is shifted 6.1°C and 5.3°C toward higher temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Epoxidized poly(N‐isopropyl acrylamide)‐b‐epoHTPB‐b‐poly(N‐isopropyl acrylamide) triblock copolymer micelle nanoparticles for 10‐hydroxycamptothecin drug release

Thermoresponsive poly(N‐isopropyl acrylamide) (PNIPAM)‐block‐hydroxy‐terminated polybutadine‐block‐PNIPAM triblock copolymers were synthesized by atom transfer radical polymerization; this was followed by the in situ epoxidation reaction of peracetic acid. The copolymers were characterized by ¹H‐NMR, Fourier transform infrared spectroscopy, and size exclusion chromatography measurements, and their physicochemical properties in aqueous solution were investigated by surface tension measurement, fluorescent spectrometry, ultraviolet–visible transmittance, transmission electron microscopy observations, dynamic light scattering, and so on. The experimental results indicate that the epoxidized copolymer micelle aggregates retained a spherical core–shell micelle structure similar to the control sample. However, they possessed a decreased critical aggregate concentration (CAC), increased hydrodynamic diameters, and a high aggregation number and cloud point because of the incorporation of epoxy groups and so on. In particular, the epoxidized copolymer micelles assumed an improved loading capacity and entrapment efficiency of the drug, a preferable drug‐release profiles without an initial burst release, and a low cytotoxicity. Therefore, they were more suitable for the loading and delivery of the hydrophobic drug as a controlled release drug carrier. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41877.