Preparation and evaluation of composites from montmorillonite and some heterocyclic polymers. II. A nanocomposite from N‐vinylcarbazole and ferric chloride‐impregnated montmorillonite polymerization system

The polymerization of N‐vinylcarbazole in the presence of FeCl₃‐impregnated montmorillonite resulted in the formation of a poly(N‐vinylcarbazole)–montmorillonite composite. XRD analysis of the composite revealed no expansion for d₀₀₁ spacing, in sharp contrast to that for the same composite prepared in the absence of FeCl₃. This indicated that the poly(N‐vinylcarbazole) was not intercalated in the montmorillonite lamellae but was glued to it in the same way as was polypyrrole in colloidal silica, zirconia, or tin oxide nanocomposite systems. TEM analysis revealed the particle size of the composite to be in the range 30–40 nm. The dc conductivity of the poly(N‐vinylcarbazole)–montmorillonite composite was in the range (3–5) × 10⁻⁵ S/cm depending upon the FeCl₃ loading of montmorillonite. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2971–2976, 1999     

Poly(N‐vinylcarbazole)–clay nanocomposite materials prepared by photoinitiated polymerization with triarylsulfonium salt initiator

A series of polymer–clay nanocomposite (PCN) materials that consist of poly(N‐vinylcarbazole) (PNVC) and layered montmorillonite (MMT) clay are prepared by effectively dispersing the inorganic nanolayers of MMT in an organic PNVC matrix via in situ photoinitiated polymerization with triarylsulfonium salt as the initiator. Organic NVC monomers are first intercalated into the interlayer regions of the organophilic clay hosts, followed by one‐step UV‐radiation polymerization. The as‐synthesized PCN materials are typically characterized by Fourier transform IR spectroscopy, wide‐angle X‐ray diffraction, and transmission electron microscopy. The molecular weights of PNVCs extracted from the PCN materials and the bulk PNVC are determined by gel permeation chromatography analysis with tetrahydrofuran as the eluant. The morphological image of the synthesized materials is observed by an optical polarizing microscope. The effects of the material composition on the optical properties and thermal stability of PNVCs and a series of PCN materials (solution and fine powder) are also studied by UV–visible absorption spectra measurements, thermogravimetric analysis, and differential scanning calorimetry, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1904–1912, 2004     

Conducting composites of poly(N‐vinylcarbazole), polypyrrole,and polyaniline with 13X‐zeolite

N‐vinylcarbazole (NVC) was polymerized by 13X zeolite alone in melt (65°C) or in toluene (110°C) and a poly(N‐vinylcarbazole) (PNVC)‐13X composite was isolated. Composites of polypyrrole (PPY) and polyaniline(PANI) with 13X zeolite were prepared via polymerization of the respective monomers in the presence of dispersion of 13X zeolite in water (CuCl₂ oxidant) and in CHCl₃ (FeCl₃ oxidant) at an ambient temperature. The composites were characterized by Fourier transform infrared analyses. Scanning electron microscopic analyses of various composites indicated the formation of lumpy aggregates of irregular sizes distinct from the morphology of unmodified 13X zeolite. X‐ray diffraction analysis revealed some typical differences between the various composites, depending upon the nature of the polymer incorporated. Thermogravimetric analyses revealed the stability order as: 13X‐zeolite > polymer‐13X‐zeolite > polymer. PNVC‐13X composite was essentially a nonconductor, while PPY‐13X and PANI‐13X composites showed direct current conductivity in the order of 10^?4 S/cm in either system. However, the conductivity of PNVC‐ 13X composite could be improved to 10^?5 and 10^?6 S/cm by loading PPY and PANI, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 913–921, 2006     

Photophysical studies of copolymers of N‐vinylcarbazole

The absorption, fluorescence excitation and emission spectroscopy, and time‐dependent spectrofluorimetry have been used to study the photophysics of copolymers of N‐vinylcarbazole with different monomers like vinyl acetate, methyl acrylate, methyl methacrylate, butyl acrylate, and butyl methacrylate in dichloromethane. In all the copolymers and at different N‐vinylcarbazole content, the absorption spectra reflect only the monomer carbazole units. The two kinds of excited monomer species of N‐vinylcarbazole are present in S₁ state. Short‐lived (～3 ns) excited monomer decays forming low energy excimer obtained by the complete overlap of the excited carbazole monomer. The long‐lived excited monomer (～8 ns) decays to ground state without formation of any excimer. The high energy excimer is relatively short‐lived and is formed by the partial overlap of the carbazole units. The presence of bulky group in the copolymer chain hinders the formation of excimers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 372–380, 2006     

Temperature‐responsive characteristics of poly(N‐isopropylacrylamide) hydrogels with macroporous structure

Macroporous poly(N‐isopropylacrylamide) (PNIPA) hydrogels were synthesized by free‐radical crosslinking polymerization in aqueous solution from N‐isopropylacrylamide monomer and N,N‐methylenebis (acrylamide) crosslinker using poly(ethylene glycol) (PEG) with three different number‐average molecular weights of 300, 600 and 1000 g mol^?1 as the pore‐forming agent. The influence of the molecular weight and amount of PEG pore‐forming agent on the swelling ratio and network parameters such as polymer–solvent interaction parameter (χ) and crosslinking density (ν_E) of the hydrogels is reported and discussed. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying different molecular weights and compositions of PEG during polymerization. At a temperature below the volume phase transition temperature, the macroporous hydrogels absorbed larger amounts of water compared to that of conventional PNIPA hydrogels, and showed higher equilibrated swelling ratios in aqueous medium. Particularly, the unique macroporous structure provides numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to external temperature changes during the swelling and deswelling process. These macroporous PNIPA hydrogels may be useful for potential applications in controlled release of macromolecular active agents. Copyright © 2006 Society of Chemical Industry     

A nanocomposite of poly(N‐vinylcarbazole) with nanodimensional alumina

A nanocomposite of poly(N‐vinylcarbazole) (PNVC) and Al₂O₃ was prepared by precipitation of a preformed PNVC in a tetrahydrofuran solution onto an aqueous suspension of nanodimensional Al₂O₃. Prolonged extraction of a PNVC–Al₂O₃ composite by benzene failed to extract the loaded PNVC from the Al₂O₃, as shown by Fourier transform infrared studies. Scanning electron microscopy analyses revealed distinct morphological features of the composite, and transmission electron microscopy analyses confirmed that the particle sizes were in the range of 120–240 nm. Thermogravimetric analyses demonstrated the enhanced stability of the nanocomposite relative to the base polymer. Direct current conductivity of the PNVC–Al₂O₃ composites was found to be about 0.14 × 10^?6 S/cm. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2233–2237, 2003     

Synthesis and thermal studies of poly(N‐acryloyl,N′‐cyanoacetohydrazide) complexes with Co(II), Fe(III), and UO2(II) ions

Polymer complexes with uranium, cobalt, and iron chlorides were synthesized and investigated by elemental analysis, electronic (uv–visible), IR vibration, and magnetic moment measurements. The thermal stabilities of N‐acryloyl,N′‐cyanoacetohydrazide (ACAH) homopolymers and polymer complexes of poly(ACAH) (PACAH) with metal chlorides were studied thermogravimetrically. The rates of polymerization of PACAH in the absence and presence of metal chlorides were studied. The activation energies of the degradation of the homopolymer and polymer complexes were calculated using the Arrhenius equation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3354–3358, 2003     

Preparation and characterization of thermosensitive poly(N‐isopropylacrylamide)/poly(ethylene oxide) semi‐interpenetrating polymer networks

Temperature‐sensitive poly(N‐isopropylacrylamide) hydrogels were successfully synthesized by using poly(ethylene oxide) as the interpenetrating agent. The newly prepared semi‐interpenetrating polymer network (semi‐IPN) hydrogels exhibited much better properties as temperature‐sensitive polymers than they did in the past. Characterizations of the IPN hydrogels were investigated using a swelling experiment, FTIR spectroscopy, and differential scanning calorimetry (DSC). Semi‐IPN hydrogels exhibited a relatively high temperature dependent swelling ratio in the range of 23–28 at room temperature. DSC was used for the determination of the lower critical solution temperature of the semi‐IPN hydrogel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3032–3036, 2003     

A conducting nanocomposite of acetylene black with preformed poly‐N‐vinylcarbazole crosslinked by anhydrous FeCl3

A conducting nanocomposite of crosslinked poly‐N‐vinylcarbazole (CLPNVC) with nanodimensional acetylene black (AB) was prepared by oxidative crosslinking of preformed PNVC through pendant carbazole moieties in presence of anhydrous FeCl₃ as an oxidant and AB suspension in CHCl₃ medium at 65°C. The incorporation of CLPNVC moieties in the CLPNVC‐AB composite was endorsed by Fourier transform infrared analysis. Scanning electron microscopic analysis showed formation of lumpy aggregates with average sizes in the 130–330 nm ranges. The thermal stability of the CLPNVC‐AB composite was appreciably higher than that of the PNVC‐AB composite. The direct current conductivities of the composites were significantly enhanced relative to that of the PNVC homopolymer (10^?12–10^?16 S/cm) and varied in the range of 10^?4–10^?2 S/cm depending on the amount of AB loading in the CLPNVC‐AB composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 819–824, 2006     

A conducting composite based on poly(N‐vinylcarbazole)–formalin resin and acetylene black

A poly(N‐vinylcarbazole) (PNVC)–formalin (FO) resin (PNVC‐FO) was prepared via copolycondensation between N‐vinylcarbazole (NVC) and FO in the presence of dry HCl gas in toluene medium at 110°C. A highly conducting composite of PNVC‐FO resin with nanodimensional acetylene black (AB) was prepared by carrying out the polycondensation reaction in presence of a suspension of acetylene black (AB) in toluene. The inclusion of PNVC in the PNVC‐FO‐AB composite was confirmed by FT‐IR analysis. Scanning electron microscopic analyses of PNVC‐FO resin and PNVC‐FO‐AB composite revealed formation of spherical particles and aggregates of irregular shapes respectively. Thermogravimetric analyses revealed the overall stability order as: AB > PNVC‐FO‐AB composite > PNVC‐FO resin > PNVC homopolymer. In sharp contrast to PNVC and PNVC‐FO resin, which were both nonconducting (10^?12 to 10^?16 S/cm), the conductivity of the composites reached values between 0.75 S/cm and 6.54 S/cm corresponding to AB loading of 28–49 wt % respectively. Temperature versus conductivity studies revealed an initial increase in conductivity upto 200°C and current–voltage characteristics of the PNVC‐FO‐AB composite showed a linear trend consistent with Ohmic behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3837–3843, 2007     

Photoemission and conductivity measurement of poly(N‐methyl aniline) and poly(N‐ethyl aniline) films

The studies involve the X‐ray photoelectron spectroscopy (XPS) and conductivity measurements of poly(N‐methyl aniline) and poly(N‐ethyl aniline) films deposited electrochemically at different pH values of −0.96, 2.22, and 3.78 for N‐methyl aniline and 1.10, 2.22, and 3.78 for N‐ethyl aniline. The results obtained reveal significant differences in the film properties of the two matrices as a function of pH of solution. These differences are explained on the basis of the competitive reaction products formed during polymerization in the two matrices along with the differences in the electron‐donating ability of the methyl and ethyl groups present on the nitrogen (N) atom. These results are further supported by the UV–Visible and IR data. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1286–1292, 1999     

Fluorescence from poly(N-vinylcarbazole) in uniaxially stretched polymer films

Steady-state and time-resolved fluorescence properties of poly(N-vinylcarbazole) (PVCz) dispersed in a polystyrene (PS) cast film were studied under tensile loadings at room temperature. The excited monomer emission of PVCz located around 350 nm decreased with increasing applied tensile strain from 0 to 0.8%. The strain enhanced the emission which was ascribed to the partial-overlap excimer of PVCz in a 360–430 nm region. The emission due to the full-overlap excimer of PVCz between 430 and 500 nm was unchanged by the action of the tensile loadings. The ratio of fluorescence intensities at 375 nm and 345 nm I₃₇₅/I₃₄₅ was proportional to the applied strain. The time-resolved fluorescence study indicated that the lifetimes of the excited monomer and of the partial-overlap excimer were not affected by the strain. The obtained results mean that the strain applied to the PS matrix increases the partial-overlap conformation of two adjacent carbazolyl chromophores in a PVCz chain and suggest that PVCz is a useful probe for detecting residual strains in polymer matrices. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1569–1573, 1997     

Thermal phase transition of poly(N‐propionylethyleneimine) hydrogel

This article presents the preparation of the hydrogel of poly(N‐propionylethyleneimine) and its interpenetrating polymer network (IPN) hydrogel containing polyacrylamide by means of γ‐ray radiation and a study of the phase transition temperature of these hydrogels. As a result, the hydrogel of the crosslinked poly(N‐propionylethyleneimine) exhibited swelling below and shrinking above the phase transition temperature (about 61°C), as well as the lower critical solution temperature (LCST) of the liner polymer–water system. The experiment also showed that the LCST of the IPN hydrogel could be adjusted by the incorporation of the second component polyacrylamide. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2457–2461, 1999     

Simultaneous lower and upper critical solution temperature‐type co‐nonsolvency behaviour exhibited in water–dioxane mixtures by linear copolymers and hydrogels containing N‐isopropylacrylamide and N,N‐dimethylacrylamide

The co‐nonsolvency behaviour in water–dioxane mixtures of linear copolymers and hydrogels consisting of N‐isopropylacrylamide (NIPAM) and N,N‐dimethylacrylamide (DMAM) was studied as a function of solvent composition and temperature. The composition of the copolymers, P(NIPAM‐co‐DMAMx), in DMAM units, x, varies from x = 0 up to x = 100%. It is shown that the copolymers combine the lower critical solution temperature (LCST)‐type co‐nonsolvency behaviour of poly‐NIPAM with the upper critical solution temperature (UCST)‐type co‐nonsolvency behaviour of poly‐DMAM. Depending on x, both the LCST‐ and UCST‐type co‐nonsolvency behaviour may be simultaneously observed in water‐rich and dioxane‐rich solvent mixtures, respectively. Due to this complex phase separation behaviour, the variation of the reduced viscosity of the linear copolymers, as well as the swelling–deswelling behaviour of the respective hydrogels, are shown to be temperature‐ and solvent‐sensitive. Copyright © 2006 Society of Chemical Industry     

Lower critical solution temperature of linear PNIPA obtained from a Yukawa potential of polymer chains

The lower critical solution temperature (LCST) behavior of a linear poly(N‐isopropylacrylamide) (PNIPA) in water is thought to result from the polymer–polymer attractive interaction. This polymer–polymer attraction is modeled by a temperature‐dependent Yukawa attractive potential, with Yukawa parameters determined by fitting the theoretical phase diagram for a pure Yukawa fluid to the experimental lower consolute boundary for a PNIPA–water solution. The predicted coexistence curve for the PNIPA–water mixtures in the temperature‐polymer volume fraction plane is reasonably close to the experimental cloud point data for the PNIPA–water system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1971–1976, 2000     

Synthesis of poly(vinyl butyral)s in homogeneous phase and their thermal properties

The condensation reaction of butyraldehyde (BA) with poly(vinyl alcohol) (PVA) to give poly(vinyl butyral) (PVB) was studied in detail using N‐methyl‐2‐pyrrolidone (NMP) as solvent for PVA and PVBs. PVBs having various degrees of acetalization were obtained. The acetalization reaction under a variety of conditions gave at best a polymer with 97% acetalization. The extent of modification and the structure of the polymer, i.e., the ratio of acetal units from meso and racemic dyads of PVA, were determined by ¹H‐NMR. The acetalization degree was reflected in the solubility of PVB; all products were soluble in NMP. PVBs were characterized by IR spectroscopy and ¹H and ¹³C‐NMR. The glass transition temperatures of PVBs, determined by DSC, increased as vinyl alcohol units increased and displayed a positive departure from linearity. Thermal degradation of PVBs was studied using differential thermal analysis (DTA) and thermogravimetry (TGA) under dynamic conditions in nitrogen. The content of hydroxyl groups had an effect on the thermal stability of PVBs; the thermal stability of PVBs decreased as vinyl alcohol units increased. The apparent activation energy of the decomposition was determined by the Kissinger and Flynn–Wall methods, which agree well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5007–5017, 2006     

The substituent effects on the structure and surface morphology of polyaniline

In this work, poly(2‐fluoroaniline), poly(2‐chloroaniline), poly(2‐methylaniline), and poly(N‐ethylaniline) were prepared by a self‐assembly method using an oxidizing system consisting of a dopant anion, p‐toluene sulfonate with ammonium peroxydisulfate. The effects of substituents on the surface morphology, conductivity, molecular weight, spectral and thermal properties of the polymers were studied. SEM results revealed that the surface morphology of the resulting polymers changed from nanofiber to spherical structure by changing the substituent on the aniline monomers. The structure and properties of these conducting films were characterized by FTIR, UV‐vis, elemental analysis, TGA, conductivity, and cyclic voltammetry. The polymer films show electroactivity in monomer free solution. Molecular weight of the polymers was determined by gel permeation chromatography. The dry electrical conductivity values of the substituted‐polyanilines were found to be lower than that of PANI. The results revealed that the molecular structures of the polymers were similar to those of the emeraldine form of polyaniline. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

New optically active poly(amide–imide–urethane) thermoplastic elastomers derived from poly(ethylene glycol diols), 4,4′‐methylene‐bis(4‐phenylisocyanate), and a diacid based on an amino acid by a two‐step method under microwave irradiation

A new class of optically active poly(amide–imide–urethane)s (PAIUs) was synthesized via a two‐step diisocyanate route under microwave irradiation. In these reactions, 4,4′‐methylene‐bis(4‐phenylisocyanate) was reacted with bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L ‐leucine and poly(ethylene glycol diol)s (PEGs), such as PEG‐400, PEG‐600, PEG‐1000, and PEG‐2000, to furnish a series of new PAIUs. The effects of different reaction conditions, such as the method of preparation (polyol or acid chain extension), the prepolymerization step (NCO‐terminated oligoamide or NCO‐terminated polyether polyol), the irradiation time and power, the reaction solvent, the soft‐segment length, and the presence or absence of reaction catalysts (e.g., triethylamine, pyridine, and dibutyltin dilaurate), on the properties of the copolymers, including the solubility, viscosity, and thermal behavior, were investigated. The resulting multiblock copolymers had inherent viscosities of 0.15–0.53 dL/g. These multiblock copolymers were optically active, thermally stable, and soluble in amide‐type solvents. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1781–1792, 2005     

Synthesis and properties of PMR type poly(benzimidazopyrrolone‐imide)s

PMR type poly(benzimidazopyrrolone‐imide) or poly(pyrrolone‐imide) (PPI) matrix resin was synthesized using the diethyl ester of 4,4′‐(hexafluoroisopropylidene)diphthalic acid (6FDE), 3,3′‐diaminobenzidine, para‐phenylenediamine, and monoethyl ester of cis‐5‐norbornene‐endo‐2,3‐dicarboxylic acid (NE) in anhydrous ethyl alcohol with N‐methylpyrrolidone. The homogeneous matrix resin solution (40–50% solid) was stable for a storage period of 2 weeks and showed good adhesion with carbon fibers, which ensured production of prepregs. The chemical and thermal processes in the polycondensation of the monomeric reactant mixture were monitored by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, etc. Thermosetting PPI as well as short carbon fiber‐reinforced polymer composites was accomplished at optimal thermal curing conditions. The polymer materials, after postcuring, showed excellent thermal stability, with an initial decomposition temperature > 540°C. Results of MDA experiments indicate that the materials showed > 70–80% retention of the storage modulus at 400°C and glass transition temperatures as high as 440–451°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1600–1608, 2001     

Hydrogel characteristics of a novel temperature‐sensitive polymer,poly(N‐2‐methoxyisopropylacrylamide)

In this study, a novel temperature‐sensitive polymer, poly(N‐2‐methoxyisopropylacrylamide), PNMIPA, in the crosslinked hydrogel form was obtained. The monomer, N‐2‐methoxyisopropylacrylamide (NMIPA) was synthesized by the nucleophilic substitution reactions of acryloyl chloride with 2‐methoxyisopropylamine. Hydrogel matrix of PNMIPA was obtained by the bulk polymerization method. The bulk polymerization experiments were performed at +4°C, by using N,N‐methylenebisacrylamide (MBA) as crosslinker, polyethyleneglycol (PEG) 4000 as diluent, and potassium persulfate (KPS) and tetramethylethylenediamine (TEMED) as the initiator and accelerator, respectively. The same polymerization procedures were applied by changing monomer, initiator, crosslinker and diluent concentrations in order to obtain crosslinked gel structures having different temperature–sensitivity properties. The equilibrium swelling ratio of PNIMPA gel matrices at constant temperature increased with increasing initiator concentration and decreasing monomer concentration. The use of PEG 4000 as diluent in the gel synthesis resulted in about two times increase in equilibrium swelling ratios in the low temperature region. A decrease in the equilibrium swelling ratios of gel matrices started at 30°C and the decrease became insignificant at 55°C. Temperature‐sensitivities were determined in two different media. Distilled water medium was used in order to observe the temperature‐sensitivity of the gel clearly and the phosphate buffer medium was used in order to represent the temperature‐sensitive swelling behavior of the gel when it is used in biological media. Step effect was applied on ambient temperature in two opposite directions in order to examine the dynamic swelling and shrinking behaviors of the gels. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008