Synthesis of chalcone‐containing methacrylate‐based hydrogen bonded side chain liquid crystalline polymer and its dielectric properties

In this work, a new methacrylate‐based hydrogen bonded side chain liquid crystalline polymer having chalcone moieties (HBCP) was prepared from poly(4‐(3‐(pyridin‐4‐yl)acryloyl) phenyl methacrylate) and 11‐(4‐cyanobiphenyl‐4(‐oxy) undekan‐1‐ol (LC11)) by molecular self‐assembly processes via hydrogen bond formation between nitrogen of the HBCP and hydroxyl group of the LC11. The formation of H bond was confirmed by using Fourier transform infrared (FTIR) spectroscopy. The phase transition temperatures and liquid crystalline phases of the HBCP were examined by DSC and POM measurements. The dielectric properties of HBCP have been determined by impedance analyzer within the frequency interval of 100 Hz–15 MHz. According to Cole–Cole plot, the equivalent circuit of the LC system has been found as a capacitor in parallel with a resistor. The resonance frequency, f_r, of the R–C circuit has also been calculated as 1.59 MHz by phase angle versus frequency curve. The dielectric relaxation type of HBCP has been determined as nearly‐Debye type because the absorption coefficient, α, equals to 0.01655. From the conductivity point of view, HBCP displays dc conductivity at the low and high frequency regions that correspond to 100 Hz–12 kHz and 3.3 MHz–15 MHz, respectively. On the other hand, it has been revealed that the ac conductivity of the LC system investigated obeys Super Linear Power Law (SLPL) at the intermediate frequency domain. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and properties of a cyanate ester containing dicyclopentadiene(II)

A 2,6‐dimethyl phenol‐dicyclopentadiene novolac (DCPDNO) was synthesized from dicyclopentadiene and 2,6‐dimethyl phenol, and the resultant DCPDNO was reacted with cyanogen bromide into 2,6‐dimethyl phenol‐dicyclopentadiene cyanate ester (DCPDCY). The structures of the novolac and cyanate ester were confirmed with Fourier transform infrared spectroscopy, elemental analysis, mass spectrometry (MS), and nuclear magnetic resonance. For the purpose of increasing the mobility of residual DCPDCY during the final stage of curing and achieving a complete reaction of cyanate groups, a small quantity of a monofunctional cyanate ester, 4‐tert‐butylphenol cyanate ester (4TPCY), was added to DCPDCY to form the cyanate ester copolymer. The synthesized DCPDCY was then cured with 4TPCY at various molar ratios. The thermal properties of the cured cyanate ester resins were studied with dynamic mechanical analysis, dielectric analysis, and thermogravimetric analysis. These data were compared with those of the commercial bisphenol A cyanate ester system. Compared with the bisphenol A cyanate ester system, the cured DCPDCY resins exhibited lower dielectric constants (2.52–2.67 at 1 GHz), dissipation factors (0.0054–0.0087 at 1 GHz), glass‐transition temperatures (261–273 °C), thermal stability (5% degradation temperature at 406–450 °C), thermal expansion coefficients (4.8–5.78 × 10^?5/°C before the glass‐transition temperature), and moisture absorption (0.8–1.1%). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 671–681, 2005     

Maleation of poly(3,4‐epoxy‐1‐butene) for accelerated crosslinking in the presence of a redox catalyst

Accelerated crosslinking of novel poly(3,4‐epoxy‐1‐butene) (3,4‐PEPB) oligomers in the presence of a cobalt‐based redox catalyst was investigated. Previous studies using model compounds, 3,4‐dimethoxy‐1‐butene and 1,4‐dimethoxy‐2‐butene, suggested that maleation of hydroxyl‐terminated 3,4‐PEPB oligomers would result in more rapid crosslinking in thin films. Novel maleated oligomers offered a unique combination of both electron‐rich and electron‐poor olefinic sites, and quantitative maleation significantly increased the crosslinking rate of 3,4‐PEPB. Efficient copolymerization between terminal maleate groups and olefinic groups in the repeating unit was proposed to account for accelerated crosslinking rates. Furthermore, the addition of novel reactive diluents, such as maleic acid mono‐ethyl ester, also effectively improved the 3,4‐PEPB crosslinking rate. Sol fraction measurements as a function of coating thickness revealed that the crosslinking rate versus oxygen diffusion was less significant for the maleated oligomers because of the presence of reactive electron‐poor olefins. Sol fractions were constant for catalyst concentrations greater than 0.25–0.50 wt % (as compared with oligomer feed). This observation suggested that a redox process was not a dominant factor in determining crosslinking rates at various experimental conditions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2789–2798, 2002     

Synthesis and characterization of poly(isobutylene‐co‐isoprene)‐derived macro‐monomers

Allylic halide displacement from brominated poly(isobutylene‐co‐isoprene) (BIIR) by carboxylate nucleophiles is used to prepare elastomer derivatives containing pendant polymerizable functionality. These solvent‐borne substitutions are conducted under homogeneous and phase‐transfer catalyzed reaction conditions to synthesize acrylate and vinylbenzoate esters in high yield. The resulting macro‐monomer derivatives are shown to crosslink efficiently with peroxide initiation to give high modulus, thermoset products that cannot otherwise be accessed from isobutylene‐rich elastomers. The extent of cure, as measured by the storage modulus of the vulcanizate, scales with RCH=CH₂ content, and can be extended by co‐oligomerization of pendant unsaturation with that contained within multifunctional coagents. An alternate approach involving the introduction of pendant sulfonyl azide functionality is described, wherein thermal decomposition to nitrene intermediates supports an efficient crosslinking process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Poly(aryl ether ketone)s with (3‐methyl)phenyl and (3‐trifluoromethyl)phenyl side groups

New bisphenol monomers, (3‐methyl)phenylhydroquinone and (3‐trifluoromethyl)phenylhydroquinone, were prepared in a two‐step synthesis. A series of poly(aryl ether ketone)s were derived from these bisphenols via a nucleophilic aromatic substitution polycondensation with various bisfluoro compounds. The polycondensation proceeded quantitatively in tetramethylene sulfone in the presence of anhydrous potassium carbonate and afforded the polymers with inherent viscosities of 0.63–0.91 dL/g. The fluorinated polymers showed lower glass‐transition temperatures and higher thermal‐decomposition temperatures than the corresponding nonfluorinated polymers. The solubility of the polymers was improved by the introduction of bulky pendant groups. All the polymers formed transparent, strong, and flexible films, with tensile strengths of 86.4–102.0 MPa, Young's moduli of 2.28–3.03 GPa, and elongations at break of 14–42%. All the polymers had low dielectric constants of 2.70–2.83 at 1 MHz. Compared with the methylated polymers, the trifluoromethylated polymers exhibited lower water sorption, which was attributed to the stronger hydrophobicity of the fluorine‐containing groups. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3392–3398, 2002     

Hydrolytic stability and high Tg of polyimides derived from the novel 4,9‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]‐diamantane dianhydride

This work reports the synthesis and characterization of diamantane‐based polyimides obtained from 4,9‐bis[4(3,4‐dicarboxyphenoxy)phenyl]diamantane dianhydride and various aromatic diamines. Interestingly, the diamantane‐based polyimides were very stable to hydrolysis. This novel polyimide exhibits a low dielectric constant (2.65–2.77), low moisture absorption (<0.67%), good solubility, high T_g and unusually high thermal stability. Dynamic mechanical analysis (DMA) reveals that the diamantane‐based polyimides have high T_g ranging from 281 to 379 °C. The high‐temperature β₁ subglass transition around 285 °C was observed in polyimide 6a derived from 2,2′‐bis(trifluoromethyl)benzidine. This class of novel diamantane‐based polyimide is very promising for electronic applications, because of its good mechanical properties, good thermal stability, low dielectric constant, excellent hydrolytic resistance, and low moisture absorption. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1673–1684, 2009     

Synthesis and characterization of novel polyimide from bis‐(3‐aminophenyl)‐4‐(trifluoromethyl)phenyl phosphine oxide

A novel diamine, bis‐(3‐aminophenyl)‐4‐(trifluoromethyl)phenyl phosphine oxide (mDA3FPPO), containing phosphine oxide and fluorine moieties was prepared via the Grignard reaction from an intermediate, 4‐(trifluoromethyl)phenyl diphenyl phosphine oxide, that was synthesized from diphenylphosphinic chloride and 4‐(trifluoromethyl)bromobenzene, followed by nitration and reduction. The monomer was characterized by Fourier transform infrared (FTIR), ¹H NMR, ³¹P NMR, ¹⁹F NMR spectroscopies; elemental analysis; melting point measurements; and titration and was used to prepare polyimides with a number of dianhydrides such as pyromellitic dianhydride (PMDA), 5,5′‐[2,2,2‐trifluoro‐1‐(trifluoromethyl)ethyliden]‐bis‐1,3‐isobenzofuranedione (6FDA), 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA), and 4,4′‐oxydiphthalic dianhydride (ODPA). Polyimides were synthesized via a conventional two‐step route; preparation of polyamic acids, followed by solution imidization, and the molecular weight were controlled to 20,000 g/mol. Resulting polyimides were characterized by FTIR, NMR, DSC, and intrinsic viscosity measurements. Refractive‐index, dielectric constant, and adhesive properties were also determined. The properties of polyimides were compared with those of polyimides prepared from 1,1‐bis‐(4‐aminophenyl)‐1‐phenyl‐2,2,2‐trifluoroethane (3FDAm) and bis‐(3‐aminophenyl) phenyl phosphine oxide (mDAPPO). The polyimides prepared from mDA3FPPO provided high glass‐transition temperatures (248–311 °C), good thermal stability, excellent solubility, low birefringence (0.0030–0.0036), low dielectric constants (2.9–3.1), and excellent adhesive properties with Cu foils (107 g/mm). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3335–3347, 2001     

2,5‐Bis[4‐methyl‐3‐(pyridin‐3‐yl)phenyl]‐1,3,4‐oxadiazole and its one‐dimensional polymeric complex with ZnCl2

2,5‐Bis[4‐methyl‐3‐(pyridin‐3‐yl)phenyl]‐1,3,4‐oxadiazole (L), C₂₆H₂₀N₄O, forms one‐dimensional chains via two types of intermolecular π–π interactions. In catena‐poly[[dichloridozinc(II)]‐μ‐2,5‐bis[4‐methyl‐3‐(pyridin‐3‐yl)phenyl]‐1,3,4‐oxadiazole], [ZnCl₂(C₂₆H₂₀N₄O)]_n, synthesized by the combination of L with ZnCl₂, the Zn^II centres are coordinated by two Cl atoms and two N atoms from two L ligands. [ZnCl₂L]_n forms one‐dimensional P (plus) and M (minus) helical chains, where the L ligand has different directions of twist. The helical chains stack together via interchain π–π and C—H...π interactions.     

Synthesis and solution properties of a pH‐responsive cyclopolymer of zwitterionic ethyl 3‐(N,N‐diallylammonio)propanephosphonate

The zwitterionic monomer, ethyl 3‐(N,N‐diallylammonio)propanephosphonate, was cyclopolymerized in aqueous solutions using t‐butylhydroperoxide or ammonium persulfate as initiators to afford a polyphosphonobetaine (PPB). The protonation of P(?O)OEtO^– and deprotonation of ? NH⁺ groups in PPB by HCl and NaOH, gave the corresponding cationic polyphosphononic acid (CPP) and anionic polyphosphonate (APP). The presence of two pH‐responsive functionalities in APP has led to establish the equilibria: APP ? PPB ? CPP, the position of which very much dictates the viscosity behavior of its aqueous solution. The PPB demonstrated “antipolyelectrolyte” viscosity behavior; however, in contrast to many polycarbo‐ and polysulfo‐betaines, it was found to be soluble in salt‐free water as well as in salt‐added solutions. Basicity constant (K₁) of the amine group in APP, as determined by potentiometric technique, were found to be “apparent,” and as such followed the modified Henderson‐Hasselbalch equation. The study demonstrated a correlation between the basicity constants and viscosity values. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Photopatternable substrate‐independent poly(glycidyl methacrylate‐ran‐2‐(acryloyloxy) ethyl 2‐methylacrylate) polymer films for immobilization of biomolecules

We report the synthesis and characterization of a photocrosslinkable copolymer containing reactive epoxy groups for binding biomolecules. The epoxide‐containing copolymer poly(glycidyl methacrylate‐ran‐2‐(acryloyloxy) ethyl 2‐methylacrylate) offers distinct advantages such as ease of application to various substrates, enhanced stability of the bound oligonucleotide, low autofluorescence, and the ability to be photopatterned allowing localization of the linkers. The copolymer uses pendant acryloyl groups to control the crosslinking without sacrificing the epoxide groups. The films were characterized using ellipsometry, atomic force microscopy, and fluorescence microscopy. The films on glass, silicon wafer, and stainless steel showed no appreciable degradation in water, tetrahydrofuran, and acetone for ～4 months. The surface topography for a given thickness of crosslinked film was dictated by the deposition conditions. A 16mer oligonucleotide was immobilized on the thin films. A linear relationship between the film thickness and amount of oligonucleotide immobilized was observed with a maximum signal‐to‐background ratio (S/B) of 225 for a 60‐nm‐thick film, a value 50% higher than the S/B for an epoxide monolayer. The crosslinked films maintained a high fluorescence signal following long aqueous washing which is appealing for biological microarrays, immobilizing proteins, and study of slow differentiating cells where stability of the scaffold is relevant. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5826–5838, 2008     

Synthesis and characterization of novel 3,6‐di[3′,5′‐bis(trifluoromethyl)phenyl]pyromellitic dianhydride for polyimide synthesis

A novel dianhydride monomer, 3,6‐di[3′,5′‐bis(trifluoromethyl)phenyl]pyromellitic dianhydride (12FPMDA), was synthesized via a three‐step process: (1) the preparation of 3,5‐bis(trifluoromethyl)benzene boronic acid (6FBB) and 3,6‐dibromo‐1,2,4,5‐tetramethylbenzene (2B4MB) via Grignard and bromination reactions, respectively; (2) the Suzuki cross‐coupling reaction of 6FBB and 2B4MB, resulting in 3,6‐di[3′,5′‐bis(trifluoromethyl)phenyl]tetramethylbenzene (12F4MB); and (3) the oxidation and cyclodehydration of 12F4MB to afford 12FPMDA. 12FPMDA was then characterized by Fourier transform infrared (FTIR), ¹H NMR, ¹⁹F NMR, elemental analysis, and a melting‐point apparatus, and it was used to prepare polyimides with aromatic diamines such as 1,1‐bis(4‐aminophenyl)‐2,2,2‐trifluoroethane and 4,4′‐diaminodiphenylether. Polyimides were synthesized via a two‐step process: (1) the preparation of poly(amic acid) in p‐chlorophenol with isoquinoline and (2) solution imidization at the reflux temperature for 12 h. They were designed to have molecular weights of 20,000 g/mol via off‐stoichiometry. The resulting polyimides were characterized by FTIR, NMR, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis, and their solubility, solution viscosity, water absorption, coefficients of thermal expansion (CTEs), and dielectric constants were also evaluated. The polyimides exhibited excellent solubility even in acetone and toluene, high glass‐transition temperatures (>311 °C), good thermal stability (>518 °C in air), and well‐controlled molecular weights (19,000–21,000 g/mol). They also provided low CTEs (35–50 ppm/°C), water absorption (1.26–1.35 wt %), and dielectric constants (2.49–2.52). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4217–4227, 2002     

Synthesis and photorefractivity of poly[methyl‐3‐(7‐dibenzo[a,g]carbazolyl)‐propylsiloxane]

7H‐Dibenzo[a,g]carbazole‐substituted polysiloxane (PSX‐[a,g]BCz) has been synthesized by hexachloroplatinate (IV) hydrate polymerization from poly(methylhydrosiloxane) and 7‐ally‐7H‐dibenzo[a,g]carbazole. PSX‐[a,g]BCz composite showed large orientational birefringences because of both large dipole moments and high‐polarizability anisotropies of P‐IP‐DC chromophore associated with the effective conjugation along the polyene. The 50‐μm thick photorefractive material containing 30 wt % 2‐[3‐[(E)‐2(piperidino)‐1‐ethenyl]‐5,5‐dimethyl]‐2‐cyclohexenyliden]malononitrile showed a diffraction efficiency of 51% at 55 V/μm, which corresponded to a Δn of 3.45 × 10^?3. PSX‐[a,g]BCz composite shows a fast time constant of 0.42 s at 34 °C and 55 V/μm, which corresponded to the space‐charge field of 12 V/μm under 70 V/μm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1783–1791, 2008     

Preparation,characterization and properties of fiber reinforced composites using silicon‐containing hybrid polymers

A novel glass fiber reinforced composite was prepared by using silicon‐containing hybrid polymers, poly(methylhydrogen‐diethynylsilyene) (PMES) and poly(phenylethynyl‐silyloxide‐phenylborane) (APABS), as matrix resins. The curing behavior and rheological properties of the matrix resins were investigated by differential scanning calorimetry (DSC) and rotational rheometer. The dynamic viscoelastic properties, mechanical properties, and microstructures of the composites were studied by dynamic mechanical analysis (DMA), universal testing machine (UTM), and scanning electron microscopy (SEM), respectively. The results show that the composite can be well cured between 200 and 300 °C through reactive groups like Si‐H, N‐H, and C≡C units, the possible thermosetting mechanism is also proposed. The composites exhibit excellent mechanical properties with bending strength reach up to 261 and 178 MPa before and after heat‐treating, respectively. SEM analysis clearly indicates that crack in the matrix, matrix/fiber interface debonding, and fiber pull out are predominate failure mechanism for the composites which are heat‐treated in different temperatures. All these obtained results can give theoretical guiding reference for their further applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and crosslinking behavior of a novel linear polymer bearing 1,2,3‐triazol and benzoxazine groups in the main chain by a step‐growth click‐coupling reaction

The click‐coupling reaction was applied to polycondensation, to synthesize a high‐molecular weight prepolymer having benzoxazine moieties in the main chain. For the polycondensation, a bifunctional N‐propargyl benzoxazine was synthesized from bisphenol A, propargylamine, and formaldehyde. The propargyl group was efficiently used for the copper(I)‐catalyzed alkyne‐azide “click” reaction with p‐xylene‐α,α′‐diazide, to give the corresponding linear polycondensate having 1,2,3‐triazole junctions. The polycondensation proceeded in N,N‐dimethylformamide (DMF) at room temperature. By this highly efficient “click‐” polycondensation reaction, the benzoxazine ring in the monomer was successfully introduced into the polymer main chain without any side reaction. The obtained polymer (=prepolymer) underwent thermal crosslinking to afford the corresponding product, which was insoluble in a wide range of organic solvents and exhibited higher thermal stability than the polymer before crosslinking. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2316–2325, 2008     

pH‐ and temperature‐sensitive statistical copolymers poly[2‐(dimethylamino)ethyl methacrylate‐stat‐2‐vinylpyridine] with Functional succinimidyl‐ester chain ends synthesized by nitroxide‐mediated polymerization

Statistical copolymerizations of 2‐(dimethylamino)ethyl methacrylate (DMAEMA) with 2‐vinylpyridine (2VP) with 80 to 99 mol % DMAEMA in the feed utilizing a succinimidyl ester‐terminated alkoxyamine unimolecular initiator (NHS‐BlocBuilder) at 80 °C in bulk were performed. The effectiveness of 2VP as a controlling comonomer is demonstrated by linear increases in number‐average molecular weight versus conversion, relatively low PDI (1.5–1.6 with up to 98% DMAEMA) and successful chain extensions with 2VP. Additional free nitroxide does not significantly improve control for the DMAEMA/2VP copolymerizations. The succinimidyl ester on the initiator permits coupling to amine‐terminated poly(propylene glycol) (PPG), yielding an effective macroinitiator for synthesizing a doubly thermo‐responsive block copolymer of PPG‐block‐P(DMAEMA/2VP). A detailed study of the thermo‐ and pH‐sensitivities of the statistical and block copolymers is also presented. The cloud point temperature of the statistical copolymers is fine tuned from 14 to 75 °C by varying polymer composition and pH. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012.     

Cyclodextrins in Polymer Synthesis: Photoinitiated Free‐Radical Polymerization of N‐Isopropylacrylamide in Water Initiated by a Methylated β‐Cyclodextrin/2‐Hydroxy‐2‐methyl‐1‐phenylpropan‐1‐one Host/Guest Complex

Methylated β‐cyclodextrin (Me‐β‐CD) was used to complex a free‐radical photoinitiator, 2‐hydroxy‐2‐methyl‐1‐phenylpropan‐1‐one ( 1 ), yielding the water‐soluble 1 : 1 host/guest complex 1 a . The structure of complex 1 a was verified by means of IR, UV/vis and ¹H NMR spectroscopy. The influence of Me‐β‐CD as the host on the photopolymerization kinetics of N‐isopropylacrylamide was studied. Compared to the photopolymerization carried out under nearly identical conditions but without cyclodextrin, an increase in the polymerization rate was registered in the presence of complex 1 a .     

Comprehensive study on the formation of polyelectrolyte complexes from (quaternized) poly[2‐(dimethylamino)ethyl methacrylate] and poly(2‐acrylamido‐2‐methylpropane sodium sulfonate)

Polyelectrolyte complexes (PECs) have been prepared from well‐defined (quaternized) poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) and high molecular weight poly(2‐acrylamido‐2‐methylpropane sodium sulfonate) (PAMPSNa) after a thorough study of their viscometric properties. The effect of pH and quaternization degree of PDMAEMA on PECs stoichiometry has been examined. PEC‐based materials have been characterized in terms of thermal stability, equilibrium swelling degree, and free/bound water composition. The stoichiometry and swellability of the physically crosslinked hydrogels obtained from fully quaternized PDMAEMA/PAMPSNa complexes do not depend on pH. In contrast, PECs made of non quaternized PDMAEMA and PAMPSNa are highly affected by pH, and could reversibly disintegrate at pH ≥ 9. Partially quaternized PDMAEMA/PAMPSNa PECs exhibit intermediate properties and form stable loose structures in the whole investigated pH range. Finally, stable dispersions of PECs nanoparticles have been successfully produced from dilute solutions of the complementary polyelectrolytes. The nanoparticle average diameter as determined by dynamic light scattering proved to depend on the molar fraction of DMAEMA‐based subunits and on the initial polyelectrolyte concentration. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5468–5479, 2006     

Investigations of the dissociation behavior and interfacial adsorption characteristics of polyelectrolytes from poly(acrylamido‐2‐methyl‐1‐propane sulfonic acid) with an octadecyl side chain

Water‐soluble polymeric amphiphiles derived from acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) and octadecyl monomers in which the linker groups vary among acryloyl [octadecyl methacrylate (ODMAc)], maleate [octadecyl maleate ester (ODME)], and maleamic acid [octadecyl maleamic acid (ODMA)] have been synthesized. The dissociation behavior in water from potentiometric titration suggests that these polymers show resistance to neutralization. This might arise from coil structures, which effect the destabilization of sulfonate ions because of a proximity effect. The effect of the ? COOH group in modifying the dissociation behavior in the copolymers AMPS–ODME and AMPS–ODMA is indicated. The ratio of the intensities of the third vibronic peak (I₃) to the first vibronic peak (I₁) of the fluoroprobe pyrene in the presence of polymer solutions shows negligible changes as a function of pH, and this suggests the retention of micropolarity. The high I₃/I₁ value observed in the presence of the ODMAc polymer suggests intermolecular association. The reduction in the reduced viscosity with the concentration of the polymers suggests the polyelectrolyte behavior of all the copolymers. The progressive decrease in the reduced viscosity from 120 to 95 mL/g when the degree of ionization increases from 0.5 to 1 for the ODME polymer suggests changes in the solution structure. AMPS–ODMA and AMPS–ODME polymers exhibit significant adsorption at the interface and exhibit equilibrium surface tensions of 58.8 and 56.3 mN/m, respectively. The lower surface activity and higher reduced viscosity of ODMAc polymer solutions further support the formation of intermolecular associated or network structures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 314–324, 2006     

Synthesis and properties of poly‐(2‐ethynylpyridinium bromide) having propargyl side chains

Poly‐(2‐ethynylpyridinum bromide) (PEPBP) having propargyl side chains was prepared by the direct polymerization of 2‐ethynylpyridine and propargyl bromide under mild reaction conditions without any initiator and catalysts. The polymerization proceeded well to give PEPBP with propargyl side chains in relatively high yields. Various spectral data for the polymer structure indicated that the conjugated polymer system having N‐propargylpyridinum substituent was formed. This ionic polymer was completely soluble in water, methanol, dimethylformamide, dimethyl sulfoxide, and N,N‐dimethylacetamide and well processable into thin homogeneous film. The photoluminescence intensity (λ_max = 760 nm) of this polymer increased as the temperature was increased. At 1 KHz and room temperature, this polymer has k′ = 2.9 and σ = 7.3 × 10^?10 (S/cm). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3151–3158, 2001     

Synthesis of highly regioregular poly[3‐(4‐alkoxyphenyl)‐thiophene]s by oxidative catalysis using copper complexes

A novel, easy, and cost‐effective synthetic procedure is reported for the production of very highly regioregular poly[3‐(4‐alkoxyphenyl)thiophene]s by means of oxidative coupling. Four copper complexes were synthesized and used as catalysts to obtain polymers with higher regioregularity compared to the previous oxidative coupling methodologies reported in the literature and similar to that obtained by McCullough and Rieke methods in the synthesis of poly‐3‐alkylthiophenes. The regioregularity of the synthesized polymers was investigated by UV–Visible characterization on polymer thin films and ¹H NMR analysis. The remarkable potentialities of these polymers have emerged from field‐effect transistor mobility measurements operated on devices with bottom‐contact configuration and hexamethyldisilazane‐treated SiO₂ gate dielectric, showing a well‐defined p‐type field‐effect response and maximum mobility values in air higher than 10^?4 cm² V^?1 s^?1. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4351–4360