Physicochemical properties of electrochemically prepared poly(pyrrole hexafluorophosphate)

Poly(pyrrole hexafluorophosphate) (PPPF₆) was prepared with the potentiostatic method to supply a constant potential of 1.21 V for 5 h in water/acetonitrile (1/99 vol %) solution of 0.2M pyrrole containing 0.1M tetraethylammonium hexafluorophosphate as a supporting electrolyte. The result of elemental analysis and Fourier transform infrared spectrum showed that it was a PPPF₆ that was doped with ∼28 wt % 6 was irreversible. Scanning electron microscopy was performed to know the morphology of PPPF₆. The result of the differential scanning calorimetry did not show any special peak in temperature range of 25–800°C. From the temperature dependence of the electrical conductivity and electron spin resonance measurement, it was suggested that a possible conduction mechanism for the PPPF₆ polymer should be a small polaron hopping conduction. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 605–612, 1998     

表面活性剂对疏水改性丙烯酰胺共聚物增粘性能的影响

采用自由基胶束聚合法合成丙烯酰胺/丁基苯乙烯疏水缔合水溶性共聚物(PSAM),所用的十二烷基硫酸钠(SDS)、辛基酚聚氧乙烯醚(OP-10)和十六烷基三甲基溴化铵(CTAB)能显著影响疏水单体在聚合产物中的含量,从而影响聚合物的溶液粘度,其中以SDS合成得到的产物的溶解性及增粘性能最好。另外,少量表面活性剂的加入能显著地提高聚合物亚浓溶液的粘度,在十二烷基苯磺酸钠(SDBS)、SDS和CTAB中,SDBS对聚合物亚浓溶液粘度的影响最大,其浓度为0.7 mmol/L时,0.3 g/dL PSAM溶液的表观粘度从237 mPa.s上升到981 mPa.s。     

Influence of electrochemically prepared poly(pyrrole-co-N-methyl pyrrole) and poly(pyrrole)/poly(N-methyl pyrrole) composites on corrosion behavior of copper in acidic medium

Poly(pyrrole-co-N-methyl pyrrole) copolymer and poly(pyrrole)/poly(N-methyl pyrrole) bilayer composites were electrochemically synthesized on copper by cyclic voltammetry from aqueous solution of 0.3 M oxalic acid and 0.1 M monomer. Synthesis of copolymers were performed with different monomer feed ratios (pyrrole:N-methyl pyrrole, 8:2, 6:4, 5:5, 4:6 and 2:8) and in order to determine the copolymer, which has the best corrosion performance, anodic polarization was applied to copolymer coated samples. It was found that the performance of coatings was strongly dependent to the monomer feed ratio and the copolymer synthesized with 8:2 concentration ratio showed the most protective property compared to others. Bilayer of poly(pyrrole)/poly(N-methyl pyrrole) was also synthesized to compare the anticorrosive properties. Polymer films were characterized by ATR-FTIR spectroscopy and SEM techniques. Corrosion behavior of polymer composites was investigated in 0.1 M H₂SO₄ solution by anodic polarization and electrochemical impedance spectroscopy. Different approaches such as phase angle at high frequency and areas under Bode plots were used to evaluate corrosion performances of the coatings. Copolymer and bilayer coatings were found to have higher protection effect than single polypyrrole coatings. Moreover, bilayer coating exhibited better protection efficiency than copolymer coating against corrosion of copper when the obtained results were compared.     

Synthesis, characterization and electrochromic properties of a conducting copolymer of pyrrole functionalized polystyrene with pyrrole

A well-defined polystyrene (PSt) based polymer containing at one end-chain 3,5-dibromobenzene moiety, prepared by atom transfer radical polymerization (ATRP), was modified in two reaction steps. First one constitutes a Suzuki coupling reaction between aromatic dibromine functional polymer and 3-aminophenylboronic acid, when a diamino-containing intermediate was obtained. The second step is a condensation reaction between the diamino functional polystyrene and 2-pyrrole aldehyde. Thus, a polymer containing a conjugated sequence having pyrollyl groups at the extremities was synthesized. The presence of oxidable pyrrole groups in the structure of the polymer permitted further electropolymerization. The structures of intermediate polymers were analyzed by spectral methods (¹H NMR, FTIR). Electrochemical copolymerization of pyrrole functionalized polymer (PStPy) with pyrrole was carried out in acetonitrile (ACN)-tetrabutylammonium tetrafluoroborate (TBAFB) solvent electrolyte couple. Characterization of the resulting copolymer were performed via Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), spectroelectrochemical analysis, and kinetic study. Spectroelectrochemical analysis show that the copolymer of PStPy with Py has an electronic band gap (due to π-π* transition) of 2.4 eV at 393 nm, with a yellow color in the fully reduced form and a blue color in the fully oxidized form. Via kinetic studies, the optical contrast %ΔT was found to be 20% for P(PStPy-co-Py). Results showed that the time required to reach 95% of the ultimate T was 1.7 s for the P(PStPy-co-Py).     

The effect of electrochemically polymerized pyrrole on the physicochemical properties and biological activity of carbon materials

Many of the vital processes in the human body are electrochemical in nature. Therefore, medical applications of electrochemistry show great promise. Particularly, detoxification by electrochemically controlled hemosorption combines biocompatibility of activated carbon with high adsorption activity toward toxic compounds. The present work involved the development of a controlled detoxification process using carbon adsorbents modified with polypyrrole. The electropolymerization of pyrrole on AG-3 activated carbon, which was initially quite aggressive towards erythrocytes, made it biocompatible. Glassy carbon and activated carbon were used to study the effect of polypyrrole on the physicochemical and biological activity of carbon materials. The magnitude and direction of open circuit potential shifts for these carbon materials depended on the conditions of electropolymerization. Adsorption activity of AG-3 activated carbon modified with polypyrrole was increased, as compared with untreated carbon.     

Improvement of conductivity of electrochemically synthesized polyaniline

The electrochemical polymerization of aqueous solution of aniline and HCl was carried out in a single compartment electrochemical cell. After 2 h of the polymerization reaction, polarity of the electrodes was reversed and kept for 1 h. By this process the conductivity of the polyaniline (PAni) formed was found to increase dramatically from 1.1 × 10^?4 to 3.0 × 10^?1 S/cm. The PAni samples obtained both by reversing the polarity (“PANI‐R”) and without reversing the polarity (“PANI”) were characterized by the infrared spectroscopy (FT‐IR), thermogravimetric analysis (TGA), ultraviolet spectroscopy (UV), Hall effect experiment, X‐ray analysis (XRD) and scanning electron microscope (SEM). The results show that the increase in the conductivity of PAni through the reversion of polarity is due to the partial reduction of over oxidized sample giving more emeraldine base and hence more polaron formation with increased charge carrier density and its mobility. The degree of crystallinity and the crystallite size is decreased marginally and the d‐spacing is increased marginally due to this reduction. The PAni behaves like a p‐type semiconductor that means the majority current carriers are holes. A plausible reduction mechanism due to reversal of polarity during electrochemical polymerization is also proposed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Electropolymerization and electrochemical properties of (N-hydroxyalkyl)pyrrole/pyrrole copolymers

In this study, the N-hydroxyalkyl derivatives of pyrrole (Py), N-(2-hydroxyethyl)pyrrole (HE) and N-(3-hydroxypropyl)pyrrole (HP), were synthesized. The corresponding homopolymers, PHE and PHP, together with the copolymers of Py/HE and those of Py/HP were prepared by galvanostatic polymerization. These monomers and polymers were characterized by FTIR spectroscopy, elemental analysis, SEM and electrochemical techniques. The result of potential-time profiles showed that a higher potential was required for HE and HP than Py for the polymerization. This was ascribed to the steric hindrance of high concentration of the N-hydroxyalkyl groups. However, a similar potential was observed for the copolymerization of Py/HE and Py/HP systems as that of Py due to the reduction of the steric effect by lower content of the substituent. The SEM micrographs showed a rougher morphology for the films synthesized from the solutions with higher Py/derivatives ratio. The cyclic voltammograms indicated that all the copolymers were larger, while the homopolymers had smaller anodic/cathodic currents and specific charges than PPy. This implied that the existence of the proper amount of the N-hydroxyalkyl pendant groups enhanced the ionic mobility of the pyrrole polymers. The results of charge/discharge measurements showed that the copolymer PYHP82 has the highest discharge capacity among the pyrrole polymers prepared.     

Characterization,surface properties and biological activity of some synthesized anionic surfactants

In this study, esterification reaction between four different fatty alcohols (octyl, dodecyl, hexdecyl and octadecyl alcohol) and phosphoric acid was performed. The produced compound was reacted with polyethylene glycol-400. Then, the reaction product was quenched using sodium hydroxide to form the desired anionic gemini surfactants. The chemical structures of the synthesized surfactants were recognized by FT-IR and ¹H NMR spectroscopy. The synthesized surfactants showed higher surface activity. The emulsion stability measurements showed the applicability of these surfactants as emulsifying agents. The foaming power measurements showed the synthesized surfactants have low ability to foam formation. The thermodynamic parameters showed their tendency toward adsorption at the interfaces and also micellization in the bulk of their solutions. The studied surfactants were evaluated as antimicrobial agents against pathogenic bacteria using inhibition zone diameters. The synthesized surfactants showed good antimicrobial activities against the tested microorganisms including Gram positive, Gram negative as well as fungi. The promising inhibition efficiency of these compounds against the pathogenic bacteria facilitates them to be applicable in the petroleum field as new categories of biocides.     

Effect of protonation media on chemically and electrochemically synthesized polyaniline

Polyaniline films have been prepared both chemically and electrochemically using formic (‘Pani‐Formic’), boric (‘Pani‐Boric’) or acetic acid (‘Pani‐Acetic’) as protonation media. Among the three, formic acid seems to be a better protonating medium because it selectively yields the conducting phase of polyaniline. The variation of potential with the amount of oxidizing agent suggests one dimensional growth of polymer chain, which proceeds through a PG/EM mechanism as indicated by spectral data. The Pani‐Boric and Pani‐Acetic acid demonstrate three‐ and four‐step decomposition patterns, respectively, with complete decomposition at about 760 °C. Pani‐Formic acid, in contrast, reveals a three‐step decomposition pattern with 90% weight loss at about 900 °C and shows a tendency to react with the Pt sample holder. The films of polyaniline generated electrochemically also suggest formic acid to be a better protonating medium for achieving a relatively greater fraction of conducting emeraldine salt. However, boric acid produces excellent quality adherent films with very high deposition rate. Morphological features give strong support to this observation. The films of Pani‐Formic and Pani‐Acetic acids show a spongy network and globular morphology, respectively, while Pani‐Boric acid yields an extremely uniform surface coating. Furthermore, cyclic voltammetry reveals different patterns depending upon the formation of different oxidation states and the results are in accordance with optical absorption studies. © 2000 Society of Chemical Industry     

Corrosion protection aspects of electrochemically synthesized poly(o-anisidine-co-o-toluidine) coatings on copper

The poly(o-anisidine-co-o-toluidine) coatings were synthesized on copper substrates by electrochemical copolymerization of o-anisidine with o-toluidine using sodium salicylate as supporting electrolyte. These coatings were characterized by cyclic voltammetry, UV-vis absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and scanning electron microscopy (SEM). The formation of the copolymer with the mixture of monomers in the aqueous sodium salicylate solution was ascertained by a critical comparison of the results obtained with the polymerization of the individual monomers, o-anisidine and o-toluidine, respectively. The corrosion protection aspects of poly(o-anisidine-co-o-toluidine) coatings to copper was investigated in aqueous 3% NaCl solution by potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The results of the potentiodynamic polarization measurements and EIS studies showed that the poly(o-anisidine-co-o-toluidine) coatings provided the effective corrosion protection to copper than that of respective homopolymers. The corrosion rate is observed to depend on the feed ratio of o-toluidine used for the synthesis of the copolymer coatings.     

Structure and properties of graft copolymer of starch and resorcinol synthesized using HRP

A modified starch tannage was synthesized by radical copolymerization of degraded starch and resorcinol (RC) using horseradish peroxidase (HRP)/H₂O₂ as an initiator. The effects of the degradation degree, system pH value, reaction temperature on the copolymerization, and tanning properties of the graft copolymer used in leather processing were investigated. The application results showed that the graft copolymer has excellent tanning properties. The shrinkage temperature (T_s) of the tanned leather reached 85.4°C, and the thickness increment ratio of the retanned leather was 23.1%. The tanning effects were significantly improved with RC modification compared with the graft copolymer of starch and vinyl monomers. The results indicated that the graft copolymer of starch and RC may be a replacement for toxic chrome and aldehyde tannage. The structure of the graft copolymer was characterized by FTIR, ¹H-NMR, GPC, and UV. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

动态硫化乙烯-辛烯共聚物/硅橡胶热塑性弹性体性能的影响因素

采用Haake转矩流变仪制备了乙烯-辛烯共聚物(POE)/硅橡胶(MVQ)动态硫化热塑性弹性体(TPV),考察了共混温度、转速、动态硫化时间对POE/MVQ共混物硫化特性、TPV物理机械性能及加工特性的影响,观察了硫化剂不同投料方式下TPV的外观形貌。结果表明,在共混温度为130℃、转速为50～60 r/min、动态硫化时间约为8 min的条件下,采用POE与MVQ混匀后分3批加入硫化剂的方式,所得POE/MVQ TPV的综合性能较好,表面光滑且有韧性。     

Influence of dialkyl ethers on the surface properties of homogeneous nonionic surfactants

Influence of the trace amounts of the corresponding dialkylethers on the surface and colloidal properties of the pure polyoxyethylene alkyl ethers were studied. The dialkyl ether, undetected by gas liquid chromatography (GLC) was found by gel permeation chromatogram (GPC) as the corresponding impurity in homogeneous pure polyoxyethylene alkyl ether and confirmed using infrared (IR), nuclear magnetic resonance (NMR) and mass spectroscopy (MS). After removing the corresponding impurity in each surfactant with a GPC separation column, the minima in the surface tension curves disappeared completely. Adding the corresponding dialkyl ether to the pure surfactant produced the minima in the surface tension curves and large values for surface aging, cloud points were lowered more than for the pure surfactants and foam height and foam stability for the aqueous solutions decreased gradually.     

Improved capacitive behavior of electrochemically synthesized Mn oxide/PEDOT electrodes utilized as electrochemical capacitors

A sequential synthetic approach and a one-step method were adopted to synthesize Mn oxide/PEDOT electrodes through anodic deposition on Au coated Si substrates from aqueous solutions. In the former case, free standing Mn oxide rods (about 10 μm long and less than 1.5 μm in diameter) were first synthesized without a template through anodic deposition from a dilute solution of Mn acetate, then coated by electro-polymerization of a conducting polymer (PEDOT) giving coaxial rods. The one-step, co-electrodeposition method produced agglomerated Mn oxide/PEDOT particles. The electrochemical behavior of the deposits depended on the morphology and crystal structure of the fabricated electrodes, which were affected by the pH of electrolyte, deposition potential, current density and polymer deposition time. Structural characterization of as-deposited and cycled electrodes was conducted using XPS, SEM, TEM and AES.The Mn oxide/PEDOT coaxial core/shell electrodes prepared by the sequential method showed significantly better specific capacity and redox performance properties relative to both uncoated Mn oxide rods and co-electrodeposited Mn oxide/PEDOT electrodes. The best specific capacitance for Mn oxide/PEDOT rods produced sequentially was ∼285 F g⁻¹ with ∼92% retention after 250 cycles in 0.5 M Na₂SO₄ at 20 mV s⁻¹.     

XPS studies of iodine complexes of pyrrole — N-methylpyrrole copolymer

Summary Simultaneous chemical copolymerization and oxidation of pyrrole and N-methylpyrrole by iodine has been carried out. The electrical conductivity, the I^– ₃ content and the amount of positively charged pyrrolylium nitrogen decrease with increasing N-methylpyrrole content in the copolymer complexes.     

Characterization and caffeine release properties of N‐isopropylacrylamide/hydroxypropyl methacrylate copolymer hydrogel synthesized by gamma radiation

Research efforts have been devoted to demonstrate that the temperature sensitivity characters of poly(N‐isopropylacrylamide)(PNIPAAm) can be applied in the field of drug carriers. A copolymer hydrogel of N‐isopropylacrylamide/hydroxypropyl methacrylate (NIPAAm/HPMA) was synthesized by gamma irradiation. The nature of bonding was characterized by FTIR spectroscopy, whereas the thermal stability was characterized by thermogravimetric analysis (TGA). The influence of NIPAAm/HPMA composition on the swelling properties in water, at different temperatures and different pH values was studied. The release characters of caffeine drug from NIPAAm/HPMA hydrogels were also investigated. The gel fraction of NIPAAm/HPMA was found to increase slightly by increasing the ratio of HPMA in the initial solution. The IR spectra indicate the formation of copolymer hydrogels, whereas the TGA study showed that the NIPAAm/HPMA copolymer hydrogels displayed higher thermal stability than NIPAAm hydrogel. PNIPAAm hydrogel showed higher swelling in water than NIPAAm/HPMA hydrogels. Based on Fick's law, it was demonstrated that the diffusion of water into NIPAAm/HPMA is controlled. It was found that the main parameters affecting the drug release behavior from the hydrogels are composition and pH. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of diblock copolymer on the morphology and properties of polystyrene/poly(dimethylsiloxane) blends

Blends of polystyrene (PS) and poly(dimethylsiloxane) (PDMS), with and without diblock copolymers (PS‐b‐PDMS), were prepared by melt mixing. The melt rheology behavior of the blends was studied with a capillary rheometer. The morphology of the blends was examined with scanning electron microscopy. The miscibility of the blends was studied with differential scanning calorimetry. The morphology of PS/PDMS blends was modified by the addition of PS‐b‐PDMS copolymers and investigated as a function of the molar mass of the diblock copolymers, viscosity ratios and the processing conditions. As investigated, the observed morphology of the melt‐blended PS/PDMS pair unambiguously supported the interfacial activity of the diblock copolymers. When a few percent of the diblock copolymers blended together with the PS and PDMS homopolymers, the phase size was reduced and the phase dispersion was firmly stabilized against coalescence. The compatibilizing efficiency of the copolymers was strongly dependent on its molar mass. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2747–2757, 2004     

丙烯酸酯共聚物在温和表面活性剂体系配方中的研究

研究了丙烯酸酯共聚物在氨基酸和烷基糖苷表面活性剂及其复配体系中的性能表现,并对表面活性剂用量、pH值以及聚合物用量对体系黏度的影响进行了研究。结果表明,丙烯酸酯聚合物对氨基酸和烷基糖苷体系具有较好的配伍性,且与甲基葡糖二油酸酯具有协同增稠能力。