Synthesis of polypyrrole nanoparticles in natural rubber–polystyrene blend via emulsion polymerization

Nanoparticles of polypyrrole (PPy) in 40/60 wt % natural rubber (NR)–polystyrene (PS) blends were synthesized by emulsion polymerization using ferric sulfate [Fe₂ (SO₄)₃], sodium dodecyl sulfate (SDS), and n‐amyl alcohol as the oxidant, surfactant, and cosurfactant, respectively. The NR/PS/PPy blends were characterized by Fourier transform infrared spectroscopy (FTIR), elemental analysis, thermogravimetric analysis (TGA), and field emission scanning electron microscopy (FESEM). FESEM micrographs showed that NR/PS/PPy blends were homogeneous, and PPy nanoparticles were well distributed throughout the binary matrix of NR/PS. The size of PPy particles in the blends was in the range of 26–80 nm. The electrical conductivities of the pellets prepared from NR/PS/PPy blends increased as the composition of PPy nanoparticles was increased, which were in the range of 8.9 × 10^?8 – 2.89 × 10^?4 S/cm. Thermal stability of the blends increased as the content of PPy was increased, as shown by TGA thermograms. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of nanosized polypyrrole–polystyrene composite particles

Nanosized polypyrrole–polystyrene (PPy–PS) composite particles were synthesized by the polymerization of pyrrole on PS nanoparticles in the presence of FeCl₃. The PS nanoparticles were prepared from microemulsion polymerizations using the cationic nonpolymerizable surfactant cetyltrimethylammonium bromide (CTAB), the nonionic polymerizable surfactant ω‐methoxy[poly(ethylene oxide)₄₀]undecyl α‐methacrylate (PEO–R–MA‐40), or the cationic polymerizable surfactant ω‐acryloyloxyundecyltrimethylammonium bromide (AUTMAB). For the latexes stabilized by CTAB, the resulting PPy–PS composite particles exhibited relatively poor colloidal stability and the pressed pellets exhibited relatively low electrical conductivities (～10^?7–10^?3 S cm^?1). However, for the latexes stabilized by polymerizable surfactants, the resulting PPy–PS composite particles exhibited relatively good colloidal stability and relatively high conductivities (～10^?5–10^?1 S cm^?1). The effect of polymerizable surfactants on the colloidal stability of composite particles and the conducting mechanism of the composites are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1360–1367, 2004     

PS/POSS复合材料的阻燃性能和流变性能研究

通过熔融共混法制备了聚苯乙烯(PS)/八苯基多面体低聚倍半硅氧烷(OPS)复合材料。采用氧指数仪和毛细管流变仪测试了复合材料的阻燃与流变性能。结果表明:PS/OPS复合材料为典型的假塑性流体;在较低的剪切速率下,复合材料的表观黏度随着OPS含量的增加而降低,但在较高的剪切速率下,其表观黏度随着OPS含量的增加而增大;与纯PS相比,PS/OPS复合材料的黏流活化能随OPS含量的增加而略有增加;OPS的加入有助于提高PS的阻燃性和热稳定性。     

Influence of the dopant on the polypyrrole moisture content: Effects on conductivity and thermal stability

Having in mind to produce electrically conductive carbon–epoxy composite materials, we have filled an insulating epoxy resin with an electronic conducting polymer, polypyrrole (PPy). To select the PPy that best suits this process, various PPys were chemically synthesized. The syntheses were performed in water via a dispersion polymerization route using, initially, either FeCl₃ (PPy–Cl⁻) or (NH₄)₂S₂O₈ (PPy–HSO₄⁻) as oxidizing agents. Then, using (NH₄)₂S₂O₈ as the oxidant, two other PPy doped with aromatic species were obtained due to the dissolution of paratoluenesulfonic acid (PPy–TS⁻) or naphtalenesulfonic acid (PPy–NS⁻) in the reaction media. The characterization of the PPy samples by conductivity measurements, together with elemental and thermal analysis, showed that PPy–TS⁻ exhibits the highest conductivity and thermal stability, with the conductivity remaining steady over 14 days. In addition, a stabilizing effect of the aromatic anions was observed. The experiments have shown that moisture in the PPy cannot be entirely removed and that, with increasing moisture content, the conductivity also increases, indicating an ionic conductivity superimposed on the electronic conductivity usually observed in PPy. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1567–1577, 1998     

The study of char forming on OPS/PC and DOPO‐POSS/PC composites

Polyhedral oligomeric octaphenyl silsesquioxane (OPS) and polyhedral oligomeric silsesquioxane containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO‐POSS) with polycarbonate (PC) were each prepared by twin screw extrusion. Their flammability was studied by cone calorimetry under different heat fluxes (35 and 50 kW/m²). In the cone calorimeter testing, thermocouples were used to measure the temperature at the top and bottom of the composites. Compared to the DOPO‐POSS/PC composite, the char layer of the OPS/PC composite is better for preventing heat transfer, the temperature change indicates that OPS/PC composite has a longer period of char formation, and the organization of their char materials are different. The DOPO‐POSS/PC composite has a harder char layer than the OPS/PC composite, but the OPS/PC composite char layer is more compact. The char layer macrostructure was studied with scanning electron microscopy (SEM) and EDS, which indicated that there are many bubbles and pores in the DOPO‐POSS/PC composite. EDS showed that there was some Si content in the exterior and interior char for the DOPO‐POSS/PC composite; there is a greater Si content in the exterior OPS/PC char residue than in the interior. The storage modulus of OPS/PC composite was higher than the PC control and DOPO‐POSS/PC composite at low frequencies. The values of η* of the OPS/PC composite were higher than the PC control and DOPO‐POSS/PC composite at low frequencies; also, the PC control exhibits a quasi‐Newtonian regime, but the OPS/PC and DOPO‐POSS/PC composites exhibit typical shear‐thinning behavior. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39892.     

Oxygen reduction on NixCo3−xO4 spinel particles/polypyrrole composite electrodes: hydrogen peroxide formation

The oxygen reduction reaction (orr) was studied on composite electrodes GC/PPy/PPy(Ni_xCo_3−xO₄)/PPy with x=0.3 and 1, in 2.5×10⁻³ M KOH+0.8 M KCl at room temperature. The orr takes place on the oxide particles with formation of hydrogen peroxide (H₂O₂), which diffuses through the polymer layers to reach the bulk of electrolyte solution. The amount of H₂O₂ produced, determined indirectly by iodine spectrometry, depended strongly on the oxide stoichiometry. The effects of the orr and of the generation of H₂O₂ on the conductivity of PPy and on the behaviour of the embedded oxide particles are discussed.     

Organic/inorganic hybrid bismaleimide resin with octa(aminophenyl)silsesquioxane

Octa(aminophenyl)silsesquioxane (OAPS) was prepared in two steps by the nitration of octaphenylsilsesquioxane (OPS) in fuming nitric acid to form octa(nitrophenyl)silsesquioxane (ONPS), followed by the mild reduction of ONPS with Pd/C as a catalyst. OPS, ONPS and OAPS were characterized by FTIR, ¹H NMR, and ²⁹Si NMR techniques. Modification of a bismaleimide (BMI) resin with OAPS and dipropargyl ether of bisphenol A (DPBPA) was investigated. The modified resins, OAPS/DPBPA/BMI, were characterized with DSC, FTIR and rheology analyses. The results showed that the modified resins have good processability. The DMA results indicated that the glass transition temperature (T_g) of the cured OAPS/DPBPA/BMI hybrid resins reached 350°C. The decomposition temperature (T_d5) of the cured resins decreased but the char yield (Y_c, 800°C) increased as the OAPS loading increased, especially in air. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Thermal and mechanical properties of blended polyimide and amine‐functionalized poly(orthosiloxane) composites

Nanocomposite films were prepared through the blending of polyimide (PI) with octaphenyl silsesquioxane (OPS) and an amino‐functionalized analogue, octaaminophenyl silsesquioxane (OAPS), with a solution‐casting method. Although the PI–OPS composites showed visible phase separation at 5 wt %, the PI–OAPS composites were transparent with visible phase separation occurring only at 50 wt % OAPS. The interfacial interactions and homogeneity of the composites were characterized with scanning electron microscopy (SEM) and dynamic mechanical analysis. SEM analysis showed a uniform fracture surface for OAPS composites at concentrations up to 20 wt %. Interestingly, OAPS‐rich particles with sizes of less than 1 μm were formed within the PI matrix for the 50 wt % composite. The PI–OAPS composites showed higher glass‐transition temperatures (T_g's) than the pure PI. The PI–OPS composites showed a T_g lower than that of the pure PI, and this suggested poor interfacial interactions. The slightly enhanced thermal stability of PI–OAPS composites (up to 20 wt %) was attributed to the inherent thermal stability of OAPS at higher temperatures. There were small increases in the modulus and strength for the composites with respect to the base polymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical,thermal properties,and flame retardancy of PC/ultrafine octaphenyl‐POSS composites

Composites of ultrafine polyhedral oligomeric octaphenyl silsesquioxane (OPS) and polycarbonate (PC) were prepared by melt blending. The mechanical and thermal properties of the composites were characterized by tensile and flexural tests, impact test, differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), and thermal gravimetric analysis (TGA). Rheological properties of these melts were tested by torque rheometer. The flame retardancy of the composites was tested by limiting oxygen index (LOI), the vertical burning (UL‐94), and cone calorimeter test. The char residue was characterized by scanning electron microscope (SEM) and ATR‐FTIR spectrum. Furthermore, the dispersion of OPS particles in the PC matrix was evidenced by SEM. The results indicate that the glass transition temperatures (T_g) and torque of the composites decrease with increasing OPS loading. The onset decomposition temperatures of composites are lower than that of PC. The LOI value and UL‐94 rating of the PC/OPS composites increase with increasing loading of OPS. When OPS loading reaches 6 wt %, the LOI value is 33.8%, UL‐94 (1.6 mm) V‐0 rating is obtained, and peak heat release rate (PHRR) decreases from 570 to 292 kJ m^?2. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Photosensitizing properties of ionic porphyrins immobilized on functionalized solid polystyrene support

The photogeneration of singlet oxygen (¹O₂) by tetrasodium salt of meso‐tetrakis(4‐sulfonatophenyl)porphyrins (H₂TPPS) and some of its metal complexes (MTPPS; M = Cd²⁺, Zn²⁺), immobilized on cationically functionalized polystyrene (PS) beads, was studied. The generation of ¹O₂ was monitored by a N,N‐dimethyl‐4‐nitrosoaniline (RNO) bleaching assay. The rate of RNO bleaching was seen to be retarded in the presence of DABCO, a specific ¹O₂ scavanger, providing evidence for the involvement of ¹O₂ as an active intermediate. The relative efficiencies of the generation of ¹O₂, with respect to immobilized rose bengal (PS–RB), by different polymer‐supported porphyrins, were determined to be 0.29, 0.27, and 0.16 for PS–H₂TPPS, PS–ZnTPPS, and PS–CdTPPS, respectively. Binding of porphyrins to a polymer has been found to decrease the efficiency of the ¹O₂ generation, which could be attributed to the structural deformation of the appended porphyrins. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3925–3930, 2003     

Preparation of conducting composites of polypyrrole using supercritical carbon dioxide

Supercritical carbon dioxide, saturated with pyrrole, was brought into contact with oxidant‐impregnated films of poly(chlorotrifluoroethylene) (PCTFE), crosslinked poly(dimethylsiloxane) (PDMS), poly(methyl methacrylate) (PMMA), and porous crosslinked polystyrene (PS) in order to form conducting composites via the in situ polymerization of pyrrole. The two nonporous hosts—PCTFE and crosslinked PDMS—did not form conducting composites with polypyrrole (PPy). On the other hand, the electrical conductivity of the PPy composites with carbon dioxide‐swollen PMMA and porous PS ranged from 1.0 × 10^?4 S/cm to 3.0 × 10^?5 S/cm. In these two cases, the level of pyrrole polymerized on the surface or in the pores of the host polymer was sufficient to attain the interconnected conducting polymer networks necessary for electrical conductivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1113–1116, 2003     

Fabrication of core-shell Fe3O4/polypyrrole and hollow polypyrrole microspheres

A facile synthesis of highly-regulated core-shell Fe₃O₄/polypyrrole (PPy) microspheres is achieved using a surfactant directed chemical oxidation polymerization in aqueous solution. The thickness of the PPy layer can be tuned by the quantity of the pyrrole monomer. The formation of core-shell Fe₃O₄/PPy microspheres lies on the static interactions between the SO₃⁻ group in sodium dodecyl sulphate molecules and Fe₃O₄ microspheres. Other surfactants such as cetyltrimethylammonium bromide and polyoxyethylene (10) isooctylcyclohexyl ether (Triton X-100) directed polymerization cannot produce such highly-regulated core-shell Fe₃O₄/PPy microspheres. XPS spectra proved the core-shell structure of the composite microspheres. XRD, FTIR, and UV–vis spectra are used to characterize the chemical structure of the composite microspheres. The electrical and magnetic properties are also investigated. Moreover, the obtained core-shell Fe₃O₄/PPy microspheres can be converted to highly-regulated hollow PPy microspheres by dissolving the Fe₃O₄ core with acid solution. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

The synthesis and characterization of polystyrene/magnetic polyhedral oligomeric silsesquioxane (POSS) nanocomposites

Fc-CHCH-C₆H₆-(C₅H₉)₇Si₈O₁₂ (POSS1, Fc: ferrocene) which contain both metal and CC double bond was firstly synthesized by Wittig reaction. The chemical structure of POSS1 was characterized by FTIR, ¹H, ¹³C and ²⁹Si NMR, mass spectrometry and elemental analysis, and the magnetic property of POSS1 have also been studied. Polystyrene composites containing inorganic-organic hybrid polyhedral oligomeric silsesquioxane (POSS1) were prepared by bulk free radical polymerization. XRD and TEM studies indicate that POSS1 is completely dispersed at molecular level in PS matrix when 1 wt% POSS1 is introduced, while some POSS1-rich nanoparticals are present when content of POSS1 is beyond 3 wt%. GPC results show that molecular weight of the PS/POSS1 nanocomposites are increased with addition of POSS1. TGA and TMA data show the thermal stabilities of PS/POSS1 nanocomposites have been improved compared to neat PS. The PS/POSS1 nanocomposites also display higher glass transition temperatures (T_g) in comparison with neat PS. Viscoelastic properties of PS/POSS1 nanocomposites were investigated by DMTA. The results show the storage modulus (E′) values (temperature>T_g) and the loss factor peak values of the PS/POSS1 nanocomposites are higher than that of neat PS. Mechanical properties of the PS/POSS1 nanocomposites are improved compared to the neat PS.     

In situ reactive compatibilization in polymer blends: Effects of functional group concentrations

Polystyrene (PS) and polyethylene (PE), along with their reactive counterparts, i.e., polystyrene having oxazoline reactive groups (OPS) and polyethylene with carboxylic acid groups (CPE), were melt blended in a Rheomix mixer. These blends were prepared by mixing these polymers in various proportions under a variety of conditions. In an alternate procedure the OPS, CPE graft polymer (OPS-g-CPE) was prepared by melt blending these two polymers beforehand, and subsequently this grafted polymer was used as a compatibilizer for PS–PE blends. The effects of the addition of OPS and CPE, on the one hand, and OPS-g-CPE, on the other hand, on the compatibility of PS–PE blends were investigated. The morphology of these blends was examined with a scanning electron microscope (SEM) and related to their tensile properties. The PS–PE blends are found to have the typical coarse morphology of incompatible blends and poor tensile properties while their reactive counterparts, OPS-CPE blends, have fine grain microstructure and show improved tensile strength throughout the range and improved elongation in the PE-rich blends. Relatively low concentrations of the reactive pair, oxazoline and carboxylic acid, are shown to be necessary to produce improved compatibility. The preblended graft copolymer OPS-g-CPE imparts compatibility to PS–PE blends also but not as effectively. This suggests that the addition of OPS and CPE during melt mixing of PS and PE forms OPS-g-CPE polymer at the interface and that these ingredients act as “in situ reactive compatibilizers” which improve physical properties.     

Preparation and properties of transparent and conducting nylon 6-based composite films

Highly transparent and conducting polypyrrole–(PPy–N) and polyaniline–nylon 6 (PAN) composite films could be easily obtained by immersing nylon 6 films containing pyrrole or aniline into an oxidant solution such as aqueous FeCl₃ solution or aqueous (NH₄)₂S₂O₈ solution containing HCl. The conductivity, transmittance, and mechanical properties of these composite films were affected by the preparative conditions. The maximum conductivity and transmittance of the PPy–N composite films were 10^?3 S/cm and about 75% at 550 nm, and in the case of the PA–N composite films, 10^?2 S/cm and 75%, respectively. The morphology of PPy–N and PA–N composite films depended on the polymerization conditions, which might be due to the difference in the polymerization speed of pyrrole or aniline in polymer matrices. These PPy–N and PA–N composite films exhibited good environmental stability and excellent mechanical properties. © 1994 John Wiley & Sons, Inc.     

Ni0.3Co2.7O4 spinel particles/polypyrrole composite electrode:: Study by X-ray photoelectron spectroscopy

In this work we have studied the multilayered polypyrrole/oxide composite electrode on glassy carbon having the structure GC/PPy/PPy(Ni_0.3Co_2.7O₄)/PPy, in which the spinel oxide Ni_0.3Co_2.7O₄ is known to be an electrocatalyst of the oxygen reduction reaction in alkaline medium. The successive GC/PPy, GC/PPy/PPy(Ni_0.3Co_2.7O₄) and GC/PPy/PPy(Ni_0.3Co_2.7O₄)/PPy parts of the electrode were examined by X-ray photoelectron spectroscopy. The results indicate that the electronic structure of the PPy is independent of the thickness of the PPy used to prepare the electrodes. The XPS data also show that cobalt is present in both divalent and trivalent states. The PPy doping degree by Cl⁻ ions (in terms of the Cl⁻/N) and the oxide/PPy mass ratio observed by XPS were 19 and 4.5%, respectively.     

Fabrication and electroanalytical characterization of label-free DNA sensor based on direct electropolymerization of pyrrole on p-type porous silicon substrates

Label-free DNA sensors based on porous silicon (PS) substrate were fabricated and electrochemically characterized. p-type silicon wafer was electrochemically anodized in an ethanolic hydrofluoric (HF) solution to construct a PS layer on which polypyrrole (PPy) film was directly electropolymerized. To achieve direct electropolymerization of PPy on PS substrate without pre-deposition of any metallic thin-film underlayer, a low resistivity wafer (0.01–0.02 Ω cm) was used. The rough surface of the PS layer allowed for a strong adsorption of the PPy film. Intrinsic negative charge of the DNA backbone was exploited to electrostatically adsorb 26 base pairs of probe DNA (pDNA) into the PPy film by applying positive bias. The pDNA was designed to hybridize with the target DNA (tDNA) which is the insertion element (Iel) gene of Salmonella enterica serovar Enteritidis. Dependence of peak current (i _p ) around 0.2 V vs Ag/AgCl on tDNA concentration and incubation time were shown from the cyclic voltammograms of PS/PPy + pDNA + tDNA substrates in a 0.01 M potassium perchlorate solution. Plot of i _p vs incubation time showed a reduction in current density (J) by ca. 29 μA cm⁻² every hour. Sensitivity obtained from a plot of i _p vs tDNA concentration was −166.6 μA cm⁻² μM⁻¹. Scanning electron microscopy (SEM) image of the cross-section of a PS/PPy + pDNA + tDNA multilayered film showed successful direct electropolymerization of PPy for a nano-PS DNA biosensor.     

Polypyrrole/NiFe2O4 composites with improved hexavalent chromium removal from aqueous solution

Polypyrrole/NiFe₂O₄ (PPy/NiFe₂O₄) composites were prepared by ultrasonic oxidative polymerization in the presence of NiFe₂O₄ nanoparticles (NPs). The nanostructure of PPy/NiFe₂O₄ was confirmed by the X‐ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM) examinations. The adsorption of Cr(VI) onto the PPy/NiFe₂O₄ composite was lowly pH dependent and the adsorption kinetics followed the Pseudo‐second‐order model. The Langmuir isothermal model well described the adsorption isotherm data and the maximum adsorption capacity increased with the increase of temperature. The maximum adsorption capacity of the PPy/NiFe₂O₄ for Cr(VI) ions was up to 50 mg/g at pH 2.0. The excellent adsorption characteristic of PPy/NiFe₂O₄ composite will render it a highly efficient and economically viable adsorbent for Cr(VI) ions removal. POLYM. COMPOS., 38:2779–2787, 2017. © 2015 Society of Plastics Engineers     

Electrochemical Biosensor Based on surfactant doped polypyrrole (PPy) matrix for lactose determination

Lactose biosensor based on surfactant doped polypyrrole (PPy) was developed. Galactose oxidase and β‐galactosidase was coimmobilized in PPy matrix during electropolymerization process with the presence of sodium dodecylbenzene sulphonic acid as surfactant. Bi‐enzyme entrapped PPy was characterized with Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), and scanning electron microscopy (SEM). The response of the enzyme electrode was measured by CV in the range of ?0.1 to 1.0 V versus Ag/AgCl which was due to the electrooxidation of enzymatically produced H₂O₂. The effect of lactose concentration was investigated. Response time of biosensor was found to be 8–10 s (the time required to obtain the maximum peak current) and upper limit of the linear working portions was found to be 1.22 mM lactose concentration with a detection limit of (2.6 × 10^?6 M). The apparent Michaelis–Menten constant was found to be 0.117 mM lactose. The effects of interferents (ascorbic acid and uric acid) were determined. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40200.     

Single step modification of micrometer-sized polystyrene particles by electromagnetic polyaniline and sorption of chromium(VI) metal ions from water

This article describes a single-step reproducible approach for the surface modification of micrometer-sized polystyrene (PS) core particles to prepare electromagnetic PS/polyaniline–Fe₃O₄ (PS/PANi–Fe₃O₄) composite particles. The electromagnetic PANi–Fe₃O₄ shell was formed by simultaneous seeded chemical oxidative polymerization of aniline and precipitation of Fe₃O₄ nanoparticles. The weight ratio of PS to aniline was optimized to produce core–shell structure. PS/PANi–Fe₃O₄ composite particles were used as adsorbent for the removal of Cr(VI) via anion-exchange mechanism. The composite particles possessed enough magnetic property for magnetic separation. The adsorption was highly pH dependent. Adsorption efficiency reached 100% at pH 2 in 120 min when 0.05 g of composite particles was mixed with 30 mL 5 mg L⁻¹ Cr(VI) solution. The adsorption isotherm fitted best with Freundlich model and maximum adsorption capacity approached 20.289 mg g⁻¹ at 323 K. The prepared composite was found to be an useful adsorbent for the removal of soluble Cr(VI) ions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47524.