Acrylamide/2-acrylamido-2-methylpropane sulfonic acid and associated sodium salt superabsorbent copolymer nanocomposites with mica as fire retardants

Acrylamide (AM) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS-H⁺) or its sodium salt (AMPS-Na⁺) were copolymerised by free-radical crosslinking polymerization to obtain poly(AM-co-AMPS-H⁺) and poly(AM-co-AMPS-Na⁺) superabsorbent polymers (SAPs). A maximum water absorbency in deionised water of 1200 g g⁻¹ was achieved for poly(AM-co-AMPS-Na⁺) at a 85% mol of AMPS-Na⁺. The inclusion of mica at 5-30% (w w⁻¹) into the preparation of poly(AM-co-AMPS-Na⁺) SAP leads to an intercalated structure, as detected by XRD and TEM analyses. Poly(AM-co-AMPS-Na⁺)/30% (w w⁻¹) mica SAP nanocomposite showed a tap water absorbency of 593 g g⁻¹ with a better thermal stability, compared to the pure SAP. Cone calorimetric analyses revealed that the wood specimens coated with the prepared poly(AM-co-AMPS-Na⁺) SAP or its 30% (w w⁻¹) mica nanocomposite provided excellent protection in delaying the ignition time after exposure to an open flame when compared to that observed with the uncoated specimen. The maximum reduction in the peak heat release rate and the greatest extension of time at peak heat release rate were observed with the nanocomposite-coated surface, but the total heat release rate was increased. The delayed burning mechanism is brought by the intercalating structure of mica in the SAP nanocomposites, which provided a better shielding effect against external heat sources, and the capability of the SAP nanocomposite in holding a large amount of water.     

Preparation of poly(vinylidene fluoride) nanocomposite membranes based on graft polymerization and sol–gel process for polymer electrolyte membrane fuel cells

Proton conducting nanocomposite membranes consisting of poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-poly(styrene sulfonic acid), i.e., P(VDF-co-CTFE)-g-PSSA graft copolymer and sulfonated silica and were prepared using a sol–gel reaction and subsequent oxidation of a silica precursor, i.e., (3-mercaptopropyl) trimethoxysilane (MPTMS). The successful formation of amorphous phase nanocomposite membranes was confirmed via FT-IR and wide-angle X-ray scattering. All membranes were semi-transparent and mechanically strong, as characterized by a universal tensile machine. Transmission electron microscopy and small-angle X-ray scattering analysis revealed that silica 5–10 nm in size were homogeneously dispersed in the matrix at up to 5 wt.% of MPTMS. At higher concentrations, the silica grew to more than 50 nm in size, which disrupted the microphase-separated structure of the graft copolymer. As a result, both proton conductivity (0.12 S/cm at 25 °C) and single cell performance (1.0 W/cm² at 75 °C) were maximal at 5 wt.% MPTMS.     

Development of novel cellulose acetate-g-poly(sodium 4-styrenesulfonate) proton conducting polyelectrolyte polymer

The development of cheap and efficient proton conducting polymers attracts scientists' attention, resulting in its potential role in fuel cell applications. This work synthesized a novel cellulose acetate-g-poly(sodium 4-styrene sulfonate) via free radical polymerization using potassium persulfate (KPS) as an initiator. The effects of varying KPS concentration, cellulose acetate (CA), sodium 4-styrene sulfonate (Na-SSA) content, reaction time, and temperature on the grafting parameters were studied. Grafting parameters, including the grafting yield (GY %), Add-on (%) and grafting efficiency (GE %) of the grafting reaction, were evaluated. Additionally, FTIR, TGA, DSC, ¹HNMR and EDX analyses were studied. The developed graft copolymers membranes illustrated increased water uptake values and ion exchange capacity (IEC) with the add-on (%). Furthermore, the proton conductivity of the developed graft copolymers was found superior (4.77 × 10⁻³ S.cm⁻¹) to the pristine CA membrane (0.035 × 10⁻³ S.cm⁻¹).     

Proton conducting membranes based on poly(vinyl chloride) graft copolymer electrolytes

The direct preparation of proton conducting poly(vinyl chloride) (PVC) graft copolymer electrolyte membranes using atom transfer radical polymerization (ATRP) is demonstrated. Here, direct initiation of the secondary chlorines of PVC facilitates grafting of a sulfonated monomer. A series of proton conducting graft copolymer electrolyte membranes, i.e. poly(vinyl chloride)‐g‐poly(styrene sulfonic acid) (PVC‐g‐PSSA) were prepared by ATRP using direct initiation of the secondary chlorines of PVC. The successful syntheses of graft copolymers were confirmed by ¹H‐NMR and FT‐IR spectroscopy. The images of transmission electron microscopy (TEM) presented the well‐defined microphase‐separated structure of the graft copolymer electrolyte membranes. All the properties of ion exchange capacity (IEC), water uptake, and proton conductivity for the membranes continuously increased with increasing PSSA contents. The characterization of the membranes by thermal gravimetric analysis (TGA) also demonstrated their high thermal stability up to 200°C. The membranes were further crosslinked using UV irradiation after converting chlorine atoms to azide groups, as revealed by FT‐IR spectroscopy. After crosslinking, water uptake significantly decreased from 207% to 84% and the tensile strength increased from 45.2 to 71.5 MPa with a marginal change of proton conductivity from 0.093 to 0.083 S cm^?1, which indicates that the crosslinked PVC‐g‐PSSA membranes are promising candidates for proton conducting materials for fuel cell applications. Copyright © 2008 John Wiley & Sons, Ltd.     

Use of amidoximated hydrogel for removal and recovery of U(VI) ion from water samples

Poly(acrylamidoxime-co-2-acrylamido-2-methylpropane sulfonic acid) (PAMSA) hydrogel was prepared by copolymerization of acrylonitrile and 2-acrylamido-2-methylpropane sulfonic acid as monomer, N,N′-methylenebis(acrylamide) as crosslinking agent and potassium peroxodisulfate as initiator. Amidoximated copolymer network was prepared by the reaction of copolymer network with hydroxylamine hydrochloride. A batch procedure was used for the determination of the characteristics of the U(VI) solid phase extraction from the amidoximated hydrogel. The determination of U(VI) was performed by spectrophotometric method using arsenazo-III as complexing agent. Optimal pH value for the quantitative preconcentration was 3, and full desorption was achieved with 3 mol L⁻¹ HClO₄. The adsorption process can be well described by the pseudo-second-order kinetic model, and the equilibrium adsorption isotherm was closely fitted with the Langmuir model. A preconcentration factor of 20 and the three sigma detection limit of 2.8 μg L⁻¹ (n = 20) were achieved for uranium(VI) ions. The PAMSA hydrogel was used for separating and preconcentrating the uranyl ion existing in sea water samples, thermal spring water samples and the certified reference materials (TMDA 64; fortified lake water sample).     

P(AA-AMPS)–PVA/polysulfone composite hollow fiber membranes for propylene dehumidification

A series of composite hollow fiber membranes, poly(acrylic acid-co-2-acrylamido-2-methyl-1-propane sulfonic acid) (P(AA-AMPS))–poly(vinyl alcohol) (PVA) membranes as skin layers and polysulfone (PS) hollow fiber membranes as support layers, were prepared for dehumidification of propylene gas. The chemical and physical structures, including inter-components interaction, crystallinity, glass transition temperature and free volume of the membranes, were systematically characterized. Through the sorption experiments, it was found that the membrane exhibited a preferential sorption toward water, and initially the water sorption increased remarkably with P(AA-AMPS) content increasing, afterwards reached the zenith, then decreased rapidly. Dehumidification performance showed that the membrane containing 50 wt.% P(AA-AMPS) exhibited the highest permeance of 363 GPU and an infinite separation factor for 0.5 wt.% water in feed at 298 K. Permeance decreased considerably with increasing operating temperature, but increased considerably with increasing water content.     

Single-step synthesis of proton conducting poly(vinylidene fluoride) (PVDF) graft copolymer electrolytes

The single-step synthesis of proton conducting poly(vinylidene fluoride) (PVDF) graft copolymer electrolytes is demonstrated. The graft copolymers of PVDF backbone with poly(sulfopropyl methacrylate) (PVDF-g-PSPMA) and poly(styrene sulfonic acid) (PVDF-g-PSSA) were synthesized using PVDF as a macroinitiator for atom transfer radical polymerization (ATRP). ¹H NMR and FT-IR spectroscopy show that the “grafting from” method using ATRP was successful and the maximum grafting degrees were 35 and 25 wt% for PVDF-g-PSPMA and PVDF-g-PSSA, respectively. The IEC values were 0.63 and 0.45 meq/g, the water uptakes were 46.8 and 33.4 wt% and the proton conductivities were 0.015 and 0.007 S/cm at room temperature, for PVDF-g-PSPMA and PVDF-g-PSSA, respectively. Both membranes exhibited excellent thermal stability up to around 350 °C, verified by thermal gravimetric analysis (TGA).     

Nanofiltration membranes based on poly(vinylidene fluoride‐co‐chlorotrifluoroethylene)‐graft‐poly(styrene sulfonic acid)

Graft copolymers comprising poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) backbone and poly(styrene sulfonic acid) side chains, i.e. P(VDF‐co‐CTFE)‐g‐PSSA were synthesized using atom transfer radical polymerization (ATRP) for composite nanofiltration (NF) membranes. Direct initiation of the secondary chlorinated site of CTFE units facilitates grafting of PSSA, as revealed by FT‐IR spectroscopy. The successful “grafting from” method and the microphase‐separated structure of the graft copolymer were confirmed by transmission electron microscopy (TEM). Wide angle X‐ray scattering (WAXS) also showed the decrease in the crystallinity of P(VDF‐co‐CTFE) upon graft copolymerization. Composite NF membranes were prepared from P(VDF‐co‐CTFE)‐g‐PSSA as a top layer coated onto P(VDF‐co‐CTFE) ultrafiltration support membrane. Both the rejections and the flux of composite membranes increased with increasing PSSA concentration due to the increase in SO₃H groups and membrane hydrophilicity, as supported by contact angle measurement. The rejections of NF membranes containing 47 wt% of PSSA were 83% for Na₂SO₄ and 28% for NaCl, and the solution flux were 18 and 32 L/m² hr, respectively, at 0.3 MPa pressure. Copyright © 2008 John Wiley & Sons, Ltd.     

Novel sulphonated poly (vinyl chloride)/poly (2-acrylamido-2-methylpropane sulphonic acid) blends-based polyelectrolyte membranes for direct methanol fuel cells

Proton-conducting and methanol barrier properties of the proton exchange membrane (PEM), as well as the high cost of direct methanol fuel cell (DMFC) components, are the key determinants of the performance and commercialization of DMFCs. Therefore, this study aimed to develop cost- and performance-effective membranes based on sulphonated poly (vinyl chloride) (SPVC)/poly (2-acrylamido-2-methyl-1-propane sulphonic acid) (PAMPS) blends. Such membranes have been simply prepared by blending SPVC and PAMPS solutions, followed by solvent evaporation via casting. Interaction of SPVC with PAMPS was confirmed by different characterization techniques such as Fourier Transform Infra-red (FTIR) and Raman scattering spectroscopy in which the two characteristic absorption bands of sulfonic groups appeared at 1093 and 1219 cm⁻¹ additionally, strong peaks at around 1656 cm⁻¹ attributed to vibration of amide groups of PAMPS portion in the polymer blend. Furthermore, the interaction of SPVC with PAMPS improves the thermal properties along with ion exchange capacity in turn decreasing the methanol permeability through the membrane in comparison with the SPVC membrane. The IEC of PVC and Nafion 117 membranes were 1.25, 0.91 meq/g; respectively. And the maximum water uptake of PVC and Nafion 117 membranes were 75 and 65.44%; respectively. Methanol permeability value of 7.7 × 10⁻⁷ cm²/s which was noticeably lower than the corresponding value recorded for Nafion® (3.39 × 10⁻⁶ cm²/s). Therefore, these fabricated membranes can be considered a low-cost efficient candidate for use in DMFC, especially for its capability to resolve the methanol cross-over issue.     

Radical copolymerization of sodium 2-acrylamido-2-methylpropane sulfonate and sodium acrylate in water-alcohol solutions

The effect of the nature of a solvent on the kinetic parameters of the process and the intrinsic viscosities of copolymers formed by the homogeneous free-radical copolymerization of the sodium salt of 2-acrylamido-2-methylpropane sulfonic acid and the sodium salt of acrylic acid initiated by potassium persulfate in water, water-methanol mixtures (92: 8, 84: 16, 75: 25, 50: 50), and water-isopropanol (50: 50) mixtures at pH 9 and 60°C is studied. The initial rate of copolymerization increases with increases in the concentrations of the comonomers and initiator, the content of 2-acrylamido-2-methylpropane sulfonic acid in the initial monomer mixture, and the content of water in a water-methanol mixture and in the sequence of solvents water-methanol < water-isopropanol. The intrinsic viscosity and yield of the copolymer grow when the content of 2-acrylamido-2-methylpropane sulfonic acid in the initial monomer mixture and water in water-methanol mixtures are increased and when isopropanol is replaced with methanol. The reactivity ratios of the monomers in water-methanol (50: 50) and water-isopropanol (50: 50) mixtures are determined.     

Water-soluble copolymers. VII. Cerium (IV) induced graft copolymerization of acrylamide and sodium-2-acrylamido-2-methylpropane sulfonate onto dextran

Studies were conducted on grafting of acrylamide (AM) and sodium-2-acrylamido-2-methylpropane sulfonate (NaAMPS) comonomers onto dextran utilizing Ce(IV) induced initiation. The effects of reaction temperature, the Ce(IV)/dextran ratio, and the AM/NaAMPS ratio on grafting yield were investigated. The graft copolymerization behavior can be explained by exchange of the AMPS anion with one of the ligands on the Ce(IV) initiator. Oxidative modification of the dextran substrate improved the yield of graft copolymer. The dextran-g-poly(acrylamido-co-sodium-2-acrylamido-2-methylpropane sulfonate) samples prepared by this method were characterized as to copolymer composition and molecular weight utilizing elemental analysis, dilute solution viscometry, and aqueous size exclusion chromatography. Relationships of molecular weight and charge density to kinematic viscosity and salt sensitivity are discussed.     

The Influence of Reaction Conditions on the Copolymer Composition in Inverse Miniemulsion

Summary: Water-soluble poly(2-acrylamido-2-methylpropane-1-sulfonic acid-co-1-vinylimidazole) (P(AMPS-co-1-VIm)) and poly(2-acrylamido-2-methylpropane-1-sulfonic acid-co-2-(dimethylamino)ethyl methacrylate (P(AMPS-co-DAMA)) are studied as it is known that the copolymer composition is affected by pH of the monomer phase in inverse miniemulsion. The distribution of the basic monomers in the continuous and dispersed phase changes due to their degrees of protonation. The amounts of the monomers in the cyclohexane phase is determined by gas chromatography, the copolymer composition is studied by elemental and thermogravimetric analysis. An insight into the monomer distribution in the polymer is provided by simultaneous potentiometric and conductometric titration of polymer solutions.     

Synthesis and characterization of grafted/crosslinked proton conducting membranes based on amphiphilic PVDF copolymer

A novel graft copolymer consisting of a poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) backbone and poly(glycidyl methacrylate) side chains, that is, P(VDF‐co‐CTFE)‐g‐PGMA, was synthesized through atom transfer radical polymerization (ATRP) using CTFE units as a macroinitiator. Successful synthesis and microphase‐separated structure of the polymer were confirmed by ¹H NMR, FTIR spectroscopy, and TEM. As‐synthesized P(VDF‐co‐CTFE)‐g‐PGMA copolymer was sulfonated by sodium bisulfite, followed by thermal crosslinking with sulfosuccinic acid (SA) via the esterification to produce grafted/crosslinked polymer electrolyte membranes. The IEC values continuously increased with increasing SA content but water uptake increased with SA content up to 10 wt %, above which it decreased again as a result of competitive effect between crosslinking and hydrophilicity of membranes. At 20 wt % of SA content, the proton conductivity reached 0.057 and 0.11 S/cm at 20 and 80 °C, respectively. The grafted/crosslinked P(VDF‐co‐CTFE)‐g‐PGMA/SA membranes exhibited good mechanical properties (>400 MPa of Young's modulus) and high thermal stability (up to 300 °C), as determined by a universal testing machine (UTM) and TGA, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1110–1117, 2010     

Intercalated Poly (2-acrylamido-2-methyl-1-propanesulfonic Acid) into Sulfonated Poly (1,4-phenylene ether-ether-sulfone) Based Proton Exchange Membrane: Improved Ionic Conductivity

A series of hybrid proton exchange membranes were synthesized via in situ polymerization of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) PMPS with sulfonated poly (1,4-phenylene ether-ether-sulfone) (SPEES). The insertion of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) PMPS, between the rigid skeleton of SPEES plays a reinforcing role to enhance the ionic conductivity. The synthesized polymer was chemically characterized by fourier-transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance ¹H NMR spectroscopy to demonstrate the successful grafting of PMPS with the pendent polymer chain of SPEES. A variety of physicochemical properties were also investigated such as ion exchange capacity (IEC), proton conductivity, water uptake and swelling ratio to characterize the suitability of the formed polymer for various electrochemical applications. SP-PMPS-03, having the highest concentration of all PMPS, shows excellent proton conductivity of 0.089 S cm⁻¹ at 80 °C which is much higher than SPEES which is ~0.049 S cm⁻¹. Optimum water uptake and swelling ratio with high conductivity is mainly attributed to a less ordered arrangement polymer chain with high density of the functional group to facilitate ionic transport. The residual weight was 93.35, 92.44 and 89.56%, for SP-PMPS-01, 02 and 03, respectively, in tests with Fenton’s reagent after 24 h. In support of all above properties a good chemical and thermal stability was also achieved by SP-PMPS-03, owing to the durability for electrochemical application.     

Preparation and characterization of PVDF‐based blend membranes as polymer electrolyte membranes in fuel cells: Study of factor affecting the proton conductivity behavior

There is a huge demand especially for polyvinylidene fluoride (PVDF) and its copolymers to provide high performance solid polymer electrolytes for use as an electrolyte in energy supply systems. In this regard, the blending approach was used to prepare PVDF‐based proton exchange membranes and focused on the study of factor affecting the ir proton conductivity behavior. Thus, a series of copolymers consisting of poly (methyl methacrylate) (PMMA), polyacrylonitrile (PAN), and poly(2‐acrylamido‐2‐methyl‐l‐propanesulfonic acid) (PAMPS) as sulfonated segments were synthesized and blended with PVDF matrix in order to create proton transport sites in PVDF matrix. It was found that addition of PMMA‐co‐PAMPS and PAN‐co‐PAMPS copolymers resulted in a significant increase in porosity, which favored the water uptake and proton transport at ambient temperature. Furthermore, crystallinity degree of the PVDF‐based blend membranes was increased by addition of the related copolymers, which is mainly attributed to formation of hydrogen bonding interaction between PVDF matrix and the synthesized copolymers, and led to a slight decrease in proton conductivity behavior of blend membranes. From impedance data, the proton conductivity of the PVDF/PMMA‐co‐PAMPS and PVDF/PAN‐co‐PAMPS blend membranes increases to 10 and 8.4 mS cm⁻¹ by adding only 50% of the related copolymer (at 25°C), respectively. Also, the blend membranes containing 30% sulfonated copolymers showed a power density as high as 34.30 and 30.10 mW cm⁻² at peak current density of 140 and 79.45 mA cm⁻² for the PVDF/PMMA‐co‐PAMPS and PVDF/PAN‐co‐PAMPS blend membranes, respectively. A reduction in the tensile strength was observed by the addition of amphiphilic copolymer, whereas the elongation at break of all blend membranes was raised.     

Novel dye removing agent based on CTS-g-P(AA-co-NIPAM)/GO composite

A novel composite Chitosan graft poly (acrylic acid-co-N-isopropylacrylamide)/graphite oxide (CTS-g-P(AA-co-NIPAM/GO) is synthesized and used to remove methylene blue (MB) and fuchsin basic (FB) from aqueous solutions by adsorption. Small amount of GO brings about great improvement of the thermostability together with the adsorption amount. Adsorption capacities of MB and FB increase from 842.1 and 633.7 mg/g, respectively, to 1496.3 and 1000.8 mg/g, respectively, with 0.02 g intercalation amount of GO. The interactions between GO and main body of CTS-g-P(AA-co-NIPAM) graft copolymer are hydrogen and amide bonds, whereas that between dye molecules and CTS-g-P(AA-co-NIPAM)/GO composite is hydrogen bond as well as electrostatic interaction. Effect of various conditions on the adsorption capacities is discussed. Adsorption isotherms and thermodynamics are studied. The adsorption of both MB and FB are spontaneous and satisfy the Redlich-Peterson equation. Kinetic study shows that the adsorption of both dyes is in accordance with the Pseudo first-order kinetic model.     

Composite polymer electrolyte membranes comprising P(VDF‐co‐CTFE)‐g‐PSSA graft copolymer and zeolite for fuel cell applications

Hybrid organic/inorganic composite polymer electrolyte membranes based on a poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) grafted membrane and varying concentrations of zeolite were investigated for application in proton exchange membrane fuel cells (PEMFC). A proton conducting comb copolymer consisting of poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) backbone and poly(styrene sulfonic acid) (PSSA) side chains, i.e. P(VDF‐co‐CTFE)‐g‐PSSA (graft copolymer) with 47 wt% of PSSA was synthesized using atom transfer radical polymerization (ATRP) and solution blended with zeolite. Upon incorporation of zeolite, the symmetric stretching band of both SO group (1169 cm^?1) and the ? OH group (3426 cm^?1) shifted to lower wavenumbers. The shift in these FT‐IR spectra suggests that the zeolite particles strongly interact with the sulfonic acid groups of PSSA chains. When the weight percent of zeolite 5A is above 7%, the proton conductivity at room temperature was reduced to 0.011 S/cm. The water uptake of the composite membranes decreased from 234 to 125% with an increase of the zeolite 5A weight percent to 10 wt%. The decrease in water uptake is likely a result of the decrease in the number of available water absorption sites because of the hydrogen bonding interactions between the zeolite particles and the graft copolymer matrix. This behavior is successfully investigated by scanning electron microscopy (SEM). The results of thermal gravimetric analysis (TGA) also showed that all the membranes were stable up to 300°C. Copyright © 2009 John Wiley & Sons, Ltd.     

Proton conducting grafted/crosslinked membranes prepared from poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) copolymer

Poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) (P(VDF‐co‐CTFE)) backbone was grafted with crosslinkable chains of poly(hydroxyl ethyl acrylate) (PHEA) and proton conducting chains of poly(styrene sulfonic acid) (PSSA) to produce amphiphilic P(VDF‐co‐CTFE)‐g‐P(HEA‐co‐SSA) graft copolymer via atom transfer radical polymerization (ATRP). Successful synthesis and microphase‐separated structure of the copolymer were confirmed by ¹H NMR, FT‐IR spectroscopy, and TEM analysis. Furthermore, this graft copolymer was thermally crosslinked with sulfosuccinic acid (SA) to produce grafted/crosslinked membranes. Ion exchange capacity (IEC) increased continuously with increasing SA contents but the water uptake increased up to 6 wt% of SA concentration, above which it decreased monotonically. The membrane also exhibited a maximum proton conductivity of 0.062 S/cm at 6 wt% of SA concentration, resulting from competitive effect between the increase of ionic groups and the degree of crosslinking. XRD patterns also revealed that the crystalline structures of P(VDF‐co‐CTFE) disrupted upon graft polymerization and crosslinking. These membranes exhibited good thermal stability at least up to 250°C, as revealed by TGA. Copyright © 2009 John Wiley & Sons, Ltd.     

TEMPO addition into pre-irradiated fluoropolymers and living-radical graft polymerization of styrene for preparation of polymer electrolyte membranes

We prepared proton exchange membranes (PEMs) by 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)-mediated living-radical graft polymerization (LRGP) of styrene into fluoropolymer films and subsequent sulfonation. Poly(vinylidene fluoride) (PVDF) and poly(ethylene-co-tetrafluoroethylene) (ETFE) films were first irradiated and then treated with TEMPO solutions in various solvents. TEMPO addition was confirmed by the test of styrene grafting into TEMPO-treated films at 60 °C, at which the LRGP never proceeds. This test enabled us to differentiate the LRGP from the conventional graft polymerization. In order to gain a deep insight about TEMPO-addition reaction, the TEMPO-penetration behavior into the base polymer films was examined by a permeation experiment and computer simulation. Xylene and dioxane were appropriate solvents for the complete introduction of TEMPO into PVDF and ETFE films, respectively. Then, the LRGP of styrene was performed based on the fully TEMPO-capped films at 125 °C with various solvents. By using an alcoholic solvent, the degree of grafting was enhanced and it reached a maximum of 38%. This grafted film was sulfonated to prepare a PEM showing an ion exchange capacity of 2.2 meq/g and proton conductivity of 1.6×10^?1 S/cm.     

Synthesis,identification and study of electrical conductivity of the doped copolymer carbazole–phenol formaldehyde

The copolymer carbazole–phenol formaldehyde doped with 4 (4-hydroxy-phenyl azo)-benzene sulfonic acid (PABS), 2,5-dimethyl benzene sulfonic acid (PXSA) and 4-hydroxy-m-benzene disulfonic acid (PDSA) were prepared. These compounds are identified by FT-IR spectroscopy.The conductivity of copolymer carbazole–phenol formaldehyde doped with 4 (4-hydroxy-phenyl azo)-benzene sulfonic acid (PABS), 2,5-dimethyl benzene sulfonic acid (PXSA) and 4-hydroxy-m-benzene disulfonic acid (PDSA) was studied as a function of weight of the dopant compounds; an increase of conductance of the copolymer by doping with PABS is noted; the conductance became equal to 0.000595 ohm⁻¹ for 0.1 g higher conductance for the copolymer when it is doping with PABS.