Proton dissociation and transfer in hydrated phosphoric acid clusters

The dynamics and mechanisms of proton dissociation and transfer in hydrated phosphoric acid (H₃PO₄) clusters under excess proton conditions were studied based on the concept of presolvation using the H₃PO₄–H₃O⁺–nH₂O complexes (n = 1–3) as the model systems and ab initio calculations and Born–Oppenheimer molecular dynamics (BOMD) simulations at the RIMP2/TZVP level as model calculations. The static results showed that the smallest, most stable intermediate complex for proton dissociation (n = 1) is formed in a low local‐dielectric constant environment (e.g., ε = 1), whereas proton transfer from the first to the second hydration shell is driven by fluctuations in the number of water molecules in a high local‐dielectric constant environment (e.g., ε = 78) through the Zundel complex in a linear H‐bond chain (n = 3). The two‐dimensional potential energy surfaces (2D‐PES) of the intermediate complex (n = 1) suggested three characteristic vibrational and ¹H NMR frequencies associated with a proton moving on the oscillatory shuttling and structural diffusion paths, which can be used to monitor the dynamics of proton dissociation in the H‐bond clusters. The BOMD simulations over the temperature range of 298–430 K validated the proposed proton dissociation and transfer mechanisms by showing that good agreement between the theoretical and experimental data can be achieved with the proposed rate‐determining processes. The theoretical results suggest the roles played by the polar solvent and iterate that insights into the dynamics and mechanisms of proton transfer in the protonated H‐bond clusters can be obtained from intermediate complexes provided that an appropriate presolvation model is selected and that all of the important rate‐determining processes are included in the model calculations. © 2015 Wiley Periodicals, Inc.     

Synthesis and evaluation of new phosphonic acid‐functionalized acrylamides with potential biomedical applications

Phosphorus‐containing acidic monomers are able to interact with the inorganic phase of mineralized tissues such as enamel, dentin, and bone. From this perspective, three phosphonic acid‐containing acrylamide monomers with different lengths of alkyl chains were synthesized to be used for both self‐etching dental adhesives and mineralized hydrogel scaffolds. Monomers were synthesized by the reaction of α‐aminophosphonates (diethyl aminomethylphosphonate, diethyl 2‐aminobutan‐2‐ylphosphonate, and diethyl 2‐aminooctan‐2‐ylphosphonate) with acryloyl chloride followed by the hydrolysis of phosphonate groups by using trimethylsilyl bromide. The properties such as pH in the range of mild self‐etching adhesives, hydrolytic stability, high rate of copolymerizations with 2‐hydroxyethyl methacrylate (HEMA) and HEMA/glycerol dimethacrylate, giving high‐molecular‐weight polymers on thermal polymerization, and strong decalcification ability of hydroxyapatite make these monomers good candidates for self‐etching adhesives, although no appreciable effect of the number and size of the α‐substituents was observed. Hydrogel scaffolds containing phosphonic acid groups were fabricated, characterized, and mineralized. Altogether, the results suggest that these phosphonic acid‐containing monomers have suitable properties to be used in fabrication of biomaterials for both dental and bone tissue engineering applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2755–2767     

Synthesis and proton conductivities of phosphonic acid containing poly‐(arylene ether)s

A novel phosphonic acid containing bisphenol was successfully synthesized from phenolphthalein and m‐aminophenylphosphonic acid. A series of homo‐ and copoly‐(arylene ether)s containing phosphonic acid groups were prepared by solution nucleophilic polycondensation. These phosphonic acid containing polymers can readily be dissolved in common organic solvents, such as dimethyl sulfoxide, N‐methyl‐2‐pyrrolidinone, and N‐cyclohexylpyrrolidinone, and can be cast into tough and smooth films. The presence of phosphonic acid pendants in the poly‐(arylene ether)s was confirmed by NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, and conductivity measurements. This is the first report on the attachment of phenylphosphonic acid groups as side chains to aromatic polyethers. These poly‐(arylene ether)s had very high glass‐transition temperatures ranging from 254 to >315 °C and high molecular weights. The conductivities of the synthesized polymers were analyzed by the Cole–Cole method, and they ranged from 10^?5 to 10^?6 Scm^?1. The synthesized polymers also exhibited good solution processability. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3218–3226, 2001     

Water‐soluble polymers from acid‐functionalized norbornenes

Unprotected exo,exo‐5‐norbornene‐2,3‐dicarboxylic acid and exo,exo‐7‐oxa‐5‐norbornene‐2,3‐dicarboxylic acid were polymerized via ring‐opening metathesis polymerization. This reaction yielded polymers with molecular weights (M_n from GPC) ranging from 31 to 242 kg/mol and polydispersity indices between 1.05 and 1.12, using Grubbs' third generation catalyst. The water solubility as a function of pH value of the polymers was investigated by dynamic light scattering (DLS). DLS and acid‐base titration revealed that the oxanorbornene polymer was water soluble over a wider pH range than its norbornene analog. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1266–1273, 2009     

Effects of different acid functional groups on proton conductivity of polymer‐1,2,4‐triazole blends

Proton transfer reactions under anhydrous conditions have attracted remarkable interest due to chemical energy conversions in polymer electrolyte membrane fuel cells. In this work, 1H‐1,2,4‐triazole (Tri) was used as a proton solvent in different polymer host matrices such as Poly(vinylphosphonic acid) (PVPA), and poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) (PAMPS). PVPATri_x and PAMPSTri_x electrolytes were investigated where x is the molar ratio of Tri to corresponding polymer repeat unit. The interaction between polymer and Tri was studied via FTIR spectroscopy. Thermogravimetry analysis and differential scanning calorimetry were employed to examine the thermal stability and homogeneity of the materials, respectively. PVPATri_1.5 showed a maximum water‐free proton conductivity of 2.3 × 10^?3 S/cm at 120 °C and that of PAMPSTri₂ was 9.3 × 10^?4 S/cm at 140 °C. The results were interpreted in terms of different acidic functional groups and composition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3315–3322, 2006     

Synthesis and properties of sulfonated poly(arylene ether) containing tetraphenylmethane moieties for proton‐exchange membrane

A novel sulfonated poly(arylene ether) containing tetraphenylmethane moieties was successfully synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place only at the para position on the pendant phenyl rings because of the specially designed parent polymer. The sulfonation degree can be easily controlled by using different ratios of sulfonation agent to polymer repeating unit. The position and degree of sulfonation were characterized by ¹H NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N′‐dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton's reagent test revealed that the membrane exhibited superior stability to oxidation. The proton conductivities of the films were determined to be equivalent with Nafion® 117 under same conditions. The new polymer with sulfonic acid function on pendent phenyl rings can be potentially used as a proton‐exchange membrane for polymer electrolyte membrane fuel cell. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6411–6418, 2005     

Solid‐State Dynamics of Uranyl Polyoxometalates

Understanding fundamental uranyl polyoxometalate (POM) chemistry in solution and the solid state is the first step to defining its future role in the development of new actinide materials and separation processes that are vital to every step of the nuclear fuel cycle. Many solid‐state geometries of uranyl POMs have been described, but we are only beginning to understand their chemical behavior, which thus far includes the role of templates in their self‐assembly, and the dynamics of encapsulated species in solution. This study provides unprecedented detail into the exchange dynamics of the encapsulated species in the solid state through Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Although it was previously recognized that capsule‐like molybdate and uranyl POMs exchange encapsulated species when dissolved in water, analogous exchange in the solid state has not been documented, or even considered. Here, we observe the extremely high rate of transport of Li⁺ and aqua species across the uranyl shell in the solid state, a process that is affected by both temperature and pore blocking by larger species. These results highlight the untapped potential of emergent f‐block element materials and vesicle‐like POMs.     

Thermal characterization and solid‐state 13C‐NMR investigation of blends of poly(N‐phenyl‐2‐hydroxytrimethylene amine) and poly(N‐vinyl pyrrolidone)

The miscibility and thermal properties of poly(N‐phenyl‐2‐hydroxytrimethylene amine)/poly(N‐vinyl pyrrolidone) (PHA/PVP) blends were examined by using differential scanning calorimetry (DSC), high‐resolution solid‐state nuclear magnetic resonance (NMR) techniques, and thermogravimetric analysis (TGA). It was found that PHA is miscible with PVP, as shown by the existence of a single composition‐dependent glass transition temperature (T_g) in the whole composition range. The DSC results, together with the ¹³C crosspolarization (CP)/magic angle spinning (MAS)/high‐power dipolar decoupling (DD) spectra of the blends, revealed that there exist rather strong intermolecular interactions between PHA and PVP. The increase in hydrogen bonding and in T_g of the blends was found to broaden the line width of CH—OH carbon resonance of PHA. The measurement of the relaxation time showed that the PHA/PVP blends are homogeneous at least on the scale of 1–2 nm. The proton spin‐lattice relaxation in both the laboratory frame and the rotating frame were studied as a function of the blend composition, and it was found that blending did not appreciably affect the spectral densities of motion (sub‐T_g relaxation) in the mid‐MHz and mid‐KHz frequency ranges. Thermogravimetric analysis showed that PHA has rather good thermal stability, and the thermal stability of the blend can be further improved with increasing PVP content. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 237–245, 1999     

Polymer electrolyte membranes based on p‐toluenesulfonic acid doped poly(1‐vinyl‐1,2,4‐triazole): Synthesis,thermal and proton conductivity properties

Throughout this work, the synthesis, thermal as well as proton conducting properties of acid doped heterocyclic polymer were studied under anhydrous conditions. In this context, poly(1‐vinyl‐1,2,4‐triazole), PVTri was produced by free radical polymerization of 1‐vinyl‐1,2,4‐triazole with a high yield. The structure of the homopolymer was proved by FTIR and solid state ¹³C CP‐MAS NMR spectroscopy. The polymer was doped with p‐toluenesulfonic acid at various molar ratios, x = 0.5, 1, 1.5, 2, with respect to polymer repeating unit. The proton transfer from p‐toluenesulfonic acid to the triazole rings was proved with FTIR spectroscopy. Thermogravimetry analysis showed that the samples are thermally stable up to ～250 °C. Differential scanning calorimetry results illustrated that the materials are homogeneous and the dopant strongly affects the glass transition temperature of the host polymer. Cyclic voltammetry results showed that the electrochemical stability domain extends over 3 V. The proton conductivity of these materials increased with dopant concentration and the temperature. Charge transport relaxation times were derived via complex electrical modulus formalism (M*). The temperature dependence of conductivity relaxation times showed that the proton conductivity occurs via structure diffusion. In the anhydrous state, the proton conductivity of PVTri1PTSA and PVTri2PTSA was measured as 8 × 10^?4 S/cm at 150 °C and 0.012 S/cm at 110 °C, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1016–1021, 2010     

Solid‐state NMR characterizations on phase structures and molecular dynamics of poly(ethylene‐co‐vinyl acetate)

Solid‐state nuclear magnetic resonance spectroscopy and relaxation measurements, together with DSC, have been used to elucidate the structures and molecular dynamics in poly(ethylene‐co‐vinyl acetate) (EVA). It has been found that besides immobile orthorhombic and monoclinic crystalline phases, the third mobile crystalline phase (possibly the phase) of a considerable amount (36% of total crystalline phases) appears in the EVA samples, which forms during room‐temperature aging as a result of the secondary crystallization and melts at temperature somewhat higher than room temperature. Such a mobile crystalline phase has not only the well‐defined chemical shift of its own, but also has different molecular mobility from the orthorhombic phase. The mobile crystalline phase is characterized by the rapid relaxation of the longitudinal magnetization, which is caused by conventional spin‐lattice relaxation, while the slow relaxation of the longitudinal magnetization occurring in the orthorhombic phase is originated from the chain diffusion. In addition, the amorphous phase also contains two components: an interfacial amorphous phase and a melt‐like amorphous phase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2864–2879, 2006     

Synthesis and characterization of partially disulfonated hydroquinone‐based poly(arylene ether sulfone)s random copolymers for application as proton exchange membranes

Partially disulfonated hydroquinone (HQ)‐based poly(arylene ether sulfone) random copolymers were synthesized and characterized for application as proton exchange membranes. The copolymer composition was varied in the degree of disulfonation. The copolymers were characterized by ¹H NMR, Differential Scanning Calorimetry (DSC), and other analytical techniques. The copolymer with a 25% degree of disulfonation showed the best balance between water uptake and proton conductivity. The copolymers showed substantially reduced methanol permeability compared with Nafion® and satisfactory direct methanol fuel cell performance. The methanol selectivity improved significantly in comparison to Nafion® 117. At a given ionic composition, the HQ‐based system showed higher water uptake and proton conductivity than the biphenol‐based (BPSH‐xx) poly(arylene ether sulfone)s copolymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 384–391, 2009     

Synthesis and characterization of poly(arylene ether sulfone) copolymers with sulfonimide side groups for a proton‐exchange membrane

A sulfonimide‐containing comonomer derived from 4,4′‐dichlorodiphenylsulfone was synthesized and copolymerized with 4,4′‐dichlorodiphenylsulfone and 4,4′‐biphenol to prepare sulfonimide‐containing poly(arylene ether sulfone) random copolymers (BPSIs). These copolymers showed slightly higher water uptake than disulfonated poly(arylene ether sulfone) copolymer (BPSH) controls, but their proton‐conductivity values were very comparable to those of the BPSH series with similar ion contents. The proton conductivity increased with the temperature for both systems. For samples with 30 mol % ionic groups, BPSI showed less temperature dependence in proton conductivity and slightly higher methanol permeability in comparison with BPSH. The thermal characterization of the sulfonimide copolymers showed that both the acid and salt forms were stable up to 250 °C under a nitrogen atmosphere. The results suggested that the presumed enhanced stability of the sulfonimide systems did not translate into higher protonic conductivity in liquid water. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6007–6014, 2006     

Parameters affecting transition temperatures of poly(lactic acid‐co‐polydiols) copolymer‐based polyester urethanes and their shape memory behavior

A series of polyester urethanes (PEUs) comprising poly(lactic acid‐co‐polydiol) copolymers as a soft segment, 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol (BDO) as a hard segment were systematically synthesized. Soft segments, which were block copolymers of L ‐lactide (LA) and polydiols such as poly(ethylene glycol) and poly(trimethylene ether glycol), were prepared via ring opening polymerization. Glass transition temperatures (T_g) of the obtained PEUs were found strongly dependent on properties of copolymer soft segments. By simply changing composition ratio, type and molecular weight of polydiols in the soft segment preparation step, T_g of PEU can be varied in the broad range of 0–57°C. The synthesized PEUs exhibited shape memory behavior at their transition temperatures. PEUs with hard segment ratio higher than 65 mole percent showed good shape recovery. These findings suggested that it is important to manipulate molecular structure of the copolymer soft segment for a desirable transition temperature and design optimal soft to hard segment ratio in PEU for good shape recovery. Copyright © 2011 John Wiley & Sons, Ltd.     

A ladder coordination polymer based on Ca2+ and (4,5‐dicyano‐1,2‐phenylene)bis(phosphonic acid): crystal structure and solution‐state NMR study

The preparation of coordination polymers (CPs) based on either transition metal centres or rare‐earth cations has grown considerably in recent decades. The different coordination chemistry of these metals allied to the use of a large variety of organic linkers has led to an amazing structural diversity. Most of these compounds are based on carboxylic acids or nitrogen‐containing ligands. More recently, a wide range of molecules containing phosphonic acid groups have been reported. For the particular case of Ca²⁺‐based CPs, some interesting functional materials have been reported. A novel one‐dimensional Ca²⁺‐based coordination polymer with a new organic linker, namely poly[[diaqua[μ₄‐(4,5‐dicyano‐1,2‐phenylene)bis(phosphonato)][μ₃‐(4,5‐dicyano‐1,2‐phenylene)bis(phosphonato)]dicalcium(II)] tetrahydrate], {[Ca₂(C₈H₄N₂O₆P₂)₂(H₂O)₂]·4H₂O}_n, has been prepared at ambient temperature. The crystal structure features one‐dimensional ladder‐like _∞¹[Ca₂(H₂cpp)₂(H₂O)₂] polymers [H₂cpp is (4,5‐dicyano‐1,2‐phenylene)bis(phosphonate)], which are created by two distinct coordination modes of the anionic H₂cpp²⁻ cyanophosphonate organic linkers: while one molecule is only bound to Ca²⁺ cations via the phosphonate groups, the other establishes an extra single connection via a cyano group. Ladders close pack with water molecules through an extensive network of strong and highly directional O—H…O and O—H…N hydrogen bonds; the observed donor–acceptor distances range from 2.499 (5) to 3.004 (6) Å and the interaction angles were found in the range 135–178°. One water molecule was found to be disordered over three distinct crystallographic positions. A detailed solution‐state NMR study of the organic linker is also provided.     

Investigation into the ROMP copolymerization of peptide‐ and PEG‐functionalized norbornene derivatives

The ring‐opening metathesis polymerizations (ROMP), using RuCl₂ (PCy₃)₂CHPh, of a series of peptide‐functionalized norbornene derivatives have been investigated. Incorporation of a PEG‐monomer was found to prevent premature precipitation of polymer strands during the course of polymerization reactions and yield water compatible polymers in high conversions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3178–3190, 2007     

Synthesis of star‐shaped poly(D,L‐lactic acid‐alt‐glycolic acid)‐b‐poly(L‐lactic acid) with the poly(D,L‐lactic acid‐alt‐glycolic acid) macroinitiator and stannous octoate catalyst

Two types of three‐arm and four‐arm, star‐shaped poly(D,L ‐lactic acid‐alt‐glycolic acid)‐b‐poly(L ‐lactic acid) (D,L ‐PLGA50‐b‐PLLA) were successfully synthesized via the sequential ring‐opening polymerization of D,L ‐3‐methylglycolide (MG) and L ‐lactide (L ‐LA) with a multifunctional initiator, such as trimethylolpropane and pentaerythritol, and stannous octoate (SnOct₂) as a catalyst. Star‐shaped, hydroxy‐terminated poly(D,L ‐lactic acid‐alt‐glycolic acid) (D,L ‐PLGA50) obtained from the polymerization of MG was used as a macroinitiator to initiate the block polymerization of L ‐LA with the SnOct₂ catalyst in bulk at 130 °C. For the polymerization of L ‐LA with the three‐arm, star‐shaped D,L ‐PLGA50 macroinitiator (number‐average molecular weight = 6800) and the SnOct₂ catalyst, the molecular weight of the resulting D,L ‐PLGA50‐b‐PLLA polymer linearly increased from 12,600 to 27,400 with the increasing molar ratio (1:1 to 3:1) of L ‐LA to MG, and the molecular weight distribution was rather narrow (weight‐average molecular weight/number‐average molecular weight = 1.09–1.15). The ¹H NMR spectrum of the D,L ‐PLGA50‐b‐PLLA block copolymer showed that the molecular weight and unit composition of the block copolymer were controlled by the molar ratio of L ‐LA to the macroinitiator. The ¹³C NMR spectrum of the block copolymer clearly showed its diblock structures, that is, D,L ‐PLGA50 as the first block and poly(L ‐lactic acid) as the second block. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 409–415, 2002     

Cross‐linked polybenzimidazole membranes for high temperature proton exchange membrane fuel cells with dichloromethyl phosphinic acid as a cross‐linker

Phosphoric acid doped polybenzimidazole (PBI) membranes have been covalently cross‐linked with dichloromethyl phosphinic acid (DCMP). FT‐IR measurements showed new bands originating from bonds between the hydrogen bearing nitrogen in the imidazole group of PBI and the CH₂ group in DCMP. The produced cross‐linked membranes show increased mechanical strength, making it possible to achieve higher phosphoric acid doping levels and therefore higher proton conductivity. Oxidative stability is significantly improved and thermal stability is sufficient in a temperature range of up to 250°C, i.e. within the temperature range of operation of PBI‐based fuel cells. Copyright © 2008 John Wiley & Sons, Ltd.     

Combining poly (methacrylic acid‐co‐ethylene glycol dimethacrylate) monolith microextraction and octadecyl phosphonic acid‐modified zirconia‐coated CEC with field‐enhanced sample injection for analysis of antidepressants in human plasma and urine

A method based on poly (methacrylic acid‐co‐ethylene glycol dimethacrylate) monolith microextraction and octadecylphosphonic acid‐modified zirconia‐coated CEC followed by field‐enhanced sample injection preconcentration technique was proposed for sensitive CE‐UV analysis of six antidepressants (doxepin, clozapine, imipramine, paroxetine, fluoxetine and chlorimipramine) in human plasma and urine. A poly(methacrylic acid‐co‐ethylene glycol dimethacrylate) monolithic capillary column was introduced for the extraction of antidepressants from urine and plasma samples. The hydrophobic main chains and acidic pendant groups of the monolithic column make it a superior material for extraction of basic analytes from aqueous matrix. After extraction, the desorption solvent, which normally provided an excellent medium to ensure direct compatibility for field‐enhanced sample injection in CE, was analyzed by CE directly. By the use of alkylphosphonate‐modified zirconia‐coated CEC for separation of the basic compounds of antidepressants, high separation efficiency and resolution were achieved because that both hydrophobic interaction between analytes and alkylphosphonate‐modified zirconia coat and electrophoretic effect work on the separation of antidepressants. The best separation was achieved using a buffer composed of 0.3 M ammonium acetate (adjusted to pH 4.5 with 1 M acetic acid) and 35% ACN v/v, with a temperature and voltage of 20°C and 20 kV, respectively. By applying both preconcentration procedures, LODs of 11.4–51.5 and 3.7–17.0 μg/L were achieved for the six antidepressants in human plasma and urine, respectively. Excellent method of reproducibility was found over a linear range of 50–5000 μg/L in plasma and urine sample.     

Hydrophobically controlled self‐association of pH‐ and thermo‐sensitive triblock copolymers based on poly(acrylic acid‐co‐tert‐butyl acrylate) and poly(propylene oxide)

Aqueous solution properties of amphiphilic P(AA‐co‐tBA)‐b‐PPO‐b‐ P(AA‐co‐tBA) copolymers having various tBA contents are presented in this article. These copolymers show pH‐sensitive behavior depending on tBA/AA ratio. Hydrophobic interactions between tBA units leading to pH‐dependent macroscopic aggregates were evidenced by turbidimetry. The aggregation behavior of the PPO middle block was concealed in presence of tBA units. The formation of water‐soluble aggregated objects was characterized by Asymmetrical Flow Field Flow Fractionation (AsF4). By increasing tBA/AA ratio, we observed an increase of aggregates size as well as a reduction of the critical concentration aggregation. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1944–1949     

Synthesis of original para‐sulfonic acid aminoethylthioethylbenzenesulfonic by telomerization,and its grafting onto poly(VDF‐co‐HFP) copolymers for proton exchange membrane for fuel cell

The synthesis of a novel aromatic sulfonic acid bearing an amino function H₂N? C₂H₄? S? C₂H₄? C₆H₄? SO₃Na ( 1 ) from the radical addition of mercaptoethylamine hydrochloride onto styrene sodium sulfonate, and its subsequent grafting onto poly(vinylidene fluoride‐co‐hexafluoropropylene), poly(VDF‐co‐HFP), copolymer are presented. First, the radical telomerization, carried out under radical conditions and in water, led to various products [monoadduct ( 1 ), multiadducts, and polymers], the amounts of which depend on the experimental conditions and [mercaptan]₀/[monomer]₀ initial molar ratio (R₀). An R₀ ≥ 1 led to the monoadduct ( 1 ) only and achieved in ～85% yield. The zwitterionic isomer was obtained mainly and its chemical modification was possible to get an original aromatic sodium sulfonate containing an amino end group. A kinetic study of the telomerization was presented for R₀ < 1. Thermogravimetric analysis of the telomer showed that this compound was stable up to 200 °C. Second, the grafting of ( 1 ) onto poly(VDF‐co‐HFP) copolymer was also investigated. Such a grafting proceeded as expected by a classic mechanism of grafting of amines. Molar percentages of grafted telomer were assessed by ¹H NMR spectroscopy and by elemental analysis. Ion exchange capacity (IEC) values of the membranes were deduced from the mol % grafted telomer. Scanning electron microscopy pictures showed a good homogeneity in the cross‐section of membranes, and energy dispersive X‐ray evidenced that all SO₃Na groups of the grafted amine were changed into SO₃H after treatment with concentrated HCl. Method involving an impedance analyzer, working at increasing high frequencies was used to assess the protonic conductivities, σ. These values were lower than that of Nafion117^®, but σ increased with the IEC to 0.4 mS/cm at room temperature and 95% relative humidity. Water and methanol uptakes were also assessed, and it was shown that σ increased when water uptakes increased. Membranes started to decompose from 170 °C under air. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 121–136, 2009