Electrochemical synthesis and properties of poly(3‐methylthiophene): Novel synthesis of poly(3‐methylthiophene) with pentachlorostannate and hexachloroantimonate

Poly(3‐methylthiophene) (P3‐MeT) doped with different anions were prepared electrochemically in the presence of tetraalkylammonium salts. The new poly(3‐methylthiophene) SnCl and SbCl (P3‐MeT SnCl₅ and P3‐MeT SbCl₆) were prepared electrochemically using tetra‐n‐butylammonium pentachlorostannate and tetra‐n‐butylammonium hexachloroantimonate as the supporting electrolytes. The effect of current density, salt concentration, reaction temperature, and the nature of solvents on the polymer yield and polymer conductivities have been investigated. Cyclic voltammetry of poly(3‐methylthiophene) has been examined at platinum electrode in 1,2‐dichloroethane medium containing n‐Bu₄NSnCl₅, Bu₄NSbCl₆, and Bu₄NClO₄ as the supporting electrolytes in the range of −1.0 to 1.7 V versus SCE in the presence and absence of 3‐methylthiophene. Electrical conductivity, magnetic susceptibility measurements, and structural determination by elemental analysis and infrared studies were also made. Scanning electron microscopy revealed a globular, branched, fibrous and a spongy, fibrous morphology of poly(3‐methylthiophene) SnCl, ClO, and SbCl, respectively. The thermal analysis of the polymers was also investigated. Possible causes for the observed lower conductivity of these polymers have also been discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 91–102, 1999     

Cationic grafting from carbon black. III. Grafting of polyesters from carbon black by ring-opening polymerization of lactones initiated by CO+ClO groups on carbon black

It was found that the cationic ring-opening polymerization of δ-valerolactone (VL), ε-caprolactone (CL), and β-propiolactone (PL) was initiated by carbon black containing CO⁺ClO groups, which were introduced by the reaction of COCl groups with AgClO₄. The polyester was propagated from CO⁺ClO groups and effectively grafted onto carbon black surface. The polymerizability of these lactones by CO⁺ClO groups decreased in the following order: VL > CL > PL. The increasing temperature of the polymerization caused an increase in the rate of the chain transfer reaction of the growing chains and brought about the decrease of grafting ratio of polyester onto carbon black.     

Use of amidoximated acrylonitrile/N‐vinyl 2‐pyrrolidone interpenetrating polymer networks for uranyl ion adsorption from aqueous systems

Poly(N‐vinyl 2‐pyrrolidone) (PVP)/acrylonitrile (AN) interpenetrating polymer networks (IPNs) were synthesized and amidoximated for the purpose of uranyl ion adsorption. The adsorption of amidoximated IPNs was studied from different uranyl ion solutions (850, 1000, 1200, 1400, and 1600 ppm). The result of all our adsorption studies showed that the bonding between UO‐amidoxime groups complied with the Langmuir‐type isotherm. The adsorption capacity was found as 0.75 g UO/g dry amidoximated IPN. In order to increase the UO ion adsorption capacity the amidoximated IPN was treated with alkali, but no significant increase could be observed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2324–2329, 2001     

Mass transport process for the adsorption of Cr(VI) onto water‐insoluble cationic starch synthetic polymers in aqueous systems

Dynamic adsorption behaviors between Cr(VI) ion and water‐insoluble amphoteric starches was investigated. It was found that the HCrO ion predominates over the initial pH ∼ 2–4, the CrO ion predominates over the initial pH ∼ 10–12, and both ions coexist over the initial pH ∼ 6–8. The sorption process occurs in two stages: the external mass transport process occurs in the early stage and the intraparticle diffusion process occurs in the long‐term stage. The diffusion coefficient of the early stage (D₁) is larger than that of the long‐term stage (D₂) for the initial pH 4 and pH 10. The diffusion rate of HCrO ion is faster than that of CrO ion for both processes. The D₁ and D₂ values are ∼ 1.38 × 10⁻⁷–10.1 × 10⁻⁷ and ∼ 0.41 × 10⁻⁷–1.60 × 10⁻⁷ cm² s⁻¹, respectively. The ion diffusion rate in both processes is concentration dependent and decreases with increasing initial concentration. The diffusion rate of HCrO ion is more concentration dependent than that of CrO ion for the external mass transport process. In the intraparticle diffusion process, the concentration dependence of the diffusion rate of HCrO and CrO ions is about the same. The external mass transport and intraparticle diffusion processes are endothermic and exothermic, respectively, for the initial pH 4 and pH 10. The k_d values of the external mass transport and intraparticle diffusion processes are ∼ 15.20–30.45 and ∼ −3.53 to −12.67 kJ mol⁻¹, respectively. The diffusion rate of HCrO ion is more temperature dependent than that of CrO ion for both processes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2409–2418, 1999     

Synthesis and electrochemistry of grafted copolymers of cellulose with 4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone,and 9-vinylcarbazole

Some new cellulosic materials, suitable for the adsorption of noble metal ions, were syn-thesized by chemical and electrochemical modification of cellulose. The polymerizable groups were introduced in cellulose with ∼ 80% yield of substitution by esterification with acryloyl chloride. The vinyl monomers (4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone, and 9-vinylcarbazole) were readily grafted into cellulose acrylate via radical polymerization in acetonitrile. The grafted copolymers of cellulose with 4-vinylpyridine and 4-vinylimidazole were reacted with methyl iodide and the corresponding 1-methylpyridinium iodide ( 6 ) and 3-methylimidazolium iodide ( 7 ) copolymers of cellulose were obtained. Copolymers 6 and 7 were transformed into new polymeric regents, differing in anions (ClO, CF₃COO⁻, NO, p-TsO⁻, BF, PF) by using a supporting electrolyte carrying the desired anions through the ion-exchange-electrochemical oxidation of the released iodide at a controlled anodic potential. © 1996 John Wiley & Sons, Inc.     

Elastic characteristics of branched-network polymers

The computed dependencies of elastic characteristics of branched-network polymers were obtained on the basis of the Takayanagi series model. The moduli ratio (λ) for branched-network and branched polymers increases as a result of an increase of the moduli ratio of network and branched phases (E/E) and the network phase fraction (V_net). The λ-increase as a function of V_net is larger than in the case of the E/E dependence. On the basis of computed dependencies, the experimental results for the radiation crosslinked SBS block copolymer were considered. The experimental results agree with the computed de-pendencies for the hetergeneous branched-network polymers with E/E ≈︁ 20. The influence of entanglements on the elastic characteristics of branched-network polymers is discussed. © 1996 John Wiley & Sons, Inc.     

Intrinsic birefringence of nylon 6

Different values are reported in the literature for the intrinsic birefringence of the crystalline (Δn) and the amorphous (Δn) phases in nylon 6. Mostly, these values have either been determined by extrapolation (and then it is assumed that Δn = Δn) or calculated theoretically. In this study, intrinsic birefringence values Δn and Δn for nylon 6 were determined using the Samuels two-phase model which correlates sonic modulus with structural parameters. Three series of fiber samples were used: (1) isotropic samples of different degrees of crystallinity for estimation of E and E moduli at two temperatures. The following modulus values were obtained: 1.62 × 10⁹ and 6.66 × 10⁹ N/m² for 28.5°C, and 1.81 × 10⁹ and 6.71 × 10⁹ N/m² for ?20°C; (2) anisotropic, amorphous fiber samples for estimation of Δn = 0.076 and E = 1.63 × 10⁹ N/m² at 28.5°C; (3) semicrystalline samples of various draw ratios for estimations of Δn = 0.089 and Δn = 0.078. All measurements were carried out with carefully dried samples to avoid erroneous results caused by moisture.     

Several features of vinyl chloride–diallyl phthalate suspension copolymerization

Vinyl chloride–diallyl phthalate (VC–DAP) suspension copolymerization was carried out in a 5‐L autoclave and 200‐mL stainless steel vessel at 45°C. The apparent reactivity ratios of VC–DAP suspension copolymerization system were calculated as r_VC = 0.77 and r_DAP = 0.37. It shows that VC–DAP copolymer contains no gel when the feed concentration of DAP (f) is lower than a critical concentration (f_cr, inside the range of 0.466–0.493 mmol/mol VC at 80–85% conversion), the polymerization degree (DP) of copolymer increases with the increase of f and conversion. VC–DAP copolymer is composed of gel and sol fractions when f is larger than f_cr. The DP of sol fraction decreases as f increases, but the gel content and the crosslinking density of gel increase. The gel content also increases as conversion increases. The results also show that the index of polydispersity of molecular weight of sol changes with f, a maximum value appears when f is close to f_cr. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 156–162, 2000     

Electrochemical preparation and properties of polypyrrole and its blend with poly(vinyl sulfonate) doped with perchlorate anions

In this article, we report polypyrrole (PPy)/poly(vinyl sulfonate) (PVS) and PPy/perchlorate (ClO) composite films generated by the electrochemical oxidation of pyrrole on a glassy carbon electrode (GCE) in an aqueous solution. The response of the produced films to an applied potential at 0.7 V was obtained by a cyclic voltammetry study in acetonitrile media. The films were significantly similar in their electrochemical behavior when ClO ions doped during the redox process. We concluded that with an increasing number of cycles, the anodic current increased because the number of the electroactive participants transported in the copolymer matrix was increased. Theoretical studies based on the Nernst and Butler–Volmer equations indicated that the ClO ion was transported during the oxidation/reduction process of the PPY/PVS and PPY/ClO films. The produced films were characterized further by means of IR spectroscopy, electrochemical impedance spectroscopy, and scanning electron microscopy to verify that the anion of ClO was doped into the copolymer matrix as well. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of anionic form on thermal degradation of TMAHP–cellulose

Trimethylammoniumhydroxypropyl (TMAHP)–cellulose in 10 anionic forms (F^?, Cl^?, Br^?, I^?, HSO, NO, OH^?, HCO, H₂PO, CH₃COO^?) was prepared, and the influence of each anion on thermal degradation in inert atmosphere was studied. With the help of dynamic and isothermal thermogravimetry (TG) it was found that H₂PO ions had the greatest retarding effect on TMAHP–cellulose degradation. From the values of rate constants it can be seen that all ionic forms of TMAHP–cellulose have the starting rate of thermal degradation greater than unmodified cellulose. The calculated values of activation energy of thermal degradation for different ionic forms are decreasing in following sequence: H₂PO > F^? > NO > I^? > Br^? > HCO > Cl^? > HSO > OH^? > unmodified cellulose > CH₃COO^?. From the results of pyrolyse measurements in combination with gas chromatography and mass spectrometry (Py–GC–MS) it follows that the products of the elimination of quarternary ammonium salts are trimethylamine, 3-hydroxy-2-propanone, and, in the case of OH^? form, water. In all other ionic forms the third product is the corresponding acid.     

Forced oscillations in continuous flow stirred tank reactors with nonlinear step growth polymerization

The self-step growth polymerization of RA_f monomers in homogeneous, continuous flow stirred tank reactors (HCSTRs) is simulated under conditions of periodic feed concentration (with frequency ω and amplitude α). By having periodic operation, the polydispersity index of the polymer is found to increase by about 35% over the values at steady state. Periodic operation of HCSTRs is found to lead to gelation only for certain values of the frequency and the dimensionless residence time τ^*. Gelling envelopes have been obtained to give conditions under which HCSTRs should be operated. These envelopes can be described in terms of two critical dimensionless residence times, τ and τ such that nongelling operation is always ensured when τ^* < τ. For τ^* > τ, periodic operation always leads to gelation, and HCSTRs cannot be used. For τ < τ^* < τ, the gelling behavior is found to depend on the functionality f, amplitude α, and the dimensionless residence time τ^*.     

Effect of pH,ionic strength,and temperature on uranyl ion adsorption by poly(N‐vinyl 2‐pyrrolidone‐g‐tartaric acid) hydrogels

Poly‐electrolyte N‐vinyl 2‐pyrrolidone‐g‐tartaric acid (PVP‐g‐TA) hydrogels with varying compositions were prepared in the form of rods from ternary mixtures of N‐vinyl 2‐pyrrolidone/tartaric acid/water. The effect of external stimuli, such as the solution pH, ionic strength, and temperature, on uranyl adsorption by these hydrogels was investigated. Uranyl adsorption capacities of the hydrogels were determined to be 53.2–72.2 (mg UO/g dry gel) at pH 1.8, and 35.3–60.7 (mg UO/g dry gel) at pH 3.8, depending on the amount of TA in the hydrogel. The adsorption studies have shown that the temperature and the ionic strength of the swelling solution also influence uranyl ion adsorption by PVP‐g‐TA hydrogels. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2219–2226, 2000     

Morphological studies of the modified materials: Low-density polyethylene/poly(acrylic acid)/europium(III) and low-density polyethylene/poly(acrylic acid)/uranyl ion

The morphology of low-density polyethylene (LDPE) modified by in situ sorption and thermal polymerization of acrylic acid (AA) in the matrix was examined. The microstructure of the LDPE/poly(acrylic acid) (PAA) materials after Eu³⁺ and UO ion exchange was investigated. The phase behavior of these materials was analyzed using X-ray diffraction, scanning electron microscopy (SEM), and thermal measurements (DSC). The X-ray dif-fraction studies showed that PAA is located at amorphous region of the matrix. The LDPE/PAA surface, as investigate by SEM, was apparently homogeneous before and after Eu³⁺ and UO ion exchange, respectively. Two T_g values were found for the LDPE/PAA material before and after Eu³⁺ ion exchange. Also, three and four T_g values were found for LDPE/PAA after UO ion exchange depending on the amount of UO in the modified matrix. This indicates microphase domains in the LPDE/PAA-, LPDE/PAA/Eu³⁺-, and LPDE/PAA/UO -modified materials, although a lack of visible phase separation in the micrographs was observed. © 1996 John Wiley & Sons, Inc.     

The influence of the equilibrium melting temperature on the supermolecular morphology of several polymers

At a constant isothermal crystallization temperature (T_c), the crystalline morphologies of several polymers have been found to be a function of the melt-liquid temperature (T₁). At a constant T_c below a critical crystallization temperature (T [about 0.9 T(K)], a transition from a nonspherulitic to a spherulitic morphology occurs when the melt liquid is heated above a melt-liquid transition temperature, (T_lt) [approximately 1.03 T_m (K)], where T_m is the observed melting temperature of the sample. The melt-liquid transition temperature, T_lt, which experimentally affects the visible morphology of a semicrystalline polymer, is apparently indistinguishable from the thermodynamic melting temperature, T, determined by the Hoffman-Weeks procedure. The X-ray powder diffraction patterns of spherulitic and nonspherulitic morphologies were identical, independent of the heating-cooling cycle. This suggests that the transition that occurs at T_It does not affect the arrangement of polymer molecules in the crystallite, but only the manner in which the crystallites are arranged in the supermolecular morphology. The evidence suggests, at least for the polymers studied, that a residual order exists in the melt until the T or T_It of the particular polymer is reached. © 1993 John Wiley & Sons, Inc.     

The viscoelastic properties of rubber–resin blends. III. The effect of resin concentration

The viscoelastic properties of a rubber–resin blend, which influences performance of the blend as a pressure-sensitive adhesive, depend upon the structure of the resin as well as its molecular weight. The effect of the concentration of a compatible resin in the blend was examined using a mechanical spectrometer. Four types of resins were used. These are the rosin esters, polyterpenes, pure monomer resins such as polystyrene and poly(vinyl cyclohexane), and petroleum stream resins. Each was examined in blends with both natural rubber and styrene–butadiene rubber over a range of concentrations. It is shown that the temperature of the tan δ peak for compatible systems can be predicted by the Fox equation, T = W₁T + W₂T, where W₁ and W₂ are the weight fractions of the resin and rubber, respectively, and the T_g's are the tan δ peak temperatures in K. The plateau modulus G for a blend can be identified as the G′ value in the rubbery plateau at the point where tan δ is at a minimum. The relationship between G and G, the plateau modulus for the undiluted elastomer, is shown to be proportional to the volume fraction of the elastomer raised to the 2.3–2.4 power for natural rubber with six different compatible resins. The exponent for styrene–butadiene rubber is 2.5–2.6 with four different resins. Using these relationships, both the tan δ peak temperature and plateau modulus can be predicted for a rubber–resin system from data on the unmodified elastomer and on one typical rubber–resin blend.     

Synthesis,characterization, and thermodynamic properties of poly(3‐mesityl‐2‐hydroxypropyl methacrylate)

Poly(3‐mesityl‐2‐hydroxypropyl methacrylate) (PMHPMA) was synthesized in a 1,4‐dioxane solution with 2,2′‐azobisisobutyronitrile as the initiator at 60°C. The homopolymer and its monomer were characterized with ¹H‐ and ¹³C‐NMR, Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, size exclusion chromatography, and elemental analysis techniques. According to size exclusion chromatography analysis, the number‐average molecular weight, weight‐average molecular weight, and polydispersity index of PMHPMA were 65,864 g/mol, 215,375 g/mol, and 3.275, respectively. According to thermogravimetric analysis, the carbonaceous residue value of PMHPMA was 14% at 500°C. The values of the specific retention volume, adsorption enthalpy, sorption enthalpy, sorption free energy, sorption entropy, partial molar free energy, partial molar heat of mixing, weight fraction activity coefficient of solute probes at infinite dilution (Ω), and Flory–Huggins interaction parameter (χ) were calculated for the interactions of PMHPMA with selected alcohols and alkanes by the inverse gas chromatography method at various temperatures. According to Ω and χ, selected alcohols and alkanes were nonsolvents for PMHPMA at 423–453 K. Also, the solubility parameter of PMHPMA (δ₂) was found to be 24.24 and 26.33 (J/cm³)^0.5 from the slope and intercept of (δ/RT) ? χ/V₁ = (2δ₂/RT)δ₁ ? δ/RT at 443 K, respectively [where δ₁ is the solubility parameter of the probe, V₁ is the molar volume of the solute, T is the column temperature (K), and R is the universal gas constant]. The glass‐transition temperature of PMHPMA was found to be 386 and 385 K by inverse gas chromatography and differential scanning calorimetry techniques, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 101–109, 2006     

Study of crosslinking density in polydimethylsiloxane networks by DSC

A calorimetric study for estimating crosslinking densities of polydimethylsiloxane (PDMS) networks is presented. It involves the experimental determination of the heat capacities of the polymer with (C) and without (C) crosslinking. The theoretical basis of the method is described as well as the procedure used for the determination of the C_ps. The crosslinking densities of PDMS networks, determined by absorbency (swelling) measurments, using the Flory-Rehner equation, and by the method described here, are compared. The PDMS, obtained by the anionic synthesis of octamethylcyclotetrasiloxane, was analyzed by gel permeation chromatography and infrared spectroscopy. Separate samples of the polymer were further crosslinked at different network densities. The C_ps and the thermal stabilities were determined by DSC and TGA, respectively. The results indicate that the crosslinking density ratios of the polymer networks calculated by the relation ΔC/C are in reasonable agreement with those obtained from absorbency measurements. The crosslinking density can also be obtained from heat capacity measurments if the density of the network is known at the temperature that ΔC_p is obtained. © 1995 John Wiley & Sons, Inc.     

Polyzwitterion-to-polyampholyte transition using pH-responsive cycloterpolymers of diallyldimethylammonium chloride, (N,N-diallylammonio)methanecarboxylate and sulfur dioxide

The cycloterpolymerizations of varying proportions of diallyldimethylammonium chloride (I) and N,N-Diallyl-N-carboethoxymethylammonium chloride (II) in the presence of sulfur dioxide afforded a series of cationic (+) polyelectrolytes (CPEs) (III) in excellent yields. CPEs, upon acidic hydrolysis of the ester functionalities of the repeating units of II, resulted in the formation of cationic/zwitterionic (+/±) polymers (IV). pH-responsive zwitterionic units of ammonioethanoate (NH⁺CH₂CO) (having unquenched valency of nitrogen) in IV was converted to its anionic counterparts (NCH₂CO) by treating with equivalent amount of NaOH to give cationic/anionic i.e., ampholytic (+/−) polymers (V) with a charge symmetry or asymmetry arising out of either excess of cationic or anionic centers. The transformations of III to IV to V have thus provided an opportunity to study the effects of the polyelectrolyte-to-polyzwitterion-to-polyampholyte transitions on the solution properties of these polymers. Basicity constants of the carboxylate group (NH⁺CH₂CO) in IV as well as the amine group (NCH₂CO) in V were found to be “apparent” and as such follow the modified Henderson–Hasselbalch equation. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Gas permeabilities of poly(trimethylsilylpropyne) membranes surface modified with CF4 plasma

Surface fluorination of poly(trimethylsilylpropyne) (PTMSP) membranes by CF₄ plasma was studied. The surface fluorination of the membranes was carried out in an atmosphere of CF₄ in a capacitively coupled discharge apparatus with external electrodes. Dramatic increase in selectivity (P/P) was observed. The effect of fluorination conditions such as duration of treatment and discharge power on the permeabilities of the membranes was studied. X-ray photoelectron spectrometric data of modified PTMSP membranes showed a drastic alternation in the surface layer. The P and P/P of the membranes were observed to be dependent on the F/C atomic ratio. At F/C > 1, the P/P value of the membranes could be more than four. © 1993 John Wiley & Sons, Inc.