Competitive adsorption between an AMPS®‐based fluid loss polymer and Welan gum biopolymer in oil well cement

Water‐soluble 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS®)‐based copolymers are commonly used to provide water retention (fluid loss control) for oil well cement slurries. Here, the fluid loss performance of a CaAMPS®‐N,N‐dimethylacrylamide copolymer (CaAMPS®‐co‐NNDMA) in the presence of Welan gum, an anionic microbial biopolymer produced by anaerobic fermentation using Alcaligenes ATCC 31555 bacteria was investigated at 80°C. Welan gum is used to control unwanted free water development at the surface of the cement slurry. The effectiveness of CaAMPS®‐co‐NNDMA fluid loss additive (FLA) solely relies on its high adsorption onto the positively charged surfaces of cement hydrates. Adsorption of the FLA is, however, perturbed by Welan gum. This anionic polysaccharide competes with CaAMPS®‐co‐NNDMA for adsorption sites on the cement surface. This effect is surprising because in cement pore solution, Welan gum exhibits a much lower specific anionic charge amount than CaAMPS®‐co‐NNDMA. The reason is that Welan gum possesses carboxylate functionalities, which are much stronger anchor groups than the sulfonate groups present in CaAMPS®‐co‐NNDMA. The superiority of the carboxylate groups regarding their affinity to the mineral surface, which possesses insufficiently coordinated Ca atoms is confirmed by a higher calcium binding capability for Welan gum than for the FLA. Thus, Welan gum can reduce effectiveness of CaAMPS®‐co‐NNDMA as fluid loss agent by preventing its adsorption or through displacement of already adsorbed FLA molecules from the surface of cement. In multiadmixture systems, which are commonly used in oil well cement, concrete or mortars, competitive adsorption between different additives for surface sites can negatively impact the performance of these additives. Understanding the reasons behind can help to develop more effective admixture systems. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Modification of the molar anionic charge density of acetone–formaldehyde–sulfite dispersant to improve adsorption behavior and effectiveness in the presence of CaAMPS®‐co‐NNDMA cement fluid loss polymer

Sulfonated aldol polycondensates were synthesized from acetone, formaldehyde, and different amounts of sodium sulfite, resulting in polymers with varying degrees of sulfonation (DS). The anionic charge amount of these macromolecules measured by polyelectrolyte titration decreased with lower DS. The effectiveness of the acetone–formaldehyde–sulfite (AFS) polycondensates as cement dispersant was found to depend on the amount of polymer adsorbed on cement. AFS adsorption decreases with lower DS. Interaction and compatibility between AFS and CaAMPS®‐co‐NNDMA fluid loss additive was studied by formulating binary additive systems composed of one of the modified AFS polymers and CaAMPS‐co‐NNDMA. At high DS, AFS adsorbs strongly and prevents CaAMPS‐co‐NNDMA from adsorbing in sufficient amounts on the cement surface. The result is poor fluid loss control of the cement slurry. AFS polymers with lower DS, however, allow simultaneous adsorption of both polymers in sufficient quantities to provide good fluid loss control and low rheology at the same time. Thus, effectiveness of both additives was retained. Obviously, effectiveness of such multi‐admixture systems depends on the adjustment of the adsorption behavior of the individual components relative to each other. Molar anionic charge density of the polymers was found to be a major parameter influencing their relative adsorption behavior. The AFS polymer with DS = 0.2 possesses a molar anionic charge density comparable to CaAMPS‐co‐NNDMA. Thus, when admixtures with similar molar anionic charge densities are used, the performance of one component is not negatively influenced by the other. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of high temperature and the role of sulfate on adsorption behavior and effectiveness of AMPS®‐based cement fluid loss polymers

The fluid loss control performance of 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS®)‐based copolymers added to cement slurries was studied at 27 and 100°C, respectively. It was found that effectiveness of these fluid loss additives solely relies on achievement of a high adsorbed amount on the surface of cement. At elevated temperature (100°C), CaAMPS®‐N,N‐dimethyl acrylamide copolymer (CaAMPS®‐co‐NNDMA) exhibits reduced adsorption and hence decreased fluid loss control of the cement slurry. The reason behind this behavior is poor calcium binding capability of the sulfonate anchor groups, which coordinate with calcium atoms present on the mineral surface. Whereas, an increase in the sulfate concentration present in cement pore solution instigates partial coiling of CaAMPS®‐co‐NNDMA and causes only a slight influence on the performance of this copolymer. The elevated sulfate content results from thermal degradation of ettringite, a cement hydrate mineral produced during the early stages of cement hydration. Incorporation of minor amounts (～ 1.3 mol %) of maleic anhydride into this copolymer produces a terpolymer, which exhibits higher and more stable adsorption, even at high temperature. This effect is owed to the presence of homopolymer blocks of polycarboxylates distributed along the polymer trunk. On mineral surfaces, they present much stronger anchor groups than sulfonate functionalities, as evidenced by their higher calcium binding capability. Consequently, fluid loss performance of CaAMPS®‐co‐NNDMA‐co‐MA is little affected by temperature. Understanding the influence of temperature on the physicochemical interactions occurring between additives and the mineral surface can help to design more effective admixtures suitable for high temperature applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Carbon‐13 nuclear magnetic resonance investigation of styrene–α‐methylstyrene copolymers

A copolymer based on α‐methylstyrene (AMS) was investigated by nuclear magnetic resonance (NMR). The styrene‐co‐α‐methylstyrene (SAMS) was analyzed by solution and solid‐state NMR techniques. Three copolymers of SAMS with different compositions presented a particular behavior. The solution results showed the copolymer microstructure and the AMS content. The carbon‐13 spectra of SAMS C indicated that the AMS CH₃ signal was detected at three distinct chemical shifts, because of the different comonomer‐sequences distribution. The proton spin–lattice relaxation time in the rotating frame (Tρ) parameter was chosen because it permits the evaluation of changes in the molecular mobility. The values of Tρ found for the copolymers confirmed the random distribution in the samples. The copolymer with a low quantity of AMS (1.7%), when analyzed by this relaxation parameter, showed lower values that were interpreted as an antiplasticization effect. The SAMS copolymer with a higher AMS quantity showed a plasticization effect. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 261–266, 2001     

Adsorption of a gold‐iodide complex (AuI2−) onto cellulose acetate‐polyaniline membranes: Equilibrium experiments

The adsorption of AuI complex onto acetate cellulose‐polyaniline membranes was investigated. Kinetic experiments showed a rapid adsorption of this complex, which was attributed to an ion‐exchange mechanism. Equilibrium adsorption results were represented by the Langmuir model, showing a correlation coefficient of 0.9852. Langmuir parameters K and Q_m were found to be 0.2937 L mg^?1 and 1.2394 mg g^?1, respectively. Approximately 94% of AuI was adsorbed when a solid/liquid ratio of 40 g L^?1 (grams of membrane/ liter of solution) was used. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Working mechanism of a high temperature (200°C) synthetic cement retarder and its interaction with an AMPS®‐based fluid loss polymer in oil well cement

A copolymer comprising of 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS®) and itaconic acid (molar ratio 1 : 0.32) was synthesized by aqueous free radical polymerization and probed as high temperature retarder for oil well cement. Characteristic properties of the copolymer including molar masses (M_w and M_n), polydispersity index and anionic charge amount were determined. The copolymer possesses a M_w of ～ 2 × 10⁵ g/mol and is highly anionic. HT/HP consistometer tests confirmed effectiveness of the retarder at temperatures up to 200°C. The working mechanism of NaAMPS®‐co‐itaconic acid was found to rely exclusively on its huge calcium binding capacity (5 g calcium/g copolymer). It reduces the amount of freely dissolved, nonbound calcium ions present in cement pore solution and thus hinders the growth of cement hydrates because of lack of calcium. The value for the calcium binding capability is 46 times higher than the stoichiometric amount per ? COO^? functionality. Consequently, calcium also coordinates to other donor atoms present in the retarder. NaAMPS®‐co‐itaconic acid also adsorbs onto cement, as was evidenced by TOC analysis of cement filtrates, zeta potential measurement and decreased rheology of cement pastes. However, adsorption plays no role in the retarding mechanism of this copolymer. Combination of NaAMPS®‐co‐itaconic acid retarder with a common CaAMPS®‐co‐NNDMA fluid loss additive (FLA) revealed that competitive adsorption on cement between these two admixtures occurs. The retarder fills interstitial adsorption sites on cement located between those occupied by the larger FLA molecules. In consequence, fewer amounts of CaAMPS®‐co‐NNDMA can adsorb and its effectiveness is reduced. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

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     

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     

Evaluation of EVA–PVAc blend behavior by 1‐D and 2‐D solid‐state NMR

Ethylene‐co‐vinyl acetate and poly(vinyl acetate) blends were prepared in different proportions by melting in a HAAKE Rheomix mixer. The blends were prepared at a fixed temperature, rotation rate, and processing time. High‐resolution solid‐state nuclear magnetic resonance was chosen to characterize the blends with respect to structure–mobility–compatibility employing magic angle spinning with cross polarization and high‐power hydrogen decoupling and the measurements of the proton spin–lattice relaxation time in the rotating frame (Tρ). The miscibility between polymer chains was also studied by two‐dimensional ¹H–¹³C shift correlation (HETCOR). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 221–226, 1999     

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.     

Synthesis,effectiveness, and working mechanism of humic acid‐{sodium 2‐acrylamido‐2‐methylpropane sulfonate‐co‐N,N‐dimethyl acrylamide‐co‐acrylic acid} graft copolymer as high‐temperature fluid loss additive in oil well cementing

Monomers of 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS®), N,N–dimethyl acrylamide (NNDMA) and acrylic acid (AA) were grafted on humic acid as backbone by aqueous free radical copolymerization in such a manner that a graft copolymer possessing lateral terpolymer chains was obtained. Molar ratios between AMPS®, NNDMA, and AA were found to be 1 : 1.54 : 0.02 and the ratio between backbone and graft chain was 20 : 80 wt %. The synthesized fluid loss additive (FLA) was characterized by size exclusion chromatography (SEC), charge titration, and Brookfield viscometry. Thermogravimetric and SEC analysis revealed stretched backbone worm architecture for the polymer whereby humic acid constitutes the backbone decorated with lateral graft chains. Grafting was confirmed by SEC data (R_g) and by ineffectiveness of a blend of AMPS®‐NNDMA‐AA copolymer with humic acid. Their performance as high temperature FLA was studied at 150°C by measuring static filtration properties of oil well cement slurries containing 35% bwoc of silica fume and 1.2% bwoc AMPS®‐co‐itaconic acid retarder. At this temperature, 1.0% bwoc graft copolymer achieves API fluid loss value of 40 mL, thus confirming high effectiveness. The graft copolymer viscosifies cement slurries less than other common synthetic FLAs. The working mechanism of the graft copolymer was found to rely on adsorption onto surface of hydrating cement, as was evidenced by adsorption and zeta potential measurements. Adsorption is hardly affected by temperature and results in constriction of the filter cake pores. The study provides insight into performance of cement additives under the harsh conditions of high temperature and high pressure. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Fundamental studies on a new series of SPSEBS‐PVA‐QPSEBS bipolar membrane: Membrane preparation and characterization

A sulfonated polystyrene ethylene butylene polystyrene (SPSEBS)‐poly(vinyl alcohol) (PVA)‐Quaternized polystyrene ethylene butylene polystyrene (QPSEBS) bipolar membrane (BPM) was prepared by lamination method using PSEBS as the starting material, the functionalization of which was modified by sulfonation and amination while PVA was used as the intermediate layer to enhance the water splitting efficiency. The cross section view of SPSEBS‐PVA‐QPSEBS BPM was studied by SEM. Fourier transform infra‐red spectroscopy (FTIR) studies indicated that the prepared BPM contained –SO, –NR, and –C‐N functional groups. The thermal stability of the prepared BPM was studied by thermogravimetric analysis (TGA). Some of the BPM characteristics results showed that the co‐ion fluxes was greater for t(0.065) when compared with t(0.051) along with a water splitting capacity value of 0.88 for SPSEBS‐PVA‐QPSEBS BPM. The water dissociation flux was 2.8 × 10^?5 mol/m²/s and 2.2 × 10^?5 mol/m²/s for the acid (H⁺) and base (OH^?), respectively. The other essential current‐voltage characteristics and permeate flux across the membrane were also evaluated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci 2013     

Atom‐transfer radical polymerization of methyl methacrylate with α,α′‐dichloroxylene/CuCl/N,N,N′,N″,N″‐pentamethyldiethylenetriamine initiation system under microwave irradiation

The atom‐transfer radical polymerization (ATRP) of methyl methacrylate (MMA), using α,α′‐dichloroxylene as initiator and CuCl/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as catalyst was successfully carried out under microwave irradiation (MI). The polymerization of MMA under MI showed linear first‐order rate plots, a linear increase of the number‐average molecular weight with conversion, and low polydispersities, which indicated that the ATRP of MMA was controlled. Using the same experimental conditions, the apparent rate constant (k) under MI (k = 7.6 × 10^?4 s^?1) was higher than that under conventional heating (k = 5.3 × 10^?5 s^?1). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2189–2195, 2004     

The effect of gel composition on the uranyl ions adsorption capacity of poly(N‐vinyl 2‐pyrrolidone‐g‐citric acid) hydrogels prepared by gamma rays

Poly(N‐vinyl 2‐pyrrolidone‐g‐citric acid) (PVP‐g‐CA) hydrogels with varying compositions were prepared from ternary mixtures of N‐vinyl 2‐pyrrolidone–citric acid–water by using ⁶⁰Co γ‐rays. The effect of gel composition on the uranyl ions adsorption capacity of PVP‐g‐CA hydrogels was investigated. Uranyl adsorption capacity of these hydrogels were found to be in the range of 18–144 mg [UO]/g dry gel from the aqueous solution of uranyl nitrate and 22–156 mg [UO]/g dry gel from the aqueous solution of uranyl acetate, depending on the content of citric acid in the hydrogel, while poly(N‐vinyl 2‐pyrrolidone) hydrogel did not sorb any uranyl ion. The swelling of PVP‐g‐CA hydrogel containing 2.7 mol % CA was observed in water (1620%), in uranyl acetate solution (1450%) and in uranyl nitrate solution (1360%), as compared to 700% swelling of pure PVP hydrogels. The diffusion coefficients were varied from 12.57 up to 4.04 • 10⁻⁸ m² s⁻¹. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1037–1043, 2000     

Synthesis,characterization, and metal‐ion uptake studies of chelating resins derived from formaldehyde‐condensed azodyes of aniline and 4,4′‐diaminodiphenylmethane coupled with phenol/resorcinol

The diazonium salts of aniline and 4,4′‐diaminodiphenylmethane coupled with phenol and resorcinol were condensed with formaldehyde in alkaline media to yield polymeric resins. These polymers were found to readily react with metal ions like Cu²⁺ and UO, forming polychelates. The azodyes, resins, and polychelates were characterized by several instrumental techniques such as elemental analysis, FTIR, ¹H‐NMR, GPC, XRD, TG–DTG, and DSC studies. The chelating capacity of the resins toward Cu²⁺ and UO ions was studied by spectrophotometry. The extent of metal loading of the resins was studied by varying the time of contact, metal‐ion concentration, and pH of the reaction medium. The alkali and alkaline earth metal ions had little effect on the metal‐ion uptake behavior of the resins. The resin derived from the azodye of 4,4′‐diaminodiphenylmethane was found to be more efficient in removing the metal ions from solution than were the resins from aniline. The optimum conditions for effective separation of Cu²⁺ from UO were determined. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3128–3141, 2000     

Determination of crystallinity ratio and some physicochemical properties of poly(4‐methyl‐1‐pentene)

It was determined that the thermal stability of poly(4‐methyl‐1‐pentene) (P4MP) was maintained up to 424°C in an inert atmosphere by thermogravimetric analysis. The retention diagrams of ethyl acetate, tert‐butyl acetate, and benzene on P4MP were plotted at temperatures between 30 and 280°C by inverse gas chromatography (IGC) technique. Melting temperature of the polymer was determined as 230 and 239.5°C by IGC and differential scanning calorimetry (DSC), respectively. The percent crystallinity of P4MP was obtained from the retention diagrams at temperatures below melting point. The percent crystallinity obtained by IGC is in good agreement with the ones obtained by DSC. Then, specific retention volume, V, weight fraction activity coefficient, Ω, Flory‐Huggins polymer‐solvent interaction parameter, χ, equation‐of‐state polymer‐solvent interaction parameter, χ, and effective exchange energy parameter, X_eff of octane, nonane, decane, undecane, dodecane, tridecane, n‐butyl acetate, isobutyl acetate, isoamyl acetate with P4MP, were determined between 240 and 280°C by IGC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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