Monodisperse and isolated microspheres of poly(N-methylaniline) prepared by dispersion polymerization

Monodisperse and isolated microspheres of poly(N-methylaniline) were successfully prepared through chemical polymerization of N-methylaniline by in adipic acid containing poly(vinylpyrrolidone) (PVP). Mean diameters of the microspheres with smooth surfaces changed from 320 to 100 nm by increasing the reaction temperature from 25 to 75 °C. The concentration of PVP did not affect much the size of microspheres, but the increased PVP concentration led to longer induction times for the onset of dispersion polymerization.     

Comparative studies of chemically synthesized polyaniline and poly(o-toluidine) doped with p-toluene sulphonic acid

Polyaniline and poly(o-toluidine) doped with p-toluene sulphonic acid (p-TSA) were synthesized by in situ chemical polymerization method using ammonium per sulphate as an oxidizing agent. This is a novel polymerization process for the direct synthesis of emeraldine salt phase of the polymer. The polymers were characterized by using UV-Vis and FT-IR spectroscopy, SEM, elemental analyzer, TGA/DSC and conductivity measurements. Thermal analysis shows that poly(o-toluidine) is less thermally stable compared to polyaniline. The less conductivity in poly(o-toluidine) is due to the cumulative steric as well as electronic effect of the bulky methyl substituent present on the benzene ring. High temperature conductivity measurements show ‘thermal activated behavior’.     

Reaction of N-methylsulfonyl-and N-(p-tolylsulfonyl)-2-(cyclopent-1-en-1-yl)anilines with bromine in the presence of potassium thiocyanate and in methanol

The reactions of N-methylsulfonyl-and N-(p-tolylsulfonyl)-2-(cyclopent-1-en-1-yl)-6-methylaniline with molecular bromine in the presence of potassium thiocyanate gave N-methylsulfonyl-and N-(ptolylsulfonyl)-2-(5-isothiocyanatocyclopent-1-en-1-yl)-6-methylanilines. N-Methylsulfonyl-2-(cyclopent-1-en-1-yl)-6-methylaniline reacted with bromine in methanol in the presence of NaHCO₃ or with CuBr₂ in MeOH to afford N-methylsulfonyl-2-(5-methoxycyclopent-1-en-1-yl)-6-methylaniline. The reaction of N-methylsulfonyl-2-(5-isothiocyanatocyclopent-1-en-1-yl)-6-methylaniline with diethylamine led to the formation of N-methylsulfonyl-2-{5-[diethylamino(thioxo)methyl]aminocyclopent-1-en-1-yl}-6-methylaniline which was converted into 5-methyl-4-methylsulfonyl-2,3,3a,4-tetrahydrocyclopenta[b]indole by heating with potassium hydroxide.     

Synthesis and characterization of novel vinyl copolymers containing N-vinylphthalimide: Comonomers reactivity ratios and thermal stability

N-Vinylphthalimide (NVPh) was copolymerized with p-methylstyrene (PMS), p-methoxystyrene (PMOS) and p-chlorostyrene (PClS) at 60 °C, with 2,2′-azo-bis-isobutyronitrile as an initiator. Copolymer composition was determined by elemental analysis in case of the N-vinylphthalimide and p-methylstyrene comonomer pair, whereas proton nuclear magnetic resonance was used for the analysis of the two other copolymers.The reactivity ratios for each comonomer pair were estimated by the classical Fineman-Ross and Kelen-Tüdõs linear techniques. These data showed that N-vinylphthalimide was less reactive in all the cases and that the comonomer distribution, that was basically random in the poly(N-vinylphthalimide-co-p-methylstyrene) and poly(N-vinylphthalimide-co-p-chlorostyrene) copolymers, was rather alternate in the third poly(N-vinylphthalimide-co-p-methoxystyrene) copolymer. The difference observed in the reactivity ratios was discussed in reference to the structure of the comonomer units and the parent radicals. The thermal properties of the copolymers and model homopolymers were investigated by differential scanning calorimetry and thermogravimetric analysis.     

Host behaviour of related compounds,TETROL and DMT,in the presence of two different classes of aromatic guest compounds

The host potential of two closely-related compounds, TETROL [(+)-(2R,3R)-1,1–4,4-tetraphenylbutane-1,2,3,4-tetraol] and DMT [(−)-(2R,3R)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol], were compared when recrystallized from two different classes of guests, namely toluene, ethylbenzene, cumene and aniline, N-methylaniline, N,N-dimethylaniline. TETROL formed complexes with only aniline and N-methylaniline (host:guest ratios, 2:3 and 2:4), while DMT included all six guests with a consistent ratio (2:1). Aniline competition experiments showed that TETROL preferred aniline (67%), followed by N-methyl- (29%) and N,N-dimethyl- (4%) aniline; surprisingly, this order was exactly reversed for DMT [N,N-dimethylaniline (62%) > N-methylaniline (32%) > aniline (6%)]. Crystal diffraction analyses revealed that TETROL formed stabilizing hydrogen bonds with guests, behaving as both donor and, for the first time, acceptor (in 2TETROL∙4N-methylaniline). DMT did not form bonds of this type with any guests. Furthermore, the host packing was isostructural for all DMT complexes but was guest-dependent for TETROL. Thermal analyses showed that complex stabilities correlated precisely with the host preferences.     

Conductivity and thermal behavior of proton conducting polymer electrolyte based on poly (N-vinyl pyrrolidone)

The polymer electrolytes based on poly N-vinyl pyrrolidone (PVP) and ammonium thiocyanate (NH₄SCN) with different compositions have been prepared by solution casting technique. The amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The shift in T_g values and the melting temperatures of the PVP-NH₄SCN electrolytes shown by DSC thermo-grams indicate an interaction between the polymer and the salt. The dependence of T_g and conductivity upon salt concentration have been discussed. The conductivity analysis shows that the 20 mol% ammonium thiocyanate doped polymer electrolyte exhibit high ionic conductivity and it has been found to be 1.7 × 10⁻⁴ S cm⁻¹, at room temperature. The conductivity values follow the Arrhenius equation and the activation energy for 20 mol% ammonium thiocyanate doped polymer electrolyte has been found to be 0.52 eV.     

Thermal studies of chitin–chitosan derivatives

New poly(azo) amino-chitosan compounds were obtained from the azo coupling reaction of N-benzyl chitosan and diazonium salts. The thermal behavior of these compounds was studied by thermogravimetric analysis (TG), differential thermogravimetric analysis (DTG), TG coupled with a Fourier-transform infrared, and differential scanning calorimetry (DSC). TG/DTG curves of chitin–chitosan polymer showed two thermal events attributed to water loss and decomposition of the polysaccharide after cross-linking reactions. Thermal analysis of the poly(azo) amino-chitosan compounds showed that the decomposition temperatures decreased when compared to the starting chitin–chitosan and N-benzyl chitosan. DSC results showed an agreement with the TG/DTG analyses. Thermal behavior of poly(azo) amino-chitosans suggest that these compounds could be considered as potential thermal sensors.     

Effects of residual metal compounds and chain-end structure on thermal degradation of poly(3-hydroxybutyric acid)

Thermal degradation behaviours of poly(3-hydroxybutyric acid) (P(3HB); bacterial poly[(R)-3-hydroxybutyric acid] and synthetic poly[(R,S)-3-hydroxybutyric acid] samples, were examined under both isothermal and non-isothermal conditions. The inverse of number-average degree of polymerisation for all P(3HB) samples decreased linearly with degradation time during the initial stage of isothermal degradation at a temperature ranging from 170-190 °C. In addition, crotonyl unit was detected in the residual polymer samples as main ω-chain-end. These results indicate that the dominant thermal degradation reaction for P(3HB) is a random chain scission via cis-elimination reaction of P(3HB) molecules. It was found that the presence of either Ca or Mg ions enhances the depolymerisation of P(3HB) molecules, while that Zn ions hardly catalyse the reaction. As a result, a shift of thermogravimetric curves toward the lower temperature regions was observed for the P(3HB) samples containing high amounts of Ca and Mg compounds.     

Thermal degradation of [poly(N-vinylimidazole)-polyacrylic acid] interpolymer complexes

Interpolymer complexes of a slightly basic polymer, poly(N-vinylimidazole) (PVIm) with a strongly acidic polymer, poly(acrylic acid) (PAA) have been prepared by mixing aqueous solutions of the respective components. Spectroscopy and thermal methods were used to reveal interaction between VIm and AA moieties. FT-IR analysis showed that the nitrogen atoms at 3rd position of imidazole ring are involved in strong H-bonding with acid groups of PAA leading to a uniform and fully miscible complex structure. As the quantity of PAA increases the thermal stability of complex increases based on TG results. In the DSC analyses, the single T_g for all IPC samples showed that IPCs have good or definite miscibility over the whole range of composition as a result of H-bond formation between acrylic acid and imidazole units.     

Synthesis and characterization of new azobenzenesulfonic acids doped conducting polyaniline

New azobenzene sulfonic acid dopants were synthesized by diazotized coupling reaction of sulphanilic acid diazonium salt with commercially available raw materials such as phenol, m-cresol and 4-phenylphenol. The structures of the dopants are confirmed by NMR and FT-IR. Polyaniline emeraldine base was doped by these new azobenzenesulfonic acid dopants in two different solvent medium such as methanol and N-methylpyrrolidinone to produce green emeraldine salt. The doping process was confirmed by FT-IR and UV-vis spectroscopy. The effect of composition of dopant on the conductivity of the polyaniline was investigated and the results suggest that the conductivity increases with the increase in the dopant concentration and attained maxima for more than 38% in the feed. The conductivity measurements reveal that all the dopants equally effective in producing in high conductivity in the range of 0.02 S/cm and the conductivity of the doped samples are insignificant to the structural difference in the dopant. WXRD and SEM analysis indicate that the doped samples are highly amorphous and porous in nature. The thermal analysis by TGA indicate that all the doped materials were highly stable up to 300 °C for high temperature applications.     

Electroactivity, electrochemical stability and electrical conductivity of multilayered films containing poly(3,4-ethylendioxythiophene) and poly(N-methylpyrrole)

Multilayered systems of poly(3,4-ethylendioxythiophene) and poly(N-methylpyrrole) have been prepared using a layer-by-layer electrodeposition technique. The electrochemical and electrical properties of films formed by 3, 5, 7 and 9 layers have been characterized and compared with those of pure polymers and copolymers prepared from mixtures of 3,4-ethylendioxythiophene and N-methylpyrrole with various concentration ratios. Results indicate that the electroactivity and electrical stability of the multilayered systems are higher than those of both poly(3,4-ethylendioxythiophene) and copolymers. Furthermore, these electrochemical properties improve when the number of layers increases. On the other hand, the electrical conductivity of the multilayered systems is slightly lower than that of pure poly(3,4-ethylendioxythiophene), and significantly higher than those of poly(N-methylpyrrole) and copolymers.     

Easily assembled,modular N,O-chelating ligands for Ta(V) complexation: a comparative study of ligand effects in hydroaminoalkylation with N-methylaniline and 4-methoxy-N-methylaniline

The influence of structurally related N,O-chelating ligands with additional heteroatoms (N, O, P, S) on the reactivity of in situ generated tantalum complexes for the hydroaminoalkylation of amines has been explored. Reactivity was probed by evaluating the catalytic ability of these N,O-chelating systems with N-methylaniline and 4-methoxy-N-methylaniline substrates. Enhanced reactivity is observed with amide proligands bearing an ortho-methoxyphenyl group on the nitrogen. 4-Methoxy-N-methylaniline is found to be more prone to undergo C–H functionalization via hydroaminoalkylation than N-methylaniline. The use of the related substrate 2-methoxy-N-methylaniline is not tolerated, and instead C(sp³)–O bond cleavage was observed.     

Solid-state electrolytes based on ionic network polymers

Interpenetrating and semi-interpenetrating polymer networks are synthesized with the use of cationic and anionic ionic monomers: N-[3-(methacryloyloxy)propyl]-N-methylpyrrolidinium bis(trifluoromethane-sulfonyl)imide, N-[2-(2-(2-(methacryloyloxy)ethoxy)ethoxy)ethyl]-N-methylpyrrolidinium bis(fluorosulfonyl)imide, and (N-butyl-N-methylpyrrolidinium 1-[3-(methacryloyloxy)propylsulfonyl] (trifluoromethanesulfonyl) imide. Their ionic conductivities, electrochemical stabilities, heat resistances, thermal stabilities, and mechanical properties and the swelling of the films in ionic liquid/lithium salt mixtures were studied. The copolymerization of N-[2-(2-(2-(methacryloyloxy)ethoxy)ethoxy)ethyl]-N-methylpyrrolidinium bis(fluorosulfonyl)imide and poly(ethylene glycol dimethacrylate) and poly(ethylene glycol methacrylate) in the presence of butadiene-acrylonitrile rubber and a solution of Li(CF₃SO₂)₂N in N-(methoxymethyl)-N-methylpyrrolidinium bis(fluorosulfonyl)imide yielded a solid-state electrolyte with a set of properties optimum among the studied films: an ionic conductivity of 1.3 × 10^?4S/cm (25°C), a tensile strength of 80 kPa, and an elongation at break of 60%.     

New optically active and thermally stable poly(ester-imide)s containing bicyclo segment in the main chain: Synthesis and characterization

New optically active diacid containing L-2-aminobutyric acid moiety was prepared by reacting bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride 1, with L-2-aminobutyric acid 2 in the acetic acid, and was polymerized with several aromatic diols 5a–f to obtain a new series of optically active poly(ester-imide)s (PEIs) through direct polycondensation using tosyl chloride/pyridine/N,N-dimethylformamide system as condensation agent. The data obtained by these methods indicate that, good yields and inherent viscosities are resulted. These polymers are readily soluble in polar organic solvents such as N,N-dimethyacetamide, N,N-dimethyformamide, dimethyl sulfoxide. The obtained polymers were characterized by FTIR, specific rotation measurements, elemental analysis and ¹H NMR spectroscopy. The thermal stability of the resulting PEIs were evaluated with thermogravimetric analysis and differential scanning calorimetry techniques under a nitrogen atmosphere.     

Cobalt ion-doped polyaniline,poly(N-methylaniline), and poly(N-ethylaniline): electrosynthesis and characterisation using electrochemical methods in acidic solutions

Cobalt ion (Co²⁺)-doped polyaniline (PANI-Co), poly(N-methylaniline) (PNMA-Co), and poly(N-ethylaniline) (PNEA-Co) films were synthesised electrochemically on a pencil graphite electrode (PGE) and their electrochemical properties were investigated for supercapacitor applications. The polymer film-coated electrodes (PGE/PANI-Co, PGE/PNMA-Co, and PGE/PNEA-Co) thus obtained were characterised by scanning electron microscopy (SEM) and different electrochemical methods. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were employed in 0.1 M H₂SO₄ solution to calculate the specific capacitance (C _S) values of the electrodes. The maximum C _S of 192.94 F g^?1, 139.83 F g^?1, and 47.12 F g^?1 were achieved for PGE/PANI-Co, PGE/PNMA-Co, and PGE/PNEA-Co at 1 mV s^?1, respectively. On the other hand, the charge/discharge stability of the electrodes was analysed using the repeating chronopotentiometry (RCP) method. The RCP measurements indicate that the electrodes could be used as an electrode active material for low voltage supercapacitor applications.     

Investigation of Spectroscopic and Thermal Properties of Poly(o‐toluidine) Doped with Polymeric Acids

Single step polymerization of poly(o‐toluidine) was carried out by using ammonium persulphate as an oxidizing agent. Formation of the conducting emeraldine salt phase of the polymer was confirmed by the UV‐visible and FT‐IR spectroscopic analysis. The elemental composition of the polymer was evaluated by using a CHNS analyzer. Thermal stability of these polymers was investigated by the thermogravimetric analysis. Among the three polymeric acids used for doping purposes, poly(acrylic acid) doped material was found to show less thermal stability compared to poly(styrene sulphonic acid) and poly(vinyl sulphonic acid) doped poly(o‐toluidine).     

Crystalline properties and decomposition kinetics of cellulose fibers in wood pulp obtained by two pulping processes

In this study two cellulose fibers, Eucalyptus grandis (CEG) and Pinus taeda (CPT), obtained through the kraft and sulfite pulping processes, respectively, were characterized. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and thermogravimetric analysis (TGA) were carried out. From the XRD analysis the interplanar distance, crystallite size and crystallinity index were calculated and the degradation kinetics parameters were determined by TGA at heating rates of 5, 10, 20 and 40 °C min⁻¹ using the Avrami, Flynn-Wall-Ozawa (FWO) and Criado methods. The results obtained by FTIR showed that the composition of the fibers is similar, while from the XRD analysis slight differences in the crystallinity were observed. The thermogravimetric analysis showed higher thermal stability for CPT than CEG while the values for the activation energy (E_a) were higher for CEG than CPT. The results obtained by Avrami and Criado methods showed that the degradation mechanism in the CEG samples involves a diffusion process while in the case of CPT the degradation process is a phase boundary controlled reaction. The degradation mechanisms demonstrated that the difference between thermal stability and E_a may be due to differences in the type of crystalline structure of the samples obtained through the two pulping processes.     

Polyanthranilides—II. Synthesis and characterization of polyamides from 6-methyl and 6,7-methylenedioxybenz-3,1-oxazin-2,4-dione

Ring-scission polymerizations of 6-methyl and 6,7-methylenedioxybenz-3,1-oxazin-2,4-dione have been studied in the presence of catalysts such as aq HCl, the corresponding anthranilamide, N-methylaniline, o-chloroaniline and acid amides under various conditions. These substances underwent ring-scission polymerization affording polyanthranilides in the presence of the first four catalysts under appropriate experimental conditions. The samples were insoluble in all organic solvents including formic acid. They were soluble in sulphuric acid with degradation. They were characterized by i.r. and thermogravimetric analysis.     

Proton‐conducting polymers based on benzimidazoles and sulfonated benzimidazoles

A sulfonated derivative of polybenzimidazole is reported, and its properties are analyzed in comparison with related polybenzimidazole proton‐conducting materials. Poly(2,5‐benzimidazole), poly(m‐phenylenebenzobisimidazole), and poly[m‐(5‐sulfo)‐phenylenebenzobisimidazole] were prepared by condensation of the corresponding monomers in polyphosphoric acid. Several adducts of these polymers with phosphoric acid were prepared. The resulting materials were characterized by chemical analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis; also, the dc conductivity of doped and undoped derivatives was measured. Similar to what has been observed for the commercial polybenzimidazole polymer (also examined here for comparison), the title polymers exhibit high thermal stability. Furthermore, their doping with phosphoric acid leads to a significant increase in conductivity from less than 10^?11 Scm^?1 for the undoped polymers to 10^?4 Scm^?1 (both at room temperature) for their acid‐loaded derivatives. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3703–3710, 2002     

Effect of magnetic nanoparticles on the thermal properties of some hydrogels

Magnetic hydrogels (ferrogels) based on poly(vinyl alcohol) (PVA) and poly(hydroxyethyl methacrylate) (PHEMA) with magnetite (Fe₃O₄) nanoparticles were prepared. PVA ferrogels were synthesised by submitting the aqueous solution of polymer and Fe₃O₄ to freezing-thawing (F-T) cycles yielding a physical gel. Different samples were prepared by varying (i) the concentration of PVA, (ii) the concentration of magnetite and (iii) the number of F-T cycles applied. PHEMA ferrogels were prepared by a crosslinking polymerization reaction in the presence of magnetite yielding chemical gels. Different samples were prepared by varying (i) the concentration of HEMA, (ii) the concentration of EGDMA and (iii) the concentration of magnetite nanoparticles. All ferrogel samples were first dried before been analysed in a thermogravimetric analyzer. The resulting thermograms showed that the concentration of magnetite nanoparticles does affect the thermal stability of either ferrogels system, a general improvement in comparison with PVA and PHEMA hydrogels, respectively, being observed. The apparent activation energy (E_a) of the thermal degradation for PVA ferrogels was evaluated and calculated applying the Flynn-Wall and the Kissinger methods. Values of apparent E_a increased with the content of Fe₃O₄ in the ferrogel sample.