Petr Holler

The effect of polymerization temperature on molecular weight, crystallinity, and electrical conductivity of polyaniline

Abstract The influence of the polymerization temperature (from −50 to +50°C) on molecular weight, crystallinity, and electrical conductivity of polyaniline has been investigated. Aniline was oxidized in aqueous medium with ammonium peroxodisulfate at equimolar and excess concentrations of hydrochloric acid. The reaction mixture freezes below −10°C and the polymerization of aniline then proceeds in the solid state. As the reaction temperature decreases, both the molecular weight of polyaniline (determined by gel permeation chromatography) and its crystallinity (observed by X-ray diffraction) increase. The morphology of polyaniline changes from granular (reaction in a liquid medium) to macroporous (polymerization in the frozen state). Electrical conductivity of polyaniline is higher for samples prepared under more acidic conditions. It was found to be independent of the polymerization temperature and, consequently, of the molecular weight.

Synthesis and characterization of conducting polyaniline 5-sulfosalicylate nanotubes

Conducting polyaniline 5-sulfosalicylate nanotubes and nanorods were synthesized by the template-free oxidative polymerization of aniline in aqueous solution of 5-sulfosalicylic acid, using ammonium peroxydisulfate as an oxidant. The effect of the molar ratio of 5-sulfosalicylic acid to aniline on the molecular structure, molecular weight distribution, morphology, and conductivity of polyaniline 5-sulfosalicylate was investigated. The nanotubes, which have a typical outer diameter of 100-250 nm, with an inner diameter of 10-60 nm, and a length extending from 0.4 to 1.5 microm, and the nanorods, with a diameter of 80-110 nm and a length of 0.5-0.7 microm, were observed by scanning and transmission electron microscopies. The presence of branched structures and phenazine units besides the ordinary polyaniline structural features was revealed by infrared and Raman spectroscopies. The stacking of low-molecular-weight substituted phenazines appears to play a major role in the formation of polyaniline nanorods. The precipitation-dissolution of oligoaniline templates as a key element in the formation of polyaniline nanotubes is proposed to explain the crucial influence of the initial pH of the reaction mixture and its decrease during the course of polymerization.

Chemical Oxidative Polymerization of Aminodiphenylamines

The course of oxidation of 4-aminodiphenylamine with ammonium peroxydisulfate in an acidic aqueous ethanol solution as well as the properties of the oxidation products were compared with those of 2-aminodiphenylamine. Semiconducting oligomers of 4-aminodiphenylamine and nonconducting oligomers of 2-aminodiphenylamine of weight-average molecular weights 3700 and 1900, respectively, were prepared by using an oxidant to monomer molar ratio of 1.25. When this ratio was changed from 0.5 to 2.5, the highest conductivity of oxidation products of 4-aminodiphenylamine, 2.5 x 10 (-4) S cm (-1), was reached at the molar ratio [oxidant]/[monomer] = 1.5. The mechanism of the oxidative polymerization of aminodiphenylamines has been theoretically studied by the AM1 and MNDO-PM3 semiempirical quantum chemical methods combined with the MM2 molecular mechanics force-field method and conductor-like screening model of solvation. Molecular orbital calculations revealed the prevalence of N prim-C10 coupling reaction of 4-aminodiphenylamine, while N prim-C5 is the main coupling mode between 2-aminodiphenylamine units. FTIR and Raman spectroscopic studies confirm the prevalent formation of linear N prim-C10 coupled oligomers of 4-aminodiphenylamine and suggest branching and formation of phenazine structural units in the oligomers of 2-aminodiphenylamine. The results are discussed with respect to the oxidation of aniline with ammonium peroxydisulfate, leading to polyaniline, in which 4-aminodiphenylamine is the major dimer and 2-aminodiphenylamine is the most important dimeric intermediate byproduct.

Multifunctional ATRP macroinitiators for the synthesis of graft copolymers

Abstract Multifunctional ATRP macroinitiators, polystyrene with 1-(2-bromopropionyloxy)ethyl or 1-(2-bromoisobutyryloxy)ethyl groups in the benzene rings and poly[4-methylstyrene- co -4-(bromomethyl)styrene], were synthesized. All the functionalized polymers were characterized by IR, 1 H and 13 C NMR spectroscopy and by size exclusion chromatography.

Thermally induced polymerization of isobutylene in the presence of SnCl4: Kinetic study of the polymerization and NMR structural investigation of low molecular weight products

The polymerization reactivity of isobutylene/SnCl4 mixtures in the absence of polar solvent, was investigated in a temperature interval from −78 to 60 °C. The mixture is nonreactive below −20 °C but slow polymerization proceeds from −20 to 20 °C with the initial rate r0 of the order 10−5 mol · l−1 · s−1. The rate of the process increases with increasing temperature up to ∼10−2 mol · l−1 · s−1 at 60 °C. Logarithmic plots of r0 and Mn versus 1/T exhibit a break in the range from 20 to 35 °C. Activation energy is positive with values E = 21.7 ± 4.2 kJ/mol in the temperature interval from −20 to 35 °C and E = 159.5 ± 4.2 kJ/mol in the interval from 35 to 60 °C. The values of activation enthalpy difference of molecular weights in these temperature intervals are ΔHMn = −12.7 ± 4.2 kJ/mol and −38.3 ± 4.2 kJ/mol, respectively. The polymerization proceeds quantitatively, the molecular weights of products are relatively high, Mn = 1500–2500 at 35 °C and about 600 at 60 °C. It is assumed that initiation proceeds via [isobutylene · SnCl4] charge transfer complex which is thermally excited and gives isobutylene radical-cations. Oxygen inhibits the polymerization from −20 to 20 °C. Possible role of traces of water at temperatures above 20 °C is discussed. It was verified by NMR analysis that only low molecular weight polyisobutylenes are formed with high contents of exo- terminal unsaturated structures. In addition to standard unsaturated groups, new structures were detected in the products.

Copolymerization and addition of styrene and N-phenylmaleimide in the presence of nitroxide

The copolymerization and addition reaction of styrene (S) with N-phenylmaleimide (PMI), either neat or in xylene, have been found to proceed at 125°C in the presence of 2,2,6,6-tetramethylpiperidin-1-yloxy (TEMPO) radicals. TEMPO-terminated alternating S-PMI copolymers and comonomer adducts were obtained. The amounts of the low molecular weight compounds increased with the increasing content of PMI in the initial mixture. The reaction suggests formation of monofunctional unimolecular initiators. In the autopolymerization of neat comonomers, a mediating role of TEMPO was observed. The synthesized copolymers containing TEMPO end groups were used as macroinitiators to initiate polymerization of styrene. The molecular weight distributions of resulting poly(styrene-alt-N-phenylmaleimide)-block-polystyrene copolymers indicated the presence of both low molecular weight termination products and some copolymer precursor. The copolymers and comonomer adducts were characterized using the nitrogen analysis, size-exclusion chromatography (SEC), and NMR spectroscopy.

The effect of urocanic acid on graft rejection in an experimental model of orthotopic corneal transplantation in rabbits

Abstract• Background: Urocanic acid (UCA) is a natural component of the stratum corneum of the skin. It has been described as a photoreceptor for ultraviolet B radiation. UCA is present in the skin as a trans-isomer and undergoes UVB irradiation-dependent isomerization from trans-to cis-isomer. An immunosuppressive effect of irradiated UCA, i.e. a mixture of cis- and trans-isomers, has been demonstrated both in vivo and in vitro. The aim of this study was to evaluate an immunosuppressive effect of irradiated UCA on graft rejection in an experimental model of orthotopic corneal transplantation. • Method: A commercially available UCA was dissolved in salt solution and irradiated by XeCl excimer laser beam in order to obtain a mixture of cis- and trans-isomers. The immunosuppressive effect of irradiated UCA, compared to controls, unirradiated UCA and salt solution, was evaluated in a high-risk orthotopic corneal transplantation model; the agents were administered subconjunctivally to rabbits. • Results: The rejection reaction was observed in all animals. The mean graft survival time in rabbits administered salt solution or unirradiated UCA was 20 days and 22 days, respectively. The irradiated solution of UCA significantly (P<0.01, Mantel-Cox test) prolonged mean graft survival time to 29 days. • Conclusion: Subconjunctival administration of irradiated UCA prolonged the graft survival time in comparison with unirradiated UCA or salt solution in recipients in a rabbit transplantation model. Although further studies are necessary, UCA seems to be an effective immunosuppressive drug after corneal transplantation.

Hydrogenation of low-molar-mass, OH-telechelic polybutadienes. I. Methods based on diimide

Low-molar-mass, OH-telechelic polybutadienes were hydrogenated (1) by diimide alone and (2) by using a novel method, consisting of the following two steps: up to some 95% degree of conversion by gaseous hydrogen with conventional Ziegler–Natta catalysts, and, only then, up to almost full saturation by diimide. The two-step method, which has been found to be equally efficient, enables one to decrease substantially the necessary feed of p-toluenesulfonylhydrazide, by the thermal decomposition of which diimide is generated. The crude saturated products, which could not be purified by a conventional (re)precipitation technique due to their low molar mass, contained a relatively large amount of a side-product, bis(p-tolyl)disulfide (TDS). It was found that free TDS can be converted quantitatively by reduction cleavage into p-tolyl mercaptan (TM) without changing the structure of the polymeric product, and TM can then be removed from the mixture by alkaline extraction. Alternatively, the crude product can be freed from TDS by chromatography. With the two-step hydrogenation method, only a small amount of the fragments and/or precursors of TDS add to the 5% residual CC double bonds of the partially hydrogenated polybutadiene chains. After any of the two purification procedures, the fully saturated products usually contained less than 1 wt % of such undesirable substituents only, which is comparable with the reported single-step diimide hydrogenation of the initial, fully unsaturated polybutadiene in the presence of a proton scavenger (tri-n-propylamine).

Chemical oxidative polymerization of dianilinium 5-sulfosalicylate

Dianilinium 5-sulfosalicylate was prepared in situ and then oxidized in aqueous solution with ammonium peroxydisulfate. The precipitated polyaniline 5-sulfosalicylate was soluble in polar aprotic solvents and showed conductivity of ∼0.1 S cm−1. Scanning electron microscopy revealed the coexistence of nanorods and granular morphology of the polyaniline 5-sulfosalicylate. The weight-average molecular weight and poly-dispersity index were determined by gel-permeation chromatography as 53000 and 9.0, respectively. FTIR spectroscopic analysis combined with AM1 and MNDO-PM3 semi-empirical quantum chemical studies of the polymerization mechanism indicate both covalent and ionic bonding of sulfosalicylate to polyaniline chains. Raman spectroscopy proved the presence of substituted phenazine structural units besides ordinary emeraldine segments.

Oxidative polymerization of anilinium 5-sulfosalicylate with peroxydisulfate in water

Anilinium 5-sulfosalicylate was prepared and characterized by elemental analysis, and FTIR and NMR spectroscopies. It was polymerized in an aqueous solution using ammonium peroxydisulfate as an oxidant. The precipitated polyaniline 5-sulfosalicylate exhibited high thermal stability and conductivity of 0.13 S cm−1. Its mass-average molar mass and polydispersity index were determined by gel-permeation chromatography as 22,900 g mol−1 and 2.7, respectively. Elemental analysis and FTIR spectroscopy study of polyaniline 5-sulfosalicylate revealed the doping level and the oxidation state between emeraldine and protoemeraldine salt while corresponding studies of the polyaniline base indicate a small extent of the covalent bonding of 5-sulfosalicylate anions to polyaniline chains.