Jiří Vohlídal

DEFINITIONS OF TERMS RELATING TO REACTIONS OF POLYMERS AND TO FUNCTIONAL POLYMERIC MATERIALS (IUPAC Recommendations 2003)

The document defines the terms most commonly encountered in the field of polymer reactions and functional polymers. The scope has been limited to terms that are specific to polymer systems. The document is organized into three sections. The first defines the terms relating to reactions of polymers. Names of individual chemical reactions are omitted from the document, even in cases where the reactions are important in the field of polymer reactions. The second section defines the terms relating to polymer reactants and reactive polymeric materials. The third section defines the terms describing functional polymeric materials.

Sulfonated polyanilines prepared by copolymerization of 3-aminobenzenesulfonic acid and aniline: The effect of reaction conditions on polymer properties

Sulfonated polyanilines (SPANs) with sulfur-to-nitrogen ratios of 0.05-0.40 were prepared by the copolymerization of aniline (ANI) and 3-aminobenzenesulfonic acid [metanilic acid (MA)] with ammonium peroxodisulfate in 1 M HCl at various MA/ANI and oxidant/monomer ratios and temperatures. The SPANs degree of oxidation, as ascertained from ultraviolet-visible and NMR spectra, and the SPAN bulk conductivity are inversely proportional to the content of MA units in the copolymer; that is, highly sulfonated SPAN samples are in a state closer to leucoemeraldine bases. The electron-withdrawing and steric effects of sulfonic groups clearly have a great impact on the structural features of SPANs and, consequently, on their properties. It has been suggested that the low conductivity of SPAN in comparison with polyaniline may be related to the low content of quinoid units in the SPAN molecules.

Terminology of polymers containing ionizable or ionic groups and of polymers containing ions (IUPAC Recommendations 2006)

This document defines the terms most commonly encountered in the field of polymers containing ionizable or ionic groups and polymers containing ions. The scope of the document has been limited to organic polymers. Inorganic materials, such as certain phosphates, silicates, etc., which also may be considered ionic polymers, are excluded from the present document. The terms selected are those that are widely used in the field of polymers containing ionizable or ionic groups and polymers containing ions. Only those terms that could be defined without ambiguity are considered. The terms are listed in alphabetical order, and cross-references to definitions given in other documents are provided.

Polybenzimidazole-supported [Rh(cod)Cl]2 complex: Effective catalyst for the polymerization of substituted acetylenes

The first heterogeneous catalyst which affords polymerization of substituted acetylenes into readily available high molecular weight polymers is reported. The catalyst (Rh/PBI) has been prepared by supporting di-mu-chloro-bis(eta4-cycloocta-1,5-diene)dirhodium(I), [Rh(cod)Cl]2, on commercial polybenzimidazole (PBI) porous beads by means of a simple quantitative adsorption from THF solution, and tested in polymerization of phenylacetylene, 4-fluorophenylacetylene, and 4-pentylphenylacetylene. The polymer molecules formed were found to be released from the Rh/PBI to surrounding solution during the polymerization performed in THF. Formation of high molecular weight ((M)w values up to 325,000) polymers in prevailing cis-transoid configuration has been observed with all monomers. In a comparison with free [Rh(cod)Cl]2 used as the homogeneous catalyst, the Rh/PBI can be used repeatedly, exhibits somewhat lower polymerization activity but almost no oligomerization activity, and provides polymers of higher molecular weight.

Poly(p-iodophenylacetylene): synthesis, characterization, polymer stability and photoelectrical properties

Abstract New functional acetylene, 1-ethynyl-4-iodobenzene, ( p -iodophenylacetylene) was prepared, characterized (i.r., n.m.r., u.v. and mass spectra) and transformed into high-molecular-weight polymers. Various WOCl 4 -based and MoCl 5 -based catalysts were used in the polymerization, the former leading to the red soluble and the latter to dark red insoluble poly( p -iodophenylacetylene) (PIPA), respectively. Both types of PIPA are non-crystalline and they differ in the configurational structure which, however, could not be assigned with certainty. A too high molecular weight and/or cross-linking is suggested as a reason of insolubility of PIPA prepared on Mo-based catalysts. The soluble PIPA was found to degrade autoxidatively in tetrahydrofuran solution at room temperature obeying the kinetic laws of polymer random degradation. The determined value of the rate constant of degradation, 2.6 × 10 −6 min −1 , is slightly higher than that found for unsubstituted poly(phenylacetylene) (PPA), under the same conditions. PIPA was found to possess a higher photo-conductivity than PPA at low and moderate electric fields. The Onsager model offers an adequate explanation for the measured dependence of the photogeneration efficiency of the applied electric field assuming the Gaussian distribution of the radii of charge-transfer states.

A brief guide to polymer nomenclature (IUPAC Technical Report)

The universal adoption of an agreed nomenclature has never been more important for the description of chemical structures in publishing and online searching. The International Union of Pure and Applied Chemistry (IUPAC) and Chemical Abstracts Service (CAS) make similar recommendations. The main points are shown here with references to original documents. Further details can be found in the IUPAC Purple Book.

MCM-41-immobilized [Rh(cod)OCH3]2 complex: A hybrid catalyst for the polymerization of phenylacetylene and its ring-substituted derivatives

The immobilization of [Rh(cod)OCH 3 ] 2 (cod = cycloocta-1,5-diene) on mesoporous molecular sieves MCM-41 provides the first inorganic-type hybrid catalyst, which affords heterogeneous polymerization of phenylacethylene and its ring-substituted derivatives, - 2-fluorophenylacetylene, 4-fluorophenylacetylene, and 4-fluorophenylacetylene - into readily isolable high-molecular-weight (M w from 50 000 to 180 000) substituted polyvinylenes of high cis-transoid structure. The activity of this catalyst is compared with that of homogeneous catalyst [Rh(cod)OCH 3 ] 2 .

Polymerization of 4-(ferrocenylethynyl)phenylacetylene with transition metal catalysts

A new conjugated polymer carrying organometallic pendant groups, poly[4-(ferrocenylethynyl)phenylacetylene], has been prepared. [Rh(nbd)(OCH 3 )] 2 as a catalyst (nbd = norbornadiene) provides a mixture of an insoluble polymer (yield 71%) free of C≡CH groups and soluble oligomers (yield 22%, MW ca. 1100). WOCl 4 /2Me 4 Sn as a catalyst provides almost exclusively a polymer (yield 60%, M w = 32. 10 3 ) containing a small amount of C≡CH groups that is soluble in aromatic and low-polarity solvents. Its solubility, however, decreases upon storage in the solid state, probably due to a subsequent crosslinking. The 13 C NMR, IR, UV-vis and Raman spectra of the monomer and polymers are reported.

Colloidal systems of silver nanoparticles and high-regioregular cationic polythiophene with ionic-liquid-like pendant groups: Optical properties and SERS.

We report tuning of structure dependent optical properties of colloidal systems of borate-stabilized silver nanoparticles (Ag NPs) and polythiophene-based cationic polyelectrolyte with ionic-liquid like side groups: poly{3-[6-(1-methylimidazolium-3-yl)hexyl]thiophene-2,5-diyl bromide} (PMHT-Br) towards obtaining local electromagnetic field enhancement effects. Surface-enhanced Raman scattering (SERS) studies showed that the strong electromagnetic field enhancement is related to the formation of aggregates of Ag NPs achieved at the components ratio providing the charge balance between Ag NPs and cationic polythiophene, at which Ag NPs are nearly single-polymer-layer coated, their zeta potential is close to zero and they easily form aggregates in which the mean inter-particle distance enables the occurrence of desired plasmonic effects. Fluorescence quenching is efficient only in the systems with low concentrations of PMHT-Br, in which almost all polymer chains directly interact with the Ag NPs surface.

Polymerization of p-nitrophenylacetylene with metathesis catalysts. Photoelectrical properties of phenylacetylene/p-nitrophenylacetylene copolymer

Preparation of substituted acetylene polymers carrying nitro group is reported for the first time. Homopolymers of p-nitrophenylacetylene (NPA) and its copolymer with phenylacetylene (PA) have been prepared by polymerizations induced by WOCl 4 /3Me 4 Sn as a catalyst in benzene and benzene/dioxane as solvents. WOCl 4 alone does not polymerize, oligomerize and/or cyclotrimerize NPA. The two-component catalysts WOCl 4 /2Ph4Sn and MoOCl 4 /3Me 4 Sn produce low amounts of oligomers only. The homopolymer of NPA is insoluble, whereas the copolymer containing one NPA unit per 4.38 units of PA is soluble in aromatic solvents and THF. The IR and NMR spectra of the homopolymer and the IR spectrum of the copolymer are reported. The photoconductive properties of the copolymer are also reported and compared with those of poly(PA). Introduction of NO 2 groups onto polymer chains was found to increase the quantum efficiency of charge carrier photogeneration but to deteriorate the charge carrier transport properties of the polymer.