Benzimidazole,benzothiazole, and benzoxazole polymers with anthracene recurring units

In an attempt to prepare polymers which might be oxidized to compounds soluble in alkali diphenyl 1,5-anthracenedicarboxylate was reacted with diaminobenzidine, dimercaptobenzidine, and diaminobiphenol in the melt and with dimercaptobenzidine dihydrochloride in polyphosphoric acid. Compounds of high molecular weight were obtained and their thermal and oxidative stability evaluated. Model compounds were prepared and their ultraviolet spectra compared with those of the polymers. Oxidation with nitric acid or chromium trioxide yielded some anthraquinone derivatives, but side reactions prevented the formation of useful products.     

Synthesis of sulfone-containing monomers and polymers using cationic cyclopentadienyliron complexes

The synthesis of sulfone-containing monomers with pendent cationic cyclopentadienyliron (CpFe⁺) moieties has been accomplished via nucleophilic aromatic substitution of dichloroarene complexes with a number aliphatic dithiols. These complexes were further oxidized using m-CPBA to give the sulfone-based monomers. Polymerization of the sulfone-based monomers with O-containing nucleophiles produced the sulfone-based polymers. Direct nucleophilic aromatic substitution of dichloroarene complexes with dinucleophiles allowed for the formation of organoiron sulfide-based polymers. Oxidation of these polymers led to the formation of sulfone polymers with the pendent iron moieties. The organometallic monomers and polymers were found to be more soluble in polar solvents in comparison to their organic analogues.     

Characterization of Electroinitiated and Radiation Polymerized Poly(Butadiene Sulfone)

Polymerization of butadiene sulfone was accomplished by using two different methods. The first method involves electrochemical polymerization of the monomer using the constant potential electrolysis technique. Oxidation of the monomer under nitrogen atmosphere in an acetonitrile-tetrabutylammonium tetrafluoroborate system yields brown, tarry polymers. On the other hand, the second initiation method, which was radiation polymerization, yields white, powdery polymers. Structural analyses of the two polymers by various spectroscopic methods suggest a structure consisting of two different units in different proportions.     

Rhodium-catalyzed, regiospecific functionalization of polyolefins in the melt

The rhodium-catalyzed, terminal-selective borylation of alkanes has been used to modify polyolefins. The functionalization of two materials, polyethylethylene (PEE) of molecular weights 1200 and 37 000, was conducted by combining bis-pinacoldiboron and 2.5 mol % [Cp*RhCl2]2 in neat polymer and heating at 150 degrees C. This procedure causes the polymer and boron reagent to melt, the catalyst to dissolve, and the reaction to form material with boryl groups at the terminal position of the polymer side chains. Oxidation of the borylated material generated polymers with hydroxyl groups at the terminal position of the side chains. The functionalization was conducted at various ratios of boron reagent to monomer. The resulting borylated and subsequent hydoxylated materials were characterized by 1H and 13C NMR spectroscopy, as well as MALDI-MS and GPC. Little change in polymer molecular weight and polydispersity was observed, and these data indicate that scission of the main chain does not occur. Measurements of the Tg of the polymers showed in increase in Tg of up to 50 degrees C after the modification. Thus, homogeneous, catalytic, selective alkane functionalization can be used to modify polymer properties.     

Oxidation and Structuring of Polydicyclopentadiene Thin Layers

It has been shown that polymeric film coatings derived from polydicyclopentadiene are subject to oxidation and structuring in air. Oxidation in air of double bonds in films gradually happens during several weeks and it comes amid an increase of adsorption band of carbonyl and hydroxyl groups in polymers infrared spectrums. Moreover, because of selective oxidation of cis-configured chains, structuring occurs around the double bonds in the polymer chain in polydicyclopentadiene films acquired by metathesis polymerization     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. VI. Polymers from 2,5-dicyanoterephthalic acid

Aromatic poly(keto ether sulfones) containing various amounts of pendant cyano groups were synthesized from 1,4-bis(p-phenoxybenzoyl)-2,5-dicyanobenzene, 1,3-bis(p-phenoxybenzenesulfonyl)benzene, and isophthaloyl chloride by a Friedel-Crafts type polymerization. These polymers softened at 160–190°C and had inherent viscosities of 0.44–0.61 in hexamethylphosphoric triamide. Crosslinkings were made by heating the polymers alone or in the presence of zinc chloride at 360–370°C to give black resinous materials that were insoluble in hexamethylphosphoric triamide in which the original polymers dissolved quite readily.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. II

1,3-Bis(p-phenoxybenzenesulfonyl)benzene and 4,4′-bis(p-phenoxybenzenesulfonyl)-diphenyl ether were polymerized with isophthaloyl and terephthaloyl chloride in Friedel-Crafts type polymerizations. These polymers had 5-cyanoisophthaloyl units in the backbone, obtained by using 5-cyanoisophthaloyl chloride as part of the acid chloride monomer. A number of catalysts were screened to effect the trimerization of the pendant nitrile groups in the polymer to the triazines. Model reactions were carried out for each polymer. Physical and thermal properties of the laminates obtained from these polymers are discussed.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. III

4,4′-Diphenoxydiphenylsulfone was polymerized with isophthaloyl chloride and terephthaloyl chloride in Friedel-Crafts polymerizations. These polymers had 5-cyanoisophthaloyl units in the backbone obtained either by using 1,3-bis(p-phenoxybenzoyl)-5-cyanobenzene or 5-cyanoisophthaloyl chloride as part of the acid chloride monomer. A terpolymer having 22 wt-% 5-cyanoisophthaloyl unit was also prepared from the Friedel-Crafts polymerization of 1,3-bis(p-phenoxybenzenesulfonyl)benzene and 5-cyanoisophthaloyl chloride. These terpolymers were crosslinked through heating to give insoluble products which proved to be thermally less stable than the uncrosslinked polymers.     

3-O-Methl-6-desoxy-L-talose,Synthese und Identifizierung mit L-Acovenose. Desoxyzucker, 43. Mitteilung

3-O-methly-6-deoxy-L -talose has been synthesized starting from 1, 2–5, 6-di-O-isopropylidene-α-D -allose ( 1 ). Methylation, selective acidic hydrolysis, sodium periodate oxidation and GRIGNARD reaction with CH₃MgBr gave a mixture of the 1, 2-isopropylidene derivatives of 3-O-methyl-6-deoxy-D -allose and 3-O-methyl-6-deoxy-D -allose ( 7 ) and 3-O-methyl-6-deoxy-L -talose ( 8 ) (L -acovenose) could be obtained. Oxidation of the latter gave the corresponding crystalline lactone, which could be indentified with a sample obtained from natural L -acovenose.     

Studies in some new initiator systems for vinyl polymerization. Part I. Molecular halogens or halates as one component

Several new initiating systems involving a molecular halogen, halates, or perhalate as one of the components and a reducing metal salt, ammonia, an amine or an organic compound as the other component, have been introduced for the aqueous (and in a few cases the non-aqueous) polymerization of methyl methacrylate. Some of the resulting polymers have been subjected to endgroup analysis by the application of the ultrasensitive dye techniques recently developed in our laboratory. Reducing metal salt—halogen-initiated polymers are found to incorporate hydroxyl and halogen endgroups, while polymers initiated by amine—halogen systems incorporate hydroxyl and halogen as well as amino endgroups. However, in the ammonia—halogen system polymers incorporate only halogen endgroups. On the basis of the results of the endgroup analysis of the polymers an attempt has been made to explain the probable initiation mechanism with regard to the nature and identity of the initiating species involved in such processes.     

Polymers with electron-deficient olefin moieties by oxidation of precursors containing “push–pull” olefin (β-alkylmercaptoenoate) moieties in the main chain

Oxidation of a polymer (1) having β-alkylmercaptoenoate moieties in the main chain by m-chloroperbenzoic acid (MCPBA) is described. Oxidation of 1 proceeded selectively to give polymers having vinyl sulfoxide or vinyl sulfone moieties in the main chain by using an appropriate amount of MCPBA. In the case of 1.1 equiv of MCPBA (relative to the sulfur atom), a polymer (4) having vinyl sulfoxide moieties selectively in the main chain was obtained in quantitative yield without side reactions. Likewise, a polymer (5) having vinyl sulfone moieties was obtained in quantitative yield by using 2.6 equiv of MCPBA. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2589–2592, 1998     

Polymer - supported cobalt (II) catalysts for the oxidation of alkenes

Polymer-supported heterogeneous catalysts in a form of complexes of 8-hydroxy- quinoline with cobalt acetate were synthesized. Conjugated polymers - polyaniline (PANI), poly-o-toluidine (POT), poly-o-anisidine (POA) - were used as supports. Oxidation reactions of aliphatic and aromatic hydrocarbons were carried out in the presence of molecular oxygen at atmospheric pressure and epoxides or ketones were obtained as the main products with high selectivity.     

Simple syntheses of (±) -β-copaene, (±) -β-ylangene and lemnalol.

The ketone 1a, which we have prepared from geranylacetone in 38% yield by a four step sequence, has been converted to β-copaene and β-ylangene by a three step sequence. Oxidation of β-ylangene with SeO₂ gives lemnalol in 76% yield.     

Bromate Exchange Resin as an Oxidizing Agent in Organic Synthesis

Bromate exchange resin has been prepared by a simple elution technique and used for the oxidation of aromatic aldehydes to the carboxylic acids. Oxidation is carried out under biphasic condition. Work up is simple. Resin immobilized bromate ions have been used for the first time as an oxidizing agent in organic synthesis.     

A BN Aromatic Ring Strategy for Tunable Hydroxy Content in Polystyrene

BN 2‐vinylnaphthalene, a BN aromatic vinyl monomer, is copolymerized with styrene under free radical conditions. Oxidation yields styrene–vinyl alcohol (SVA) statistical copolymers with tunable hydroxy group content. Comprehensive spectroscopic investigation provides proof of structure. Physical properties that vary systematically with hydroxy content include solubility and glass transition temperature. BN aromatic polymers represent a platform for the preparation of diverse functional polymeric architectures via the remarkable reaction chemistry of C−B bonds.     

Cerate oxidimetry: Oxidation of glycerol,glycol and other organic compounds

1. Oxidation ot tartronic acid has been studied and it has been shown that the oxidation of glycerol by ceric sulphate does not proceed via this acid by was presumed by earlier workers. 2. It has been shown that the oxidation of formic acid by pure ceric sulphate is negligible, but using chromium sulphate as catalyst, formic acid can be quantitatively oxidized. 3. Oxidation of glycol and glycerol can be carried out quantitatively either to the -formic acid stage or completely to carbon dioxide and water. A combination of the above provides a method for the estimation of the two compounds when present together in a mixture.     

Cerium masquerading as a group 4 element: synthesis,structure and computational characterisation of [CeCl(N(SiMe3)2)3

Oxidation of the three-coordinate cerium amide [Ce(N-(SiMe3)2)3] with TeCl4 in toluene solution yields purple, diamagnetic [CeCl(N(SiMe3)2)3], whose structure has been examined by X-ray crystallographic and computational methods.     

Charakterisierung von Organokieselsäurepolymeren durch thermoanalytische Untersuchungen

Four organosilicate polymers synthesized by addition of vinyl- and H-substituted double four-ring silicic acid derivatives were characterized using DSC and simultaneous TG-DTA measurements. Thermooxidative decomposition proceeds in several steps: Oxidation of (Si?H) groups, oxidation of (Si?CH₂?CH₂?Si) bridges, and oxidation of (Si?CH₃) groups, with formation of new (Si?O?Si) bonds.²⁹Si-NMR-spectroscopic measurements confirm this interpretation. Thermoanlytical methods of investigation proved useful to characterize these organosilicate polymers.     

Living polymers. Their discovery,characterization, and properties

The story of the discovery of living polymers is presented. Living polymers are polymers that retain their ability to propagate and grow to a desired size while their degree of termination or chain transfer is still negligible. Theoretical and mechanistic considerations are discussed. The living polymerization technique provides access to uniform polymers (Poisson molecular weight distribution) of controllable size, block copolymers, functional polymers, and star and comb-shaped polymers. The quantitative aspects of electron transfer are fully discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: ix–xv, 1998     

Synthesis, manipulation and conductivity of supramolecular polymer nanowires

The synthesis of supramolecular conducting nanowires can be achieved by using DNA and pyrrole. Oxidation of pyrrole in DNA-containing solutions yields a material that contains both the cationic polypyrrole (PPy) and the anionic DNA polymers. Intimate interaction of the two polymer chains in the self-assembled nanowires is indicated by FTIR spectroscopy. AFM imaging shows individual nanowires to be continuous, approximately 5 nm high and conformationally flexible. This feature allows them to be aligned by molecular combing in a similar manner to bare DNA and provides a convenient method for fabricating a simple electrical device by stretching DNA/PPy strands across an electrode gap. Current-voltage measurements confirm that the nanowires are conducting, with values typical for a polypyrrole-based material. In contrast to polymerisation of pyrrole on a DNA template in bulk solution, attempts to form similar wires by polymerisation at surface-immobilised DNA do not give a continuous coverage; instead, a beads-on-a-string appearance is observed suggesting that immobilisation inhibits the assembly process.