Search results for "Hydrogen"

Phase transitions and distortion of [BiCl6]3- octahedra in (C3H5NH3)3[BiCl 6] - DSC and single-crystal X-ray diffraction studies

2004

The DSC diagram of tris(allylammonium) hexachlorobismuthate(III), (C3H5NH3)3[BiCl6], revealed three anomalies at 152, 191 and 299 K. The structure of the salt was determined at 200 and 315 K, below and above the high-temperature phase transition at 299 K. In both phases the crystals are monoclinic. At 200 K the space group is C2/c whereas at 315 K it is C2/m. The structures, at both temperatures, are composed of [BiCl6]3− octahedra and allylammonium cations. The organic and inorganic moieties are attracted to each other by a network of the N-H. . .Cl hydrogen bonds. The relationship between corresponding parameters of the unit cells has been found. The phase transition at 299 K, of the orde…

Rheological Consequences of Hydrogen Bonding: Linear Viscoelastic Response of Linear Polyglycerol and Its Permethylated Analogues as a General Model …

2014

Viscoelastic properties of linear, hydroxyl-functional polymers are only little understood with respect to the effect of functional group interactions. Melt rheology and thermal phase transitions of linear polyethers (polyglycerol, linPG-OH) and their methylated analogues (linPG-OMe) in a broad molecular weight range (Mn = 1–100 kg/mol) with low polydispersities (PDI) have been investigated as a general model for hydroxyl-functional polymers with respect to their functionality and hydrogen bond interactions. We provide detailed insight into the rheodynamics of nonentangled and well-entangled polyethers bearing one functional group per monomer unit. Booij–Palmen plots (BBP) revealed failure …

1991

Thermoanalytical studies on an order-disorder transition resulting from supramolecular organization of hydrogen bond motifs in an unpolar (polymer-) matrix are reported. Functional groups having two potential sites for hydrogen bonding (4-carboxyphenylarazole) are located statistically along the polybutadiene backbone. Multistep hydrogen bond formation leads to the formation of association chains whose lengths can be controlled by addition of monofunctional groups (phenylurazole) like in conventional stepgrowth polymers. The association chain length is estimated from the variation of transition enthalpy and «melting» temperature

Hydrogen bonds in unpolar matrix — Comparison of complexation in polymeric and low molecular-weight systems

1991

By ene-reaction of 4-phenyl-1,2,4-triazoline-3,5-dione with double bonds, polar 4-phenyl-1,2,4-triazolidine-3,5-dione (phenyl urazole) groups are introduced into unpolar matrices. Hydrogen-bond complexes are formed between two amide-like units. The temperature dependence of complex formation in dilute hydrocarbon medium is obtained from remperature-dependent IR spectra in the region of the C=O stretching vibration. Results obtained for a low molecular-weight model system are compared with modified polybutadienes, where the groups are attached statistically along the polymer backbone. The enthalpy and the entropy of complex formation (ΔH f =−28.6 kJ/mol; ΔS f =−52 J/mol K−1) obtained for the…

Water-Soluble Poly(vinylferrocene)-b-Poly(ethylene oxide) Diblock and Miktoarm Star Polymers

2012

We describe the synthesis of water-soluble diblock and miktoarm star polymers consisting of poly(vinylferrocene) (PVFc) and poly(ethylene oxide) (PEO) blocks. First, end-functionalized poly(vinylferrocene) was generated by end-capping the living carbanionic PVFc chains with benzyl glycidyl ether (BGE) or ethoxy ethyl glycidyl ether (EEGE). Acidic hydrolysis of the EEGE-terminated PVFc partially oxidized the PVFc backbone. However, the dihydroxyl end-functional PVFc was obtained in quantitative yields by hydrogenolysis of the BGE-terminated PVFc. A series of block copolymers and AB2 miktoarm star copolymers was obtained in a second polymerization step, utilizing the respective end-functional…

Cooperative structure formation by combination of covalent and association chain polymers: 4. Designing functional groups for supramolecular structur…

1991

Abstract A small number of polar functional groups are attached to polybutadiene by a polymer analogous reaction. Depending on their molecular structure, different degrees of supramolecular ordering result from the aggregation of these polar groups. In the case of phenylurazole units, which carry a single site for hydrogen-bond complexation, binary contacts are formed; whereas linear association chain structures are formed in the case of polybutadiene carrying phenylurazole units additionally substituted with a carboxy group in meta or para positions of the phenyl ring. In the latter case, association chains aggregate cooperatively to an ordered supramolecular structure. The different struc…

Hairy Aramide Rod−Coil Copolymers

2010

We have synthesized monodisperse “hairy rod oligomers” based on oligo(p-benzamide)s carrying alkyl side chains and conjugated them with polydisperse poly(ethylene glycol) (PEG) chains. The well-defined oligomers were synthesized from 4-amino-2-hexyloxybenzoic acid using a commercial peptide synthesizer. The PEG conjugated hairy rod−coil block copolymers self-assemble in polar and nonpolar organic solvents. The self-organization in solution was investigated by dynamic light scattering (DSL) and transmission electron microscopy (TEM) as a function of solvent, equilibration time, and polarity of the substrate. Individual fibers and fiberlike bundles of aggregates could be observed. As all hydr…

Chemoenzymatic synthesis of a poly(hydroquinone)

1999

Chemoenzymatic synthesis of a poly(hydroquinone) was achieved by enzymatic oxidative polymerization of 4-hydroxyphenyl benzoate, followed by alkaline hydrolysis of the resulting polymer. The polymerization of 4-hydroxyphenyl benzoate was performed using a peroxidase and hydrogen peroxide as catalyst and oxidizing agent, respectively, in an aqueous organic solvent. Soybean peroxidase afforded the polymer in good yields. IR analysis of the polymer showed the formation of the polymer consisting of a mixture of phenylene and oxyphenylene units. By alkaline hydrolysis of the resulting polymer, benzoate moiety was completely removed to give poly(hydroquinone).

pH-sensitive hydrogel based on a novel photocross-linkable copolymer.

2004

A pH sensitive hydrogel has been prepared by a UV irradiation technique. Starting polymer was the PHM (poly hydroxyethylaspartamide methacrylated) obtained from polyaspartamide (PHEA) partially derivatized with methacrylic anhydride (MA). This new copolymer has been further derivatized with succinic anhydride (SA) to obtain PHM-SA that has been cross-linked by UV irradiation to form a pH sensitive hydrogel. The network, recovered after washing as a powder, has been been characterized by FT-IR spectrophotometry and particle size distribution analysis. Moreover, to have information about water affinity of the prepared sample, swelling measurements have been carried out in aqueous media mimick…

The effect of potassium on the selective oxidation ofn-butane and ethane over Al2O3-supported vanadia catalysts

1995

The catalytic properties of undoped and K-doped (K/V atomic ratio of 0.5) Al2O3-supported vanadia catalysts (∼4.5 wt% of V2O5) for the oxidation ofn-butane and ethane were studied. Isolated tetrahedral V5+ species are mainly observed in both undoped and K-doped samples. The incorporation of potassium decreases both the reducibility of surface vanadium species and the number of surface acid sites. Potassium-free vanadium catalysts show a high selectivity during the oxidative dehydrogenation (ODH) of ethane but a low selectivity during the ODH ofn-butane. However, the presence of potassium on the vanadium catalysts strongly influences their catalytic properties, increasing the selectivity to …