Zur Darstellung von Cyclophosphaten,Cyclophosphatophosphonaten, Diphosphonaten und Diphosphiten in Harnstoffschmelzen

Preparation of Cyclophosphates, Cyclophosphatophosphonates, Diphosphonates, and Di-phosphites in Urea Melts Ammonium cyclotriphosphate (NH₄)P₃O₉, ammonium cyclotetraphosphate [P^IV? P^IV ? O? ]₂, ammonium cyclotriphosphatophosphonates Ammonium organyldiphosphonates And ammonium diphosphites are prepared in high yields on heating acidic phosphates, phosphonates, and phosphites in urea or urea/ammonium nitrate melts. The mechanism of the dehydration of phosphorus compounds containing POH groups in molten urea is discussed.     

Electrostatically Dissipative Polystyrene Nanocomposites containing Copper Nanowires

Summary: A scalable synthesis of copper nanowires by alternating current electrodeposition into porous aluminium oxide was used to produce multigram quantities of 16 nm diameter by >2 µm long nanowires. Polystyrene nanocomposites were prepared by solution processing. The composites containing unpassivated nanowires were non‐uniformly dispersed and showed electrical percolation at ≈2 vol.‐% Cu loading, while the composites containing HSC₁₈H₃₇‐passivated nanowires were uniformly dispersed, but remained resistive up to at least 10 vol.‐% Cu loading.

Copper nanowires prepared by alternating current electrodeposition into porous aluminium oxide templates.     

Effects of molecular weight,rubber toughening,and environment on fatigue crack propagation behavior of block amide copolymers

The Fatigue Crack Propagation (FCP) behavior of block amide copolymers is investigated as a function of molecular weight, rubber toughening as well as environmental conditions. The enhancement of FCP resistance with increasing average molecular weight is shown and correlated to features observed on the fracture surface. Particular attention is paid to hysteretic heating, measured with an infrared camera, in the crack tip zone of different average molecular weight copolymers and rubber-toughened copolymer. A FCP approach of stress-cracking in an aqueous solution of zinc chloride is proposed here. An improvement in FCP resistance as the average molecular weight increases, similar to that exhibited in normal environment, appears. The shift in da/dN values over the tested range of can be approximated by an exponential function:      

Synthesis of titanium polythioethers

The synthesis of polythioethers of the form was effected, where C_p denotes cyclopentadienyl. Four reaction systems were studied and evaluated. Two proved to be undesirable (the “reverse” interfacial and organic solution methods), while two proved acceptable (the “normal” interfacial and aqueous solution methods). A number of added bases were evaluated. Et₃N and NaOH were found to be acceptable. Yield increases with reaction time for aqueous solution syntheses, while yield remains constant with reaction time for synthesis via the normal interfacial method.     

Reactivity Study of Elementary Steps in the Polymerization Mechanism of Acrylfuranic Compounds by Frontier Molecular Orbital Theory

A reactivity study of the most important elementary steps (propagation, intermolecular degradative transfer, and re‐initiation) in free‐radical polymerization of acrylfuranic systems, furfuryl acrylate (FA), and furfuryl methacrylate (FM), using the frontier molecular orbital theory is described. A qualitative explanation of reactivity trends of these steps for both systems is given based on absolute values of the SOMO/HOMO gap. The small difference between values of k_p for FA and FM compared to that found for MA and MMA ( ) is justified semi‐quantitatively by applying a formulation for the change of energy in the transition state using second‐order perturbation theory.

     

Oxazolidines versus schiff bases

The formation of oxazolidines from propionaldehyde and aliphatic β-aminoalcohols is complicated by the appearance of appreciable amounts of unsaturated Schiff bases. The simple Schiff base, often the dominant species when aromatic aldehydes react with amines, could not be detected in the present aliphatic systems. We conclude that in aliphatic systems the order of stability is and . The gem-dimethyl group α to nitrogen stablizes the heterocyclic ring remarkably.     

The Ring Opening Metathesis Polymerisation Toolbox

Summary: The success of metathesis chemistry techniques has sparked a tremendous interest in polymer and material chemistry. This contribution provides an overview of the state of the art in ring opening metathesis polymerisation (ROMP). It is intended to provide the reader with useful information on the interplay of initiators, monomers, and reaction conditions, thus aiding polymer chemists to utilise the ROMP toolbox. Prominent and illustrative examples from current research are given in the article.

The “ROMP toolbox”.     

Polymer/Laponite Composite Latexes: Particle Morphology,Film Microstructure,and Properties

Transparent film materials with excellent mechanical and thermal properties were elaborated by drying a latex suspension of armored polymer/Laponite composite particles. Low‐temperature TEM observation of ultrathin cross‐sections of the films indicated a unique network morphology characterized by a “honeycomb” distribution of the Laponite platelets remindful of the original particles morphology.

     

Synthesis of titanium polyesters

Titanium polyesters of the form where Cp denotes cyclopentadiene, have been synthesized by utilizing both the interfacial and solution techniques. Polymer yield increases with reaction time. The reactive titanium reactant in the solution polycondensations is believed to be the Cp₂Ti⁺² cation.     

Kinetics,mechanism, and endo selectivity of Diels–Alder reactions of alkylmonosubstituted ethenes with cyclohexa-1,3-diene in the gas phase

The reactions where Y = CH₃ (M), C₂H₅ (E), i? C₃H₇ (I), and t? C₄H₉ (T) have been studied between 488 and 606 K. The pressures of CHD ranged from 16 to 124 torr and those of YE from 57 to 625 torr. These reactions are homogeneous and first order with respect to each reagent. The rate constants (in L/mol·s) are given by The Arrhenius parameters are used as a test for a biradical mechanism and to discuss the endo selectivity of the reactions.     

Synthesis of POSS‐Functionalized Polyisobutylene via Direct Initiation

POSS‐functionalized polyisobutylenes (PIBs) were synthesized by carbocationic polymerization using an epoxy‐POSS/TiCl₄ initiating system in hexane/methyl chloride (60:40 v/v) solvent mixture at −80 °C. ¹H NMR spectroscopy verified the incorporation of one epoxy‐POSS per polymer chain. Light scattering and TEM analysis demonstrated the formation of 50–100 nm sized aggregates and micron‐sized clusters.

     

Reductive Formation of Isospecific Ti Dinuclear Species on a MgCl2 (110) Surface in Heterogeneous Ziegler‐Natta Catalysts

Dinucleation of TiCl₄ on the MgCl₂ (100) surface has been conventionally believed as the origin of the stereospecificity of heterogeneous Ziegler‐Natta catalysts for propylene polymerization, while the MgCl₂ (110) surface has been regarded as non‐stereoselective in the absence of organic donors. Based on periodic density functional calculations, we propose a new isospecific Ti dinuclear species on the MgCl₂ (110) surface, which is formed as a result of reduction of Ti from 4+ to 3+. The new species closely resembles the dinuclear species on the (100) surface, but two Ti ions are obliquely stacked along the (110) surface through Cl bridges. The results address the importance of the reduction and re‐distribution of surface Ti species after contacting with cocatalysts in considering the origin of the stereospecificity.

     

Electron impact studies. CVII—Negative ion mass spectra of the oxime group. Monoximes derived from α-dicarbonyl systems

Specific losses of water are observed from the molecular anions of monoximes of α-diketones. Labelling studies, kinetic energy release values and the +E spectra of ions have been used to aid in the elucidation of the fragmentation pathways. It is proposed that the majority of ions have α-keto nitrile structures.     

Photoelectrochemistry with Colloidal Semiconductors; Laser Studies of Halide Oxidation in Colloidal Dispersions of TiO2 and α-Fe2O3

Aqueous sols of TiO₂ (anatase, particle radius 25 Å) were excited with (347.1 nm)-laser light and the reaction of valence-band holes with halide ions (X = I^?, Br^?, Cl^?) was investigated. Hole transfer takes place within the duration of the (10 ns)-laser pulse and results in the formation of anion radicals according to the sequence: The quantum yield of X increases in the order Cl < Br < I, attaining 0.8 for I at pH 1. It is affected by pH, halide concentration and the presence of a protective agent for the sol. RuO₂ deposited onto TiO₂ enhances markedly Cl and Br -formation, but has no effect on the yield of I. Laser-photolysis investigation of halide oxidation were also carried out with colloidal Fe₂O₃ (particle radius 600 Å). For I_2?formation, the quantum yield exceeds 0.9 indicating almost quantitative hole scavenging by iodide.     

Effect of Molecular Weight on Photoinduced Birefringence in a Chiral Liquid Crystalline Azodye Polymer

Summary: The evolution of the photoinduced birefringence in thin films of narrow polymer fractions is studied and compared with the behavior of the non‐fractionated polymer. The Δn_ind value decreases by increasing the degree of polymerization ( ) within the oligomeric range but becomes independent of molecular weight starting from a of ≈70. Thermal pretreatment of the films results in higher photoinduced birefringence. The films show good stability of the photorecording.

Birefringence induced after 10 min, Δn_ind(600) and its growth rate at the same moment versus molecular weight.     

Structure of the tetramer of α-methylstyrene

The structure of the tetrameric dianion formed by α-methylstyrene in tetrahydrofuran by reaction with sodium has been examined. Mass spectral, NMR, infrared, and kinetic data all indicate that the structure is rather than the structure which had previously been assumed for this species.     

Synthesis of phosphorus-containing poly-o-acylamideoximes from polyacrylonitrile

The synthesis of phosphorus-containing poly-O-acylamideoximes from polyacrylonitrile has been accomplished by the reaction sequence: Reaction is believed to occur at the NH₂ nitrogen as well as at the oxime group, but reaction is not believed to occur at both groups in the amide oxime unit. Inclusion of the phosphorus moiety occurs in the medium to high range.     

The double-melting behavior of poly(ether diphenyl ether ketone)

Poly(ether diphenyl ether ketone) (PEDEK) synthesized by the nucleophilic route has the following chemical structure: At some given temperatures for a given time isothermally crystallized PEDEK sample exhibits two endothermic peaks which are similar to PEEK and PEEKK. The melting behavior of PEDEK crystallized from the glassy state is investigated through differential scanning calorimeter (DSC). We consider that the high-melting peak is related to the perfect crystals and the low-melting peak is associated with a few imperfect crystals. © 1997 John Wiley & Sons, Inc.     

Clay Functionalization and Organization for Delamination of the Silicate Tactoids in Poly(L‐lactide) Matrix

Summary: Three kinds of organoclay, i.e., Cloisite15A® (C15A), Cloisite20A® (C20A), and Cloisite30B® (C30B) were modified with silane to prepare twice functionalized organoclay (TFC). The pristine Cloisite® clays and the TFC were melt compounded with poly(L ‐lactide) (PLLA) and morphology of the composites was observed to elucidate the effects of the d₀₀₁ gallery distance, the epoxy content of TFC, and the compatibility between the organic ammonium surfactant and PLLA on the degree of exfoliation of the clay layers.

Plots of I_TFC/I_Cloisite versus epoxy content for PLLA composites with (a) Cloisite15A® (C15A), (b) Cloisite20A® (C20A), (c) Cloisite30B® (C30B).     

Azoalkanes: A Novel Class of Flame Retardants

Summary: The synthesis of azoalkanes such as azocyclohexane ( 1 ) and 4,4′‐bis(cyclohexylazocyclohexyl)methane ( 2 ) and their use as flame retardants in polymeric substrates is reported. For the first time it is demonstrated that azoalkanes alone can effectively provide flame retardancy and self‐extinguishing properties to poly(propylene) films at a very low concentration of 0.25 to 0.5 wt.‐%. All the poly(propylene) formulations passed DIN 4102‐1/B2 standards and the instant azoalkane‐containing poly(propylene) blends show no discoloration.

4,4′‐bis(cyclohexylazocyclohexyl)methane.