Improved thermal stability of polybenzoxazines by transition metals

The incorporation of various transition metal salts increases the char formation of polybenzoxazines. It is shown that the effect of the transition metal salt is not simply additive and is independent of the amine and phenol structures. While the metal salts have an insignificant effect on the polymerization, their presence in benzoxazine favors the formation of carbonyl functional groups. It is proposed that reduced flammability of polybenzoxazines is achieved through the evolution of CO₂ during thermal degradation.     

An organic p-type dopant with high thermal stability for an organic semiconductor

To overcome the thermal instability of a p-doped organic hole transporting layer using the state-of-the-art p-type dopant, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, a potent electron accepter, 3,6-difluoro-2,5,7,7,8,8-hexacyanoquinodimethane, has been found to possess superior thermal stability and proved to be an excellent p-type dopant.     

Effect of fluorination on the stability of carbon nanofibres in organic solvents

Beneficial effects of fluorination on the stability of carbon nanofibre (CNF) dispersion in organic solvents as a function of time are evidenced. Because of their excellent friction properties, fluorinated CNFs (CF_0.85) can be used as nanoparticles of tribo-active phase in lubrication; however, they have to be added into a matrix. We have shown that mixtures of CF_0.85 are more stable than CNF solutions. Investigations by ultraviolet–visible spectroscopy have been carried out 2 h after sonication and after an ageing of 4 months. Hansen solubility theory was used, and after ageing, tribological and Raman spectroscopy experiments showed no significant modification of physicochemical properties of the CF_0.85.     

Improved stability of molecular organic EL devices

Influence of emission sites on emission efficiency and running durability of molecular organic electroluminescent devices was investigated. When fluorescent dye rubrene was doped into TPD diamine hole transport layer, rubrene molecule emitted bright yellow light with a max. luminance of 61 000 cd/m². The device had the highest efficiency of 9.8 Im/W at 100 cd/m². Half-decay time of the device from initial luminance of 530 cd/m² under constant direct current was 3 600 h. On the other hand, when rubrene was doped into BeBq₂ complex electron transport layer, the efficiency was 4.4 Im/W and the half-decay time was 110 h. Thus doping site is found to exert significant influence both on the emission efficiency and the running durability.     

Improved thermal stability of phenolic resin by graphene-encapsulated nano-SiO2 hybrids

Phenolic resin (PR) modified with hybrids of reduced graphene oxide (RGO)-encapsulated nano-SiO₂ (SiO₂–RGO) was prepared by a simple method. The synergistic effect of RGO and nano-SiO₂ was achieved in the thermal decomposition of the modified PR. Thermal stability of SiO₂–RGO and the modified PR was evaluated by thermogravimetric analysis (TG). With 1 mass% loading of SiO₂–RGO, the maximum decomposition temperature (T_dmax) of the modified PR was increased by 32.50 °C and the residual mass at 800 °C was increased by 6.54%. The structure of the resin char was characterized to study the mechanism of ameliorative thermal stability. SiO₂–RGO hybrids were conducive to induce the PR to form graphitized carbon in the pyrolysis process. Thus, SiO₂–RGO can facilitate the application of PR in the fields of heat insulation and ablation resistance.

     

Improved thermal stability of Langmuir-Blodgett films through an intermolecular hydrogen bond and metal complex

Langmuir-Blodgett (LB) films of N-octadecanoyl-L-alanine and its silver and zinc complexes have been investigated by variable-temperature Fourier transform infrared transmission spectroscopy. The thermal stability of LB films is improved through an intermolecular hydrogen bond and metal complex. The intermolecular hydrogen-bonding interaction between hydrophilic head groups in the same monolayers and the metal complex between one head group and another in the neighboring monolayers considerably increase the interaction between the corresponding hydrophobic alkyl chains. It is shown that the transformation of the triclinic subcell packing of the molecules in the LB films prior to and after the silver complex into hexagonal packing occurs before the phase transition accompanied with a change in molecular orientation. The phase transition behavior of the LB films is varied from a small temperature interval to large one depending on the hydrogen bond and metal complex.     

Enhanced thermal stability of polypyrrole hexagonal microplates fabricated by organic crystal surface-induced polymerization

The stability of polypyrrole hexagonal microplates (PHMs) fabricated by organic crystal surface-induced polymerization (OCSP) in the presence of 4-sulfobenzoic acid monopotassium salt (SBAK) crystals was examined during thermal aging at 150 °C for 10 h under air and nitrogen atmospheres. Thermal stability of PHMs and conventional polypyrroles (CPPys) was evaluated in terms of the resistivity (R_t) after aging for t h, normalized to the initial resistivity (R₀) before aging, R_t/R₀. Although the PHMs maintained R₁₀/R₀ values of 21.9 and 3.0 under air and nitrogen, respectively, the CPPys exhibited much higher R₁₀/R₀ values, of 853.8 and 14.6, respectively. A possible explanation for the enhanced thermal stability of the PHMs is the higher thermal stability and the antioxidant effect of SBAK dopant molecules. Thermo-oxidative degradation was accelerated due to direct chemical attack on the cationic pyrrole rings of atmospheric water and oxygen, leading to a steep increase in surface resistivity. The development of carbonyl defects on PPy chains during thermal aging was monitored using Fourier transform-infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Ultraviolet-visible (UV-vis) spectroscopy revealed that the PHMs essentially retained the bipolaron structures, even after thermal aging for 10 h in air, whereas the CPPys showed almost no bipolaron structures.     

Synthesis of ferrierite-type zeolite by microwave method using ethylenediamine as an organic structure-directing agent

A new method for the synthesis of ferrierite-type zeolite has been developed using microwave irradiation in the presence of structure-directing agents (templates). The physicochemical characteristics of the synthesized zeolites were investigated by X-ray diffraction analysis, low-temperature nitrogen adsorption–desorption and SEM-EDX. When comparing the synthesis products, it was found that microwave irradiation significantly reduces the crystallization time of the synthesized zeolites compared to traditional hydrothermal treatment     

Solvent-free fluorination of organic compounds using N-F reagents

Efficient fluorination of 1,3-dicarbonyl compounds, enol acetates of aromatic ketones, and activated aromatic compounds was achieved under solvent-free conditions using Selectfluor™ F-TEDA-BF₄ or Accufluor™ NFSi.     

Selective fluorination of adamantanes by an electrochemical method

Selective fluorination of adamantanes was achieved by the electrochemical fluorination method, using Et 3N-5HF as electrolyte and a fluorine source. Mono-, di-, tri-, and tetrafluoroadamantanes were selectively prepared from adamantanes by controlling the oxidation potential, and the fluorine atoms were introduced selectively at the tertiary carbons. Adamantanes that have functional groups such as ester, cyano, and acetoxymethyl were also fluorinated selectively.     

Reactions of organic exhausts and the thermal stability of catalysts

The catalytic combustion of various organic compounds has been investigated over noble and non-noble metal catalysts using a fixed bed. It was concluded that the activity order of different organic compounds on a noble metal catalyst, is toluene > 2-butanone > benzene >n-heptane≈isopropyl alcohol > acrylonitrile > cyclohexane. On non-noble metal catalyst, it is isopropyl alcohol > 2-butanone > acrylonitrile > toluene >n-heptane > cyclohexane > benzene. In order to compare the thermal stability of catalysts, the catalytic reaction of toluene has been studied over noble and non-noble metal catalysts which were calcined at various temperatures up to 900°C for 3 h.     

The fluorination of organic substrates with tetraphenyl-phosphonium hydrogendifluoride

Tetraphenylphosphonium hydrogendifluoride acts as a powerful source of F^? in various reactions with organic substrates to give fluorine containing-products     

Improved thermal stability of crosslinked PTFE using fluorine gas treatment

Crosslinked PTFE (XF) samples were fluorinated at 293-593 K under 0.7-101 kPa F₂ and for 1 h to 7 days to improve its thermal stability. Because the weight uptake which may be caused by the fluorine addition was detected at room temperature, CC bonds in XF can be fluorinated and the fluorine content was saturated after 72 h. Weights of all samples increased more than that of original XF through additional fluorination of CC bonds, whereas it decreased by the chain-scission to form gaseous fluorocarbons such as CF₄. The intensity ratio in IR spectra of the peaks correspond to the double bond (CFCF₂) at 1785 cm⁻¹ and the characteristic peaks of PTFE at 1794 cm⁻¹, I_PTFE/I_PTFE was smaller for the fluorinated XF rather than that for XF. Average values of heat of crystallization (ΔH_c) for all fluorinated XF samples were about 2 J/g higher than that of the original XF. The decomposition temperature calculated from the TG curves increased with increasing reaction temperature and reaction time up to 72 h. Thermal stability of XF was improved through fluorine gas treatment.     

Electroytic partial fluorination of organic compounds. 52. Regio- and diastereoselective anodic fluorination of thiazolidines

Anodic fluorination of N-benzoyl, N-acethyl-, and N-formylthiazolidine derived from L-cysteine was carried out in dimethoxyethane (DME) and acetonitrile containing various supporting fluoride salts using an undivided cell. Highly regioselective fluorination proceeded to provide the corresponding 5-monofluorinated thiazolidine derivatives in good yields in DME, and the diastereoselectivitiy was moderate to high regardless of the supporting fluoride salts. The diastereoselectivitiy of the fluorination was greatly affected by the bulkyness of the subsitituent on the nitrogen atom, and N-benzoylthiazolidine gave much higher diastereoselectivity compared with N-formyl derivative. The fluorination of the thiazolidines was not achieved by commercially available fluorinating reagents such as N-fluoropyridinium salts.     

Evaluation of thermal stability,an overview

A systematic application of thermal analytical techniques for the assessment of the thermal stability of a material is emphasized. This approach employs ASTM E-27.02 (Methods of Test) and is illustrated using a sulfur—nitrogen heterocyclic compound model.     

Influence of purity on the thermal stability of solid organic compounds

DSC method was used to study thermal stability of nitrocompounds. It was assumed the model to estimate stability of solid phase in which perfect solid phase is totally stable and amorphous-liquid domains connected with impurities decompose according to the kinetic model determined for the liquid phase above the melting point. The influence of sample purity on relative stability, which is k _l/k _s — ratio of decomposition rate constants in liquid and solid phase, at temperature 20 K below the melting point was predicted. The increase of liquid domains in solid phase causes decrease of k _l/k _s ratio (relative stability) at chosen temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Electrolytic partial fluorination of organic compounds. Part 78: Regioselective anodic fluorination of 2-oxazolidinones

Various 2-oxazolidinones were galvanostatically electrooxidized in the presence of various fluoride salts. It was found that a fluorine atom was introduced to the α-position of the nitrogen atom of N-acyl- and N-alkoxycarbonyl-2-oxazolidinones to provide the corresponding α-fluorinated products in moderate to good yields. In the case of N-phenoxycarbonyl derivative, fluorination took place on the phenyl group selectively.     

Advances in fluorination of organic compounds with sulphur tetrafluoride

Sulphur tetrafluoride has been known since 1958 as an efficient fluorinating agent for replacing oxygen atoms in carbonyl groups by fluorines. In the past fifteen years a number of new reactions of sulphur tetrafluoride with carbonyl compounds have been discovered. These include formation of bis(1,1-difluoroalkyl) ethers from alkanecar☐ylic acids, bis(1-fluoroalkyl) ethers from aliphatic aldehydes, and cyclic fluoroethers from difunctional car☐ylic acids and aldehydes. In the reactions with branched aldehydes rearrangements of hydrogen and fluorine atoms and also of the carbon skeleton were observed. Tertiary amides were successfully converted to 1,1-difluoroamines and tertiary formamides to trifluoromethylamines. This last reaction involves simultaneous fluorination of the carbon-oxygen and carbon-hydrogen bonds.Participation of carbocations in the mechanism of fluorination of carbonyl groups has been proved and a revised mechanism proposed. Evidence for a reduction-oxidation mechanism for the replacement of formyl hydrogen by fluorine has also been found.