Fluoride catalysis at 175°C. of the reaction: Glycerol plus fatty acid

1. In uncatalyzed reactions the esterification of stearic, oleic, and linolenic acid proceeded at the same general rate though the speed was somewhat enhanced as the degree of unsaturation of the fatty acid increased. None of the reactions went to completion, after 15 hours being 72%, 83%, and 84%, respectively, completed. Only a small fraction of the distearate was converted to the triglyceride; a greater amount of the dioleate was esterified to the trioleate and about half the dilinolenate was changed to the trilinolenate.
2. Of 15 metallic fluorides studied, all afforded some catalysis, but only antimony trifluoride and zinc and cobalt fluorides were outstanding. Antimony trifluoride was the most active although in large amount it caused severe decomposition and charring of the products. Zinc fluoride had the best general properties, approaching antimony trifluoride yet causing practically no decomposition even in high concentration. Its activity was enhanced with an increase in amount, the best concentration apparently being 0.1 mole per 100 grams fatty acid. Antimony trifluoride was also better in larger amount within limits, but cobalt fluoride did not exhibit this property.
3. With zinc fluoride as catalyst the reactions of stearic, oleic and linolenic acids after 15 hours were 95%, 94%, and 92%, respectively, completed. At least three-fourths of the diglycerides were converted to triglycerides. From a study of reaction velocities, zinc fluoride caused the monoglyceride to form at a rate approximately four times that of the uncatalyzed reaction and the diglyceride at a six-fold rate. The triglyceride was formed at an almost undiminished rate whereas in the uncatalyzed reaction the formation of triglyceride was diminished rapidly.
4. Unsaturation and viscosity were not affected seriously in the presence of the fluorides except antimony trifluoride. Certain other fluorides caused severe darkening but without accompanying serious decomposition.

     

Synthesis and Characterizations of Triphenylamine End-Functionalized Polymers via Reversible Addition-Fragmentation Chain Transfer Polymerization

A novel reversible addition-fragmentation chain transfer (RAFT) reagent bearing triphenylamine (TPA) group, 4-diphenylamino-dithiobenzoic acid benzyl ester (DDABE), was designed and synthesized. It was used in the RAFT polymerizations of styrene (St) and methyl acrylate (MA) to prepare end-functionalized polymers. The results of the polymerization showed that the RAFT polymerizations could be well controlled using DDABE as the RAFT agent. Number-average molecular weight (M_n,GPC) increased linearly with monomer conversion, and molecular weight distributions were relatively narrow (PDI< 1.50). The results of chain-extension reaction, ¹H NMR spectra and UV/Vis spectra confirmed that most of the polymers chains were end-capped by the functional triphenylamine (TPA) groups. The effect of feed molar ratios of St/DDABE/AIBN on polymerization was investigated.     

Synthesis and physicochemical characterization of a well-defined poly(butadiene 1,3)-block-poly(dimethylsiloxane) copolymer

For the first time, order-order and order-disorder transitions were detected and characterized in a model diblock copolymer of poly(butadiene-1,3) and poly(dimethylsiloxane) (PB-b-PDMS). This model PB-b-PDMS copolymer was synthesized by the sequential anionic polymerization (high vacuum techniques) of butadiene 1,3 (B) and hexamethylciclotrisiloxane (D₃), and subsequently characterized by nuclear magnetic resonance (¹H and ¹³C NMR), size exclusion chromatography (SEC), Fourier Transform infrared spectroscopy (FTIR), Small-Angle X-ray scattering (SAXS) and rheology. SAXS combined with rheological experiments shows that the order-order and order-disorder transitions are thermoreversible. This fact indicates that the copolymer has sufficient mobility at the timescale and at the temperatures of interest to reach their equilibrium morphologies.     

Stability of hydrogenated nanodiamonds under extreme ultraviolet irradiation

It is generally accepted that diamond is resistant to a wide spectrum of electromagnetic radiation from the ultraviolet through to the soft X-ray range, which makes it very attractive for the fabrication of diamond-based photodetectors. However the effect of photon radiation on the diamond structure has not yet been examined. In the work presented here, photoelectron spectroscopy has been used to study the graphitization of nanodiamond crystallites exposed to extreme ultraviolet radiation. Under such irradiation, the surface hydrogen groups and graphite species are found to prevent graphitization. The mechanism of radiation-induced nanodiamond graphitization is discussed.     

Efficient allylation of cellulose in dimethyl sulfoxide/tetrabutylammonium fluoride trihydrate

The cellulose solvent dimethyl sulfoxide (DMSO)/tetrabutylammonium fluoride trihydrate (TBAF) was successfully applied as reaction medium for the synthesis of allyl cellulose by conversion of the polymer with allyl chloride in the presence of solid NaOH. Samples with degree of substitution from 0.50 to 2.98 were accessible by varying the molar ratio anhydroglucose unit:allyl chloride:NaOH and reaction time. DMSO/TBAF was found to be an efficient reaction medium for the preparation of highly functionalized samples from spruce sulfite pulp with degree of polymerization of about 500 even in a scale of 50 g. The allyl cellulose samples were characterized by means of FTIR- and NMR spectroscopy. Size exclusion chromatography revealed negligible polymer degradation during synthesis and purification of the samples.     

Molecular weight effect on the obtainment of parallel and perpendicular orientation in thermotropic poly(diethylene glycol <Emphasis Type="Italic">p,p′</Emphasis>-bibenzoate)

Summary The effect of molecular weight on the uniaxial orientation process has been analyzed in two samples of thermotropic poly(diethylene glycol p,p′-bibenzoate), evaluating the influence of that parameter on the type of orientation obtained. Several strain rates and deformation temperatures have been tested in order to map out the conditions for obtaining the two different kinds of orientation. The results show that in the lower molecular weight PDEB sample (M_w=31200) it is rather easy to get exclusively perpendicular “anomalous” orientation, with the molecular axes aligned transversely to the stretching direction. However, it is extremely difficult to obtain 100% parallel “normal” orientation. On the contrary, either type of orientation or a mixture of them can be easily developed for the higher molecular weight PDEB sample (M_w=102900).     

Effect of vibration condition and inter-particle frictions on the packing of uniform spheres

We present a numerical study of the packing of uniform spheres under three-dimensional vibration using the discrete element method (DEM), focusing on the effects of vibration condition (amplitude and frequency) and inter-particle frictions (sliding and rolling frictions). The results are analysed in terms of packing density, coordination number (CN), radial distribution function (RDF) and pore structure. It is shown that increasing either the vibration amplitude or frequency causes packing density to increase initially to a maximum and then decrease. Both vibration frequency and amplitude should be considered to characterize the effect of vibration process on packing structure. The sliding and rolling frictions between particles can decrease packing density since they dissipate energy, although the effect of rolling friction is less significant. In line with the change of packing density, microstructural properties such as CN, RDF and pore distribution also change: a looser packing often corresponds to smaller CN, less peaked RDF and larger but more widely distributed pores.     

Synthesis of TiO<Subscript>2</Subscript> Hybrid Molecular Imprinted Polymer for Ethofumesate Linked by Silane Coupling Agent

TiO₂ hybrid molecular imprinted polymer (MIP) for ethofumesate using methacrylic acid (MAA) as the functional monomer and silane coupling agent 3-(trimethoxysilyl) propylmethacrylate (KH570) as organic–inorganic connective bridge was synthesized via photo-excitation method. Hydrogen bond was proved to act between MAA and ethofumesate for pre- and post-polymerization binding properties as testified by UV spectrometric method. KH570 modified TiO₂ nanoparticles were prepared via sonochemical reaction, which can accelerate hydrolysis, increase collision chance for the reactive system and improve the dispersion of the nanoparticles. Scanning electron microscope (SEM), transmission electron microscope (TEM), binding and the adsorption kinetics experiments as well as thermogravimetric analysis (TGA) were employed for characterization. The results indicated that the hybrid MIP revealed a larger surface area and more ordered imprinting cavities with improved thermal stability compared to organic-only MIP. Furthermore, faster adsorption kinetics and enhancive adsorption capacity were achieved, which made it promising in chemical sensor applications.     

Metathesis as a versatile tool in oleochemistry

Olefin metathesis, awarded with the Nobel Prize in Chemistry 2005 for Chauvin, Grubbs and Schrock, has emerged as a powerful tool for organic as well as polymer chemistry. In oleochemistry, this reaction is well known and has been applied for many decades. Examples include the functionalization of the double bonds of different oleochemicals or the (direct) polymerization of plant oils via metathesis. More recent developments, particularly the development of better and more robust catalysts, allow for highly efficient cross‐metathesis reactions opening new possibilities for the direct introduction of chemical functionalities. Within this contribution, the development of metathesis in oleochemistry will be discussed, covering self‐metathesis as well as more recent developments in the field of cross‐metathesis that lead to desired platform chemicals.     

Luminescence from praseodymium doped AlN thin films deposited by RF magnetron sputtering and the effect of material structure and thermal annealing on the luminescence

Thin films of Praseodymium doped AlN are deposited on silicon (111) substrates at 77 K and 950 K by rf magnetron sputtering method. About 500–1000 nm thick films are grown at 100–200 watts RF power and 5–8 mTorr nitrogen, using a metal target of Al with Pr. X-rays diffraction results show that films deposited at 77 K are amorphous and those deposited at 950 K are crystalline. Cathodoluminescence studies are performed at room temperature and luminescence peaks are observed in a wide range from ultraviolet to infrared region. The most intense peak is obtained in green at 526 nm from amorphous films as a result from ³P₁→³H₅ transition. In crystalline films the intense peak was obtain in red at 648 nm as a result from ³P₀→³F₂ transition. Films are thermally activated at 1300 K for half an hour in a nitrogen atmosphere. Thermal activation enhances the intensity of luminescence. Two peaks at 488 nm and 505 nm merged after thermal activation, giving rise to a single peak at 495 nm.