Synthesis, characterization and thermal properties of new aromatic quaternary ammonium bromides: precursors for ionic liquids and complexation studies

Series of new aromatic R₂R′₂N⁺Br⁻ (R=benzyl, 4-methylbenzyl, 2-phenylethyl, 3-phenylpropyl; R′=ethyl, methyl, isopropyl) or RR′₂NH⁺Br⁻-type (R=benzyl, R′=isopropyl) quaternary ammonium bromides were prepared by using novel synthetic route in which a formamide (N,N-diethylformamide, N,N-dimethylformamide, N,N-diisopropylformamide) is treated with aralkyl halide in presence of a weak base. The compounds were characterized by ¹H-NMR and ¹³C-NMR spectroscopy and mass spectrometry. Structures of the crystalline compounds were determined by X-ray single crystal diffraction, and in addition the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. Three of the compounds crystallized in monoclinic, two in orthorhombic and one in triclinic crystal system, showing ion pairs, which are interconnected by weak hydrogen bonds and weak π-π interactions between the phenyl rings. Three of the compounds appeared as viscous oil or waxes. Finally, TG/DTA and DSC methods were used to analyze thermal properties of the prepared compounds. The lowest melting points were obtained for diethyldi-(2-phenylethyl)ammonium bromide (122.2 °C) and for diethyldi-(3-phenylpropyl)-ammonium bromide (109.1 °C). In general, decomposition of the compounds started at 170-190 °C without identifiable cleavages, thus liquid ranges of 30-70 °C were observed for some of the compounds.     

The effect of side-chain length of cellulose fatty acid esters on their thermal,barrier and mechanical properties

Currently, long-chain cellulose esters are not produced commercially because of high price, and since their preparation typically requires a large quantity of chemicals. To reduce the chemical consumption, cellulose reactivity needs to be increased without losing its quality. One way to increase the reactivity of cellulose is to decrease its molar mass in a controlled manner. In this study, we have synthesized cellulose esters with different side-chain length (C6–C18) in a homogeneous system using ozone molar mass-controlled cellulose. The target was to keep the degree of substitution as low as possible while still ensuring the suitability of cellulose esters for solvent casting. Thermal, barrier and mechanical properties were studied depending on cellulose fatty acid ester side-chain length. All our molar mass-controlled cellulose esters form optically transparent, flexible and heat-sealable films with good water barrier properties and are processable without the addition of an external plasticizer. Furthermore, the films have mechanical properties comparable to some generally used plastics. These good properties suggest that our molar mass-controlled cellulose esters could be potential candidates for various applications such as films and composites.     

Copolymerization of glycolic,d,l-lactic and d,l-2-hydroxybutyric acid mixtures present in kraft black liquors

A series of copolymers of glycolic acid (GA), d,l-lactic acid (dl-LA) and d,l-2-hydroxybutyric acid (dl-2HBA) were prepared via melt condensation polymerization. The utilized monomers represent mixtures that are present and potentially obtainable from kraft black liquor by fractionation. Polymerizations were performed in 165 °C at nitrogen atmosphere and reduced pressure using stannous octoate as catalyst. Copolymerizations were conducted with varying dl-2HBA content in order to observe how the presence of the dl-2HBA monomer affects the properties of the polymers. Prepared copolymers were characterized with ¹H NMR and ¹³C NMR, size exclusion chromatography, differential scanning calorimetry and thermogravimetric analysis. The obtained copolymers had molecular weights between M_w = 3500–10,000 g/mol. dl-2HBA had a lowering effect on the glass transition temperatures and molecular weights of the copolymers. However, significant lowering of molecular weight was observed only when the amount of dl-2HBA in the feed exceeded 60%. The results indicate that dl-2HBA can be copolymerized with GA and dl-LA and therefore the corresponding kraft black liquor fractions can be utilized for polymerizations.     

在JYFL开展的研究工作：等离子体势的测量、电子加热的模拟、JYFL-MMPS及高温炉子

Extensive plasma potential measurements have been carried out using a device developed at JYFL. In this article the main results of the measurements will be summarized.A new simulation code to study the electron heating is being developed.One objective of the code is to determine the change of the electron loss cone when the magnetic field component of the electromagnetic wave is taken into account along with the permittivity of the plasma.As a part of the work,accurate X-ray measurements have been initiated. A new plasma chamber based on the MMPS-concept(Modified MultiPole Structure)has successfully been constructed and tested with the JYFL 6.4GHz ECRIS.The results and conclusions will be presented elsewhere in these proceedings.In the same article,a new concept of ECRIS and first results will be presented.The active development work of evaporation ovens has been carried out in a joint European collaboration(ISIBHI). The objective of the task is to make the operation of the oven reliable at 2000℃for several days.Both resistively and inductively heated ovens have been studied and further developed.The status of this work will be presented.     

Die Bestimmung der Butter- und Caprons?ure im Butterfett

Ohne Zusammenfassung     

Thermal and X‐ray powder diffraction studies of aliphatic polyester dendrimers

The syntheses and thermal and X‐ray powder diffraction analyses of three sets of aliphatic polyester dendrimers based on 2,2‐bis(hydroxymethyl)propionic acid as a repeating unit and 2,2‐dimethyl‐1,3‐propanediol, 1,5‐pentanediol, and 1,1,1‐tris(hydroxymethyl)ethane as core molecules are reported. These dendritic polyesters were prepared in high yields with the divergent method. The thermal properties of these biodendrimers were evaluated with thermogravimetric analysis and differential scanning calorimetry. The thermal decomposition of the compounds occurred around 250 °C for the hydroxyl‐ended dendrimers and around 150 °C for the acetonide‐protected dendrimers. In addition, the crystallinity of the lower generation dendrimers was evaluated with X‐ray powder diffraction. The highest crystallinity and the highest melting points were observed for the first‐generation dendritic compounds. The higher generation dendrimers showed weaker melting transitions during the first heating scan. Only the glass‐transition temperatures were observed in subsequent heating scans. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5574–5586, 2004     

对ECR离子源多极磁场结构的改进

Experiments have shown that especially the radial magnetic field component plays a crucial role in the production of highly charged ions with Electron Cyclotron Resonance Ion Sources(ECRIS).However, in several room temperature operating ECRISs the radial magnetic field strength is below the optimum value, mainly due to the limits in permanent magnet technology.Remarkable radial magnetic field improvement can be reached with a relatively simple and cost-effective idea called Modified MultiPole Structure(MMPS).The MMPS differs strongly from the former structures because here the magnetic field is increased only locally without affecting the plasma size.The idea was studied experimentally with a new MMPS plasma chamber prototype,which was designed and constructed for the JYFL 6.4GHz ECRIS.The new chamber is versatile and made it possible to perform several new types of measurements.These showed that the MMPS is especially applicable to increase very high charge-state ion production.Typically the ion current increases more than a factor of 2 in the case of highly charged ions such as Ar~(16 ).     

Thermoplastic Cellulose-Based Compound for Additive Manufacturing

The increasing environmental awareness is driving towards novel sustainable high-performance materials applicable for future manufacturing technologies like additive manufacturing (AM). Cellulose is abundantly available renewable and sustainable raw material. This work focused on studying the properties of thermoplastic cellulose-based composites and their properties using injection molding and 3D printing of granules. The aim was to maximize the cellulose content in composites. Different compounds were prepared using cellulose acetate propionate (CAP) and commercial cellulose acetate propionate with plasticizer (CP) as polymer matrices, microcellulose (mc) and novel cellulose-ester additives; cellulose octanoate (C8) and cellulose palmitate (C16). The performance of compounds was compared to a commercial poly(lactic acid)-based cellulose fiber containing composite. As a result, CP-based compounds had tensile and Charpy impact strength properties comparable to commercial reference, but lower modulus. CP-compounds showed glass transition temperature (Tg) over 58% and heat distortion temperature (HDT) 12% higher compared to reference. CAP with C16 had HDT 82.1 °C. All the compounds were 3D printable using granular printing, but CAP compounds had challenges with printed layer adhesion. This study shows the potential to tailor thermoplastic cellulose-based composite materials, although more research is needed before obtaining all-cellulose 3D printable composite material with high-performance.     

Self‐Assembly of Amphiphilic Janus Dendrimers into Mechanically Robust Supramolecular Hydrogels for Sustained Drug Release

Compounds that can gelate aqueous solutions offer an intriguing toolbox to create functional hydrogel materials for biomedical applications. Amphiphilic Janus dendrimers with low molecular weights can readily form self‐assembled fibers at very low mass proportion (0.2 wt %) to create supramolecular hydrogels (G′?G′′) with outstanding mechanical properties and storage modulus of G′>1000 Pa. The G′ value and gel melting temperature can be tuned by modulating the position or number of hydrophobic alkyl chains in the dendrimer structure; thus enabling exquisite control over the mesoscale material properties in these molecular assemblies. The gels are formed within seconds by simple injection of ethanol‐solvated dendrimers into an aqueous solution. Cryogenic TEM, small‐angle X‐ray scattering, and SEM were used to confirm the fibrous structure morphology of the gels. Furthermore, the gels can be efficiently loaded with different bioactive cargo, such as active enzymes, peptides, or small‐molecule drugs, to be used for sustained release in drug delivery.