Biphenyl-tricarbonylchrom-komplexe, 9. Mitt.: Synthesen,chromatographische Enantiomerentrennung,Circulardichroismus und Chiralität von mono- und bis-(Tricarbonylchrom)-Komplexen di- und tetrasubstituierter sowie überbrückter Biphenyle

Chiral title compounds have been resolved by medium pressure liquid chromatography (MPLC) on triacetylcellulose in ethanol. Whereas a quantitative separation was achieved for16 and20, a recycling technique had to be applied to1,4,6,10 and15 leading to a 100% e.e. for1,6 and15 and to ca. 60% e.e. for4 and10.An unambiguous assignment of the chirality (+)-(R) _a -(S) _m for tricarbonylchromium-6,6-dimethyl-diphenicacid dimethylester (4) was deduced both from the photochemical decomplexation to (-)-5 with the known chirality (R) _a (whose e.e. was determined by MPLC on triacetylcellulose) and by comparison of the¹H-n.m.r. spectra of4 and5 thereby proving the structure 4 for the former.Other chiralities both for mono and bis(tricarbonylchromium)biphenyl complexes were established by chemical correlations and comparison of the CD spectra with those of key compounds.

Herrn Prof. Dr.H. Tuppy mit besten Wünschen zum 60. Geburtstag gewidmet.     

Thermal stability and degradation of the post-use reclaim milk pouches during multiple extrusion cycles

In the present study, the recyclability of the post-use milk pouches (50/50 LDPE–LLDPE blend) was evaluated with or without adding stabilizer. Thoroughly washed and dried post-use milk pouch films were extruded five times at high temperature (483–513 K) in the open atmosphere. The mode of degradation during extrusion operation was studied by melt flow index (MFI), rheological properties, gel content and FT-IR analysis. The differential scanning calorimetry (DSC) analysis was carried out to evaluate the thermal stability of the stabilized and un-stabilized recycled mass from post-use milk pouch under this investigation. Mechanical properties (tensile strength, % elongation at break, tensile modulus and hardness) of the un-stabilized extruded material were significantly affected as a result of thermooxidative degradation during extrusion in presence of air. After all, stabilization with 0.4% anti-oxidant satisfactorily retains all the initial properties of the recycled material.     

Investigations on the recycling of hemp and sisal fibre reinforced polypropylene composites

Microscopic, mechanical, rheological and thermal tests were carried out in order to determine the recycling behaviour of PP/vegetal fibre composites. Different composites using hemp and sisal were characterized. All results were compared with PP-g-MA/hemp composites and PP/glass fibre composites.The results prove that mechanical properties are well conserved with the reprocessing of PP/vegetal fibre composites but that there is poor adhesion between the fibres and PP without any treatment. The addition of PP-g-MA shows an improvement of the bonding evidenced by MEB pictures. Vegetal fibres induce an increase in the percentage of crystallinity χ_c and in the crystallization temperature T_c which can be explained by the nucleating ability of the fibres improving crystallization of PP. The Newtonian viscosity η₀ decreases with cycles, indicating a decrease in molecular weight and chain scissions induced by reprocessing. The decrease of fibre length with reprocessing could be another reason for viscosity decrease.     

Alkyd resins derived from glycolized waste poly(ethylene terephthalate)

In this investigation the production of secondary value-added products, such as alkyd resins, derived from the glycolysis of poly(ethylene terephthalate) (PET) is examined as an effective way for its recycling. PET was taken from common soft-drink bottles and diethylene glycol (DEG) was used for the depolymerization at several initial molar ratios. The oligomers obtained were analyzed according to their average molecular weights. Furthermore, the glycolyzed PET products (oligomers) were reacted with maleic anhydride, phthalic anhydride and propylene glycol to form unsaturated polyester resins. These were subsequently mixed with styrene and cured using the benzoyl peroxide/amine initiator system to carry out the reaction in ambient temperature. The curing characteristics of the resins produced were investigated with respect to the initial molar ratio of DEG/PET as well as the initial initiator concentration. Finally, the mechanical properties (tensile strength and elongation at the break point) of the resins were compared with the conventional general purpose resin and were found to be comparable.     

Two stage electrostatic separator for the recycling of plastics from waste electrical and electronic equipment

The aim of study was to evaluate the effectiveness of a new facility for recycling of plastics from granular waste electrical and electronic equipment. The installation consists of two sections, the products of a first tribo-aero-electrostatic separator being subsequently treated in two free-fall electrostatic separators. The tests were performed on a mixture of polycarbonate (PC) and polyamide (PA). Analysis of the purity of the products obtained was performed using a program of image processing in MATLAB. Products of very high purity (roughly 95% for both PC and PA) were obtained at a recovery rate higher than 70%.     

液体空分流程形式浅析

通过对全液体空分装置不同流程组织形式进行分析和模拟计算、能耗与投资的比较,根据不同规格的产品要求,进行合适的流程形式选择,以可达到节能降耗的目的。     

Sensitive chemiluminescence aptasensor based on exonuclease-assisted recycling amplification

We report herein an exonuclease-assisted aptamer-based target recycling amplification strategy for sensitive and selective chemiluminescence (CL) determination of adenosine. This aptasensor is based on target-induced release of aptamers from capture probes immobilized on the 96-well plate surface, and thus leading to a decreased hybridization with gold nanoparticle-functionalized reporter sequences followed by a CL signal. The introduction of exonuclease III catalyzes the stepwise removal of mononucleotides from 3′-hydroxyl termini of duplex DNAs of aptamers, liberating the adenosine. Therefore, a single copy of target adenosine can lead to the release and digestion of numerous aptamer strands from the 96-well plates and ultimately an enhanced sensitivity is achieved. Experimental results revealed that the exonuclease-assisted recycling strategy enabled the monitoring of adenosine with wide working ranges and low detection limits (LOD: 0.5 nM). This new CL strategy might create a novel technology for the detection of various targets and could find wide applications in the environmental and biomedical fields.     

Mild conversion of propargylic alcohols to α,β-unsaturated enones in ionic liquids (ILs); a new ‘metal free’ life for the Rupe rearrangement

A mild and selective transition metal free protocol for the conversion of propargylic alcohols to cyclic and acyclic α,β-unsaturated enones via the Rupe rearrangement is reported. The method utilizes the Brønsted acidic ionic liquid [BMIM-SO₃H][OTf] as catalyst and [BMIM][PF₆] as solvent and offers the potential for recycling and reuse of the IL solvent. The feasibility to synthesize bicyclic fused cyclopentenone derivatives via a Rupe → Aldol → Nazarov sequence utilizing this protocol has also been demonstrated.     

Recycling of waste from polymer materials: An overview of the recent works

Polymer recycling is a way to reduce environmental problems caused by polymeric waste accumulation generated from day-to-day applications of polymer materials such packaging and construction. The recycling of polymeric waste helps to conserve natural resource because the most of polymer materials are made from oil and gas. This paper reviews the recent progress on recycling of polymeric waste form some traditional polymers and their systems (blends and composites) such as polyethylene (PE), polypropylene (PP), and polystyrene (PS), and introduces the mechanical and chemical recycling concepts. In addition, the effect of mechanical recycling on properties including the mechanical, thermal, rheological and processing properties of the recycled materials is highlighted in the present paper.     

Methanolysis of poly(lactic acid) (PLA) catalyzed by ionic liquids

Poly(lactic acid) (PLA) was depolymerized by methanol in the presence of a novel catalyst: ionic liquids. It was found that the purification method of the main products in the methanolysis catalyzed by ionic liquids was simpler than that of traditional compounds, such as sulfuric acid. Qualitative analysis indicated that the main product in the methanolysis process was methyl lactate. The influences of experimental parameters, such as the amount of ionic liquids, methanolysis time, reaction temperature, and dosages of methanol on the conversion of PLA, yield of methyl lactate were investigated. Under the optimum conditions, using ionic liquid 1-butyl-3-methylimidazolium acetate ([Bmim][Ac]) as catalyst, results showed that the ionic liquid could be reused up to 6 times without apparent decrease in the conversion of PLA and yield of methyl lactate. The kinetics of the reaction was also investigated. The results indicated that the methanolysis of PLA was a first-order kinetic reaction with activation energy of 38.29 kJ/mol. In addition, a possible catalysis mechanism of the methanolysis of PLA was proposed.