Engineering plastics from lignin. VI. Structure–property relationships of PEG-containing polyurethane networks

Hydroxypropyl lignin-based thermosetting polyurethanes were synthesized with excess hexamethylene diisocyanate (HDI) and tolylene diisocyanate (TDI) by solution casting. Four polyethylene glycols (PEG) of molecular weight 400, 600, 1000, and 4000 were mixed with lignin polyol to incorporate different proportions of soft segment into the network prior to crosslinking. Neither thermal nor mechanical and limited small angle x-ray scattering (SAXS) analysis provided distinct evidence for phase separation and microstructure formation. The study examines the effect of the soft segment in relation to chain length and weight contribution on the thermal and mechanical properties of the final networks. A significant sensitivity of glass transition temperature (T_g), of swelling in DMF, and of the mechanical properties to soft segment content was observed. Some of this sensitivity must, however, be attributed to differences in crosslink density since the polyol to diisocyanate weight ratio was kept constant throughout the synthesis series. The magnitude of the change of the different properties was found to be influenced by both glycol content and glycol molecular weight. The T_g of the network decreased from 105°C to as low as 38°C (HDI), and from 158°C to 70°C (TDI), with incorporation of up to 17.8% glycol, and it was greater with lower molecular weight glycols than with higher ones at any weight fraction. Swelling in DMF increased as expected with soft segment content. Mechanical properties were affected most if HDI and lower molecular weight glycols were used. The uniformity in structure, reduction in brittleness, and considerable improvement in mechanical properties with inclusion of minor PEG contents indicates that lignin-based network polyurethanes can be synthesized with controllable performance characteristics.     

Produkte der thermischen En-Reaktion von ungesättigten Fettstoffen und Maleinsäureanhydrid

Products of the Thermal Ene-Reaction of Unsaturated Fatty Compounds and Maleic Anhydride The thermal ene reaction of the methylates of unsaturated fatty acids 10-undecenoic acid, oleic acid and (E)-10-eicosendioic acid with maleic anhydride was carried out at 190°C. The mono addition products were isolated and their stereochemistry was deduced from ¹HNMR- and ¹³C-NMR-spectroscopy.     

Structural control in radical polymerization with 1,1 diphenylethylene: 2. Behavior of MMA-DPE copolymer in radical polymerization

Copolymers of 1,1-diphenylethylene (DPE) behave in a very special way in radical polymerization. Particularly, the behavior of MMA-DPE copolymers in radical polymerization is investigated. The results reveal that the semiquinoid structure of the precursor polymer identified in a previous contribution is activated by the attack of free radicals and thus, in a second stage polymerization with a second monomer, block copolymers are formed. The block copolymer yield depends strongly on the ratio between the amount of DPE-containing precursor polymer and the initiator and monomer concentration used in the second stage. The mechanism proposed is able to explain at least qualitatively all experimental results including the restriction of this mode of control of radical polymerization to the formation of diblock copolymers only.     

Lyso platelet activating factor (LysoPAF) and its enantiomer. Total synthesis and carbon-13 NMR spectroscopy

Described is a reaction sequence for the total synthesis of lyso platelet activating factor (lysoPAF; 1-O-alkyl-sn-glycero-3-phosphocholine) and its enantiomer. The procedure is versatile and yields optically pure isomers of defined chain length. The synthesis is equally suited for the preparation of lysoPAF analogues and its enantiomers with unsaturation in the long aliphatic chain. First,rac-1(3)-O-alkylglycerol is prepared by alkylation ofrac-isopropylideneglycerol with alkyl methanesulfonate followed by acid-catalyzed removal of the ketal group. The primary hydroxy group of alkylglycerol is then protected by tritylation, the secondary hydroxy group is acylated, and the protective trityl group is removed under mild acidic conditions with boric acid on silicic acid, essentially without acyl migration. Condensation of the diradylglycerol with bromoethyl dichlorophosphate in diethyl ether, hydrolysis of the resulting chloride, and nucleophilic displacement of the bromine with trimethylamine givesrac-1-O-alkyl-2-acylglycero-3-phosphocholine in good overall yield. The racemic alkylacylglycerophosphocholine is finally treated with snake venom phospholipase A₂ (Ophiophagus hannah) which affords 1-O-alkyl-sn-glycero-3-phosphocholine (lysoPAF) of natural configuration in optically pure form. The “unnatural” 3-O-alkyl-2-O-acyl-sn-glycerol-1-phosphocholine enantiomer, which is not susceptible to phospholipase A₂ cleavage, gives 3-O-alkyl-sn-glycero-1-phosphocholine upon deacylation with methanolic sodium hydroxide. Homogeneity and structure of the intermediates and final products were ascertained by carbon-13 nuclear magnetic resonance spectroscopy on monomeric solutions.     

Elastic properties of adhesive polymers. II. Polymer films and bond lines by means of nanoindentation

Seven different polymers used frequently as adhesives and/or matrix polymers in wood, wood composites, and natural fiber‐reinforced composites were studied by uniaxial tensile tests and nanoindentation. It was shown that the elastic modulus, the hardness, the creep factor, and the elastic‐, plastic‐, and viscoelastic work of indentation of the seven different polymers is essentially the same regardless whether the polymers were tested in the form of pure films or in situ, i.e., in an adhesive bond line with spruce wood. An excellent correlation was found between the elastic modulus measured by tensile tests and the elastic modulus measured by nanoindentation. In spite of the good correlation, the elastic modulus measured by nanoindentation is significantly higher than the elastic modulus measured by tensile tests. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1234–1239, 2006     

Charakterisierung und Störstoffanalyse von rückgewonnenen Stoffströmen aus Wärmedämmverbundsystemen

Due to the growing energy requirements, the proportion of external thermal insulation composite systems (ETICS) installed has increased significantly during the past 50 years. Due to the longevity of these systems, ETICS waste is currently accumulating. Owing to the complex construction as well as a multitude of differently installed materials and substances of the past generations, there are many uncertainties and problems with the clean and low-pollutant processing of such systems. In the frame of this work, the ETICS were processed and sorted before being screened for ingredients or pollutants as well as for the purity of the recovered material fractions.     

Dealuminated Y Zeolite for Water-Driven Adsorption Heat Pumps: Hydrothermal Stability

Silica gel or zeolites AlPO-5 and SAPO-34 are recommended as adsorbents in water-driven heat pumps because of their selective water uptake. Secondary energy, like solar energy, can be used for regeneration of loaded adsorbers. In case of the availability of only low energy levels, the use of dealuminated Y zeolite (DAY) is the better choice because of the infinitely variation of its hydrophilic properties by tailoring of the framework Si/Al ratio. Actual data on the hydrothermal stability of DAY are lacking. Thus, we report on the long-term behavior of DAY zeolites with different Si/Al ratios.     

Segmentation of the fascia lata and reproducible quantification of intermuscular adipose tissue (IMAT) of the thigh

Magnetic Resonance Materials in Physics, Biology and Medicine - To develop a precise semi-automated segmentation of the fascia lata (FL) of the thigh to quantify IMAT volume in T1w MR images and...     

Investigation of wetting behaviour of hardenable copper based-alloys for brazing applications

ABSTRACT

Tools for machining are exposed to high loads, wear, and elevated temperatures. Commonly, such tools consist of cemented carbides and tool steel. To combine the advantages of both materials, high-quality-joints with high strengths are desired. When brazing these materials, the main challenge is the mismatch of the Coefficient of Thermal Expansion (CTE) and the poor wettability of cemented carbides by molten filler alloys. In this regard, the feasibility of two custom-made alloys (CuNi12Si5, CuNi12Si5B0.4) was analysed. Besides being a cost-efficient alternative, these alloys offer the possibility to modify their mechanical properties by precipitation hardening to reduce stresses within the final joints. Thus, this paper shows that a temperature of 1060°C is suitable for wetting and brazing tests on different substrates.