Photoreactions of radicals during polyolefin photooxidation

Polypropylene (PP) and polyethylene (PE) peroxy radicals undergo photoreactions, but under commonly encountered photodegradation conditions these reaction rates are much lower than those of conventional radical reactions; for example, for PP peroxy radicals in noon summer sunlight at 25°C their rate of photolysis to alkyl radicals is less than one-tenth of their rate of hydrogen abstraction from the polymer. At lower temperatures( < ?10°C) or when more intense radiation is used, however, peroxy radical photolysis becomes a proportionately more important source of alkyl radicals. In addition, occurrence of photoinduced radical combination is confirmed but is shown to be important only when photolysis generates an alkyl radical sufficiently close to a peroxy radical that termination can occur before oxygen reconverts the alkyl radical to a peroxy radical. This termination mechanism therefore becomes more important for radicals generated at lower temperatures when the average separation of a radical pair is lower.     

Dialysis cells for controlled DNA: drug binding studies.

An efficient small volume accurate dialysis system has been designed, built and tested for proflavine binding to DNA based upon the side by side design used in the Franz diffusion cell. In a typical experiment 3 cm3 of DNA solution is added to one side and 3 cm3 of ligand to the other with a dialysis membrane between the two sides of 1 cm in diameter, thereby minimizing the area of dialysis membrane that the solutions are in contact with.     

Polyolefin photo-stabilisation mechanisms. Reactions of tetramethylpiperidine derivatives in model systems

The relative rate of cyclohexyl radical scavenging by oxygen or 4-oxo-2,2,6,6-tetramethylpiperidino-N-oxyl has been measured at 25°C, together with the relative rates of cyclohexyl peroxy radical attack on cyclohexane or substituted hydroxylamines derived from 2,2,6,6-tetramethylpiperidine. These competitive processes are important in the stabilisation of polymers against photo-oxidative destruction by piperidine derivatives. Peroxy radical scavenging by the substituted hydroxylamine appears to be considerably more important than alkyl radical scavenging by the nitroxide, although both processes are essential for prolonged ultra violet (uv) stabilisation of a polymer. However, a comparison of experimental photo-protection with that predicted by the measured rate constant ratios shows that other processes are needed to account entirely for the observed stabilisation. Other factors which may be involved in piperidine photo-protection of polymers include thermal decomposition of the substituted hydroxylamine to reform nitroxide in polar(oxidised) zones and especially the association of nitroxides with hydroperoxide groups (the dominant photo-initiator in degrading polyolefins).     

Demonstration-scale evaluation of a novel high-solids anaerobic digestion process for converting organic wastes to fuel gas and compost

Early evaluations of the bioconversion potential for combined wastes such as tuna sludge and sorted municipal solid waste (MSW) were conducted at laboratory scale and compared conventional low-solids, stirred-tank anaerobic systems with the novel, high-solids anaerobic digester (HSAD) design. Enhanced feedstock conversion rates and yields were determined for the HSAD system. In addition, the HSAD system demonstrated superior resiliency to process failure. Utilizing relatively dry feedstocks, the HSAD system is approximately one-tenth the size of conventional low-solids systems. In addition, the HSAD system is capable of organic loading rates (OLRs) on the order of 20-25 g volatile solids per liter digester volume per d (gVS/L/d), roughly 4-5 times those of conventional systems

Current efforts involve developing a demonstration-scale (pilot-scale) HSAD system. A two-ton/d plant has been constructed in Stanton, CA and is currently in the commissioning/startup phase. The purposes of the project are to verify laboratory- and intermediate-scale process performance; test the performance of large-scale prototype mechanical systems; demonstrate the long-term reliability of the process; and generate the process and economic data required for the design, financing, and construction of full-scale commercial systems. This study presents conformational fermentation data obtained at intermediate-scale and a snapshot of the pilot-scale project

     

An efficient, continuous flow technique for the chemoselective synthesis of thioacetals

By optimizing a reagent’s residence time within a packed-bed reactor, it is possible to overcome selectivity issues frequently encountered in stirred reaction vessels. This important feature is demonstrated for the chemoselective protection of 4-acetylbenzaldehyde whereby 1-[4-1,3-dithian-2-yl-phenyl]ethanone is obtained in excellent yield and purity. In addition, the generality of the technique is highlighted via the protection of numerous aldehydes and ketones affording the respective thioacetal/ketal in excellent yield (>99.1%) and purity (>99.9%), with space-time yields in the range of 0.44-1.10 g h⁻¹.     

Photostabilisation mechanisms in polymers: A review

Key degradative processes for various polymers are itemised, together with photostabilisation mechanisms which can minimise these processes. Polymers can be conveniently classified as inherent absorbers, which absorb large amounts of solar uv, and as ‘non-absorbers’, that is polymers transparent in the near uv. The former group which includes aramids, polycarbonates and polyesters is predominantly photodegraded by primary processes causing direct bond scission and stabilisation is best effected by the use of uv absorbing additives or opaque pigments. The ‘non-absorbers’ include polyolefins and poly(vinylchloride) which are degraded as the result of oxidative chain processes initiated by chromophoric impurities. For polypropylene the dominant photooxidation product is hydroperoxide which photocleaves to initiate further oxidation. Various uv. stabilisers for polyolefins appear to owe their effectiveness to their ability to decompose hydroperoxide groups and/or to their ability to scavenge free radical intermediates in the oxidative process.     

Oriented polyolefin laminates: A refractometry and infrared study

A series of polypropylene-copolymer laminates produced by biaxial orientation in the 120–155°C range has been characterized by refractometry and infrared (IR) spectroscopy. The copolymer was a random ethylene-propylene resin and the IR techniques included tilted-film transmission as well as internal reflection, both using polarized radiation. The IR techniques yielded spectra corresponding to the machine, transverse, and through directions. Similarly, the refractometry gave refractive indices of both components of each laminate along all three axes. Results from the three techniques were compared and contrasted and the validity of the calculated internal reflectance spectra discussed. Practical methods to estimate the source and extent of errors in the latter technique from false radiation and contact problems were explored.     

Die Chroms?ure?tzung von Polyolefinoberfl?chen und Adhiisivbindung

Ohne Zusammenfassung     

Role of polymer morphology in the oxidation of polypropylene

The γ-initiated oxidation and presensitized photooxidation of polypropylene films and fibers are shown to be insensitive to sample thickness (if <150 μm) and a range of morphological parameters such as molecular orientation (in drawn samples) and fibrillar and void content. The relevance of these observations is discussed in the light of the many previous assertions as to the influence of morphological effects on oxidation rates. The γ-initiated oxidation was studied in preference to conventional thermal or photoinitiated oxidation because of the greater control over the rate of radical production available by this method.