Additives photodegradants

The photodegradation of unstabilized bisphenol A polycarbonate films is described as an autoaccelerating process initiated by formation of products arising from a formal photo-Fries reaction. Oxidation also contributes as an additional photodegradation pathway. Photosensitive polymers... 

Studies have appeared where photolysis in natural bodies of water under normal sunlight conditions has been examined. For example, metolachlor was slowly photodegraded by sunlight in lake water, with a half-life of 22 days in summer and 205 days in winter (28). Addition of a 5% solution of dissolved organic matter to the water extended the half-Hves two to three times longer, depending on the season (see PHOTOCHEMICAL TECHNOLOGY, photocatalysis). ... 

The exterior durabiHty of relatively stable coatings can be enhanced by use of additives. Ultraviolet absorbers reduce the absorption of uv by the resins and hence decrease the rate of photodegradation. Eurther improvements can be gained by also adding free-radical trap antioxidants (qv) such as hindered phenols and especially hindered amine light stabilizers (HALS). A discussion of various types of additives is available (113). 

PL can be used as a sensitive probe of oxidative photodegradation in polymers. After exposure to UV irradiation, materials such as polystyrene, polyethylene, polypropylene, and PTFE exhibit PL emission characteristic of oxidation products in these hosts. The effectiveness of stabilizer additives can be monitored by their effect on PL efficiency. 

Photodegradation may involve use of inherently photo-unstable polymers or the use of photodegradant additives. An example of the former are ethylene-carbon monoxide polymers in which absorption of light by the ketone group leads to chain scission. The polymer becomes brittle and forms a powder. Such materials are marketed by Dow and by Du Pont. Other examples are the copolymers of divinyl ketone with ethylene, propylene or styrene marketed by Eco Atlantic. 

The final possible mode of action for an antioxidant is as a peroxide decomposer. In the sequences that lead to photodegradation of a polymer the ready fragmentation of the hydroperoxide groups to free radicals is the important step. If this step is interfered with because the peroxide has undergone an alternative decomposition this major source of initiation is removed. The additives which act by decomposing hydroperoxide groups include compounds containing either divalent sulfur or trivalent phosphorus. The mechanism involves... 

LC-tandem MS was recently used for polymer/additive characterisation. In cases of soft ionisation processes (e.g. ESI, APCI, etc.), MS/MS is often necessary to confirm the ionic species. QITMS has the potential to improve the detection limits for organotin analysis compared to QMS. HPLC-UV and LC-API-MS/MS have been employed for the characterisation of the products of photodegradation of benzotriazole-based UV absorbers (Tinuvin P/328/900) under mild conditions [642]. Among the photoproducts identified... 

The photodegradation of synthetic polymers can be considerably reduced upon addition of ultraviolet stabilizers. The UV stabilizers (preferably derivatives of o-hydroxy-benzophenone or of 2-(2 -hydroxys -methylphenyl)benzotriazole (Tinuvin) transform the absorbed light energy into thermal energy thus preventing all sorts of photochemically initiated reactions. For review articles see the papers of Otter-stedt (.l), Heller and Blattmann ( 2, 2), Kloepffer (jl, j ), Gysling (JS) and Trozzolo (19 ) ... 

The photodegradation of PVCa solutions has been studied to determine a mechanism for the photodegradation process and identify the excited states involved. The polymer was secondary grade (Aldrich Chemical Company) that was further purified by reprecipitation three times from methylene chloride solution by the dropwise addition into methly alcohol. Solutions in methylene chloride were found to yellow rapidly in air upon exposure to 360 nm light, whereas solutions degassed by the freeze-pump-thaw technique showed little yellowing. 

Solvents, Additives, and Extraneous Impurities. The rate of PVC photodegradation under air at wavelengths >250 nm is said to be increased by small amounts of residual tetrahydrofuran (THF) or dichloroethane (56). On the other hand, residual THF has been reported not to enhance the dehydrochlorination of the polymer during irradiation under nitrogen at X >240 nm (41). Nevertheless, under the conditions of the latter study, THF was found to Increase the relative concentrations of the shorter polyene products (41). This effect was attributed to a facile... 

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