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Degradation of Polymers by Ultra-Violet Light

Abstract

To reach an understanding of the complex processes which occur when polymers are degraded by ultra-violet light under service conditions it is first judicious to try to elucidate the photochemistry of relatively simple polymer reactions. For this reason, emphasis is given to studies in which purified polymers, in bulk, were exposed to monochromatic radiations in the absence of oxygen. In respect of product analysis, emphasis is given to methods for estimating quantum yields for fractures and crosslinks. Photochemical mechanisms are illustrated by discussion of polystyrene, polytethylene terephthalate) and cellulose. Special emphasis is given to the role of free radicals. Attention is drawn to reports that the course of photolysis may be changed by application of an external pressure of a chemically inert gas, such as nitrogen. The explanation suggested in the literature is that this depends on the ease of escape of hydrogen atoms which, alternatively, might react with trapped polymer radicals. The course of photolysis may also be affected by polymer radicals acting as strongly absorbing chromophores and consequently undergoing further chemical reaction. This is illustrated by reference to the conversion of allyl radicals to alkyl radicals in polyethylene and also by changes observed in the ESR spectrum of  More>>
Authors:
Turner, D. T. [1] 
  1. Camille Dreyfus Laboratory, Research Triangle Institute, Research Triangle Park, NC (United States)
Publication Date:
Oct 15, 1968
Product Type:
Conference
Resource Relation:
Conference: Study Group on Impregnated Fibrous Materials, Bangkok (Thailand), 20-24 Nov 1967; Other Information: 40 refs., 6 figs., 2 tabs.; Related Information: In: Impregnated Fibrous Materials. Report of a Study Group on Impregnated Fibrous Materials| 395 p.
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALLYL RADICALS; CELLULOSE; ELECTRON SPIN RESONANCE; ETHYLENE; FRACTURES; MONOCHROMATIC RADIATION; NATURAL RUBBER; PHOTOLYSIS; POLYETHYLENES; POLYSTYRENE; RADIOLYSIS; SPECTRA
OSTI ID:
22262924
Research Organizations:
International Atomic Energy Agency, Vienna (Austria)
Country of Origin:
IAEA
Language:
English
Contract Number:
Contract NAS1-7553
Other Identifying Numbers:
TRN: XA14M5778084151
Submitting Site:
INIS
Size:
page(s) 93-105
Announcement Date:
Sep 16, 2014

Citation Formats

Turner, D. T. Degradation of Polymers by Ultra-Violet Light. IAEA: N. p., 1968. Web.
Turner, D. T. Degradation of Polymers by Ultra-Violet Light. IAEA.
Turner, D. T. 1968. "Degradation of Polymers by Ultra-Violet Light." IAEA.
@misc{etde_22262924,
title = {Degradation of Polymers by Ultra-Violet Light}
author = {Turner, D. T.}
abstractNote = {To reach an understanding of the complex processes which occur when polymers are degraded by ultra-violet light under service conditions it is first judicious to try to elucidate the photochemistry of relatively simple polymer reactions. For this reason, emphasis is given to studies in which purified polymers, in bulk, were exposed to monochromatic radiations in the absence of oxygen. In respect of product analysis, emphasis is given to methods for estimating quantum yields for fractures and crosslinks. Photochemical mechanisms are illustrated by discussion of polystyrene, polytethylene terephthalate) and cellulose. Special emphasis is given to the role of free radicals. Attention is drawn to reports that the course of photolysis may be changed by application of an external pressure of a chemically inert gas, such as nitrogen. The explanation suggested in the literature is that this depends on the ease of escape of hydrogen atoms which, alternatively, might react with trapped polymer radicals. The course of photolysis may also be affected by polymer radicals acting as strongly absorbing chromophores and consequently undergoing further chemical reaction. This is illustrated by reference to the conversion of allyl radicals to alkyl radicals in polyethylene and also by changes observed in the ESR spectrum of polymer radicals trapped in poly (ethylene terephthalate) as a result of exposure to light. It is suggested that this effect is primarily responsible for the evolution of hydrocarbon gases on photolysis of polyethylene or natural rubber. In contrast, radiolysis of these polymers yields almost pure hydrogen because, in this case, energy is absorbed by relatively non-selective processes, i.e. free radicals do not absorb high energy radiation much more strongly than does their polymeric environment. (author)}
place = {IAEA}
year = {1968}
month = {Oct}
}