Poly photodegradation reactions

Frequently B will also undergo a back hydrogen transfer which regenerates the parent ketone, as well as cyclization (in most cases a minor reaction) as a result of this competition the quantum yields of fragmentation are typically in the 0.1-0.5 range in non-polar media. When the Norrish Type II process takes place in a polymer it can result in the cleavage of the polymer backbone. Poly(phenyl vinyl ketone) has frequently been used as a model polymer in which this reaction is resonsible for its photodegradation, reaction 2. 

We have also used poly(propynoic acid) in our studies of the photochemical interaction of PCSs with dienophiles, such as maleic anhydride, tetracyanoethylene, and styrene. This photochemical reaction of Diels-Alder type is accompanied by the breakdown of the conjugation system and the formation of slightly colored adducts266. Together with the cycloaddition reaction, photodegradation of PPA and its adducts takes place. A cycloaddition reaction is always preceded by the formation of a donor-acceptor complex of a PCS with a dienophile. 

The photodegradation of synthetic polymers can be prohibited (or at least reduced) upon addition of UV-stabilizers. These compounds transform the absorbed light energy into thermal energy thus preventing all sorts of photochemically initiated reactions. Films of poly-(m-phenylene-isophthalamide) were used which contained appropriate amounts of UV-stabilizers of the 2-(2 -hydroxy-5 -methylphenyl)benzotriazole type or their 21-methoxy derivatives. The following results were obtained ... 

The chemistry of the oxidative and nonoxidative photodegradation of poly(vinyl chloride) is reviewed with emphasis on work that has been published since the early 1970 s. Topics covered include the nature of the photoinitiating species, the photoinitiation mechanism, and the structural consequences and reaction mechanism of the overall photodegradation process. Also included is a summary of recent studies on the determination of structural defects in poly(vinyl chloride) by carbon-13 NMR. 

During photolysis, the double bond content of the polysilane(P-l)(15mol% in this experiment) decreased to 10mol%, as measured by 1H-NMR spectroscopy. However, the ratio, quantum yield of scission(Q(S))/quantum yield of crosslinking(Q(X)), was not affected by the reaction of the double bond. West and his coworkers have reported that poly((2-(3-cyclohexenyl)-ethyl)methylsilane-co-methylphenylsilane) crosslinked upon irradiation(55). The difference between our results and West s may lie in the amount of the double bond and inhibitation of the radical closslinking by the phenol moiety. Polysilane with a halogen moiety, P-8, photodecomposed rapidly, compared with P-1 or P-3. The introduction of a chloride moiety was effective for the sensitization of the photodegradation. Similar results has already been reported(55). 

Radiation initiated or photodegradation - free radical reactions (see Chapter 18 on photodegradation and photostabilization of poly (ethylene terephthalate)). 

Polymer Photochemistry. The occurrence of these reactions in polymeric ketones was first demonstrated by Guillet and Norrish (6, 7), who studied poly (methyl vinyl ketone) in solution and showed that the main features of the photodegradation could be accounted for quantitatively on the basis of Type I and Type II reactions. The conclusion was later confirmed by Wissbrun (13). Recent studies of the ethylene-carbon monoxide polymer (9) confirm that both Type I and Type II reactions occur. The Type I reaction results in the formation of two polymer radicals, one of which is an acyl radical which may subsequently decarbonyl-ate (Reaction 4). 

The dielectric strength of polyethylene has been measured as a function of additive concentration while in stabilised polymers the depth of degradation was found to be uniform . HALS have been found to be effective stabilisers for UV cured coatings and do not influence the cure rate . Bleached wood pulps can be effectively stabilised by ascorbic acid and wool by hydroxy-benzotriazoles and HALS . Hydroxybenzotriazole stabilisers also protect wood pulp and polyurethanes by co-reaction . The spectroscopic properties of monomeric and polymeric benzotriazoles have also been compared . UV absorbers are effective in clear coats and when grafted to wood . Dihydroxybenzophenone stabilisers inhibit the chain scission in the photodegradation of poly(methoxyacrylophenone) while tin stabilisers have also been found to photostabilise PVC . 

Since 1971 our department is Involved in study of photodegradation, sensitized photooxidation and photostabilization of polymers. A big effort is made in the study of singlet oxygen oxidation of several important polymers, such as polydienes, poly(vinyl chloride), polystyrene and polyesters, reactions of atomic oxygen and ozone with polydienes and photostabilization of these polymers. 

Poly(acrylates) and (alkyl acrylates). - Structured nanopore films of poly(styrene-block-methyl methacrylate) copolymers have been made with controlled spectral sensitivity, such that each block is sensitive to a specific degradation wavelength. In copolymers of 2,2,2-trifluoroethyl methacrylate with vinyl ethers, the photosensitivity is controlled by the vinyl ether units. Photodegradation occurs at the tertiary positions of the ether units followed by lactone formation and chain scission processes. Furthermore, the fluorinated side chains have been found to inhibit cyclization reactions. 

Photosensitized degradation of poly(olefin sulfones) similar to the Hg(3P) photosensitized reactions of olefin sulfones make them subject to photodegradation in easily accessible wavelength regions. Almost all poly(olefin sulfones) have been reported only as positive tone electron beam resists (4). As the only exception, poly(5-hexene-2-one sulfone) has been reported as a positive tone photoresist with or without a photosensitizer, benzophenone (5). Because this polymer has a carbonyl chromophore, its photosensitivity is clearly derived from the polymer structure itself. 

Poly(methylvinyl ketone) in which carbonyl groups are also in side-group photolyse by the Norrish Type II reaction (88989) It has been shown9that when the ketone groups are isolated from each other by copolymerization of methyl vinyl ketone with methyl acrylate9the photodegradation process increases (90). This effect can be partially explained by intramolecular energy transfer. 

ESR investigation indicates that the radical resulting from scission of the methyl side group is formed on irradiation of a highly concentrated glassy solution of poly-a-methylstyrene [43]. One can thus conclude that the following reactions are more likely to occur as the initial steps of the photodegradation of poly-a-methylstyrene ... 

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