Photodegradation-Poly

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 ... 

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. 

Although poly(vinyl chloride) (PVC) is one of the most important commercial polymers, its outdoor use has been restricted by its photochemical instability. The reasons for this instability are incompletely understood, but some progress has been made recently on this problem, and the present paper attempts to summarize the current status of fundamental knowledge in this field. This survey is not intended to be comprehensive it is concerned primarily with work published since the early 1970 s and with basic chemical principles rather than technological developments. The photodegradation of PVC has been discussed in other recent reviews (1,2, 3 4) ... 

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. 

Photophysical Processes and Photodegradation of Poly(ethylene terephthalate-co-2,6-naphtha1enedi carboxyl ate) Copolymers. We have recently reported the photophysical processes and the photo-degradative behavior of Doly(ethylene terephthalate-co-2,6-naphthalenedicarboxyl ate), PET-2,6-ND, copolymer yarns containing 0.5 - 4.0 mole percent 2,6-naphthalenedicarboxyl ate, 2,6-ND (1) and the parent naphthalenedicarboxyl ate monomer, Figure 3 and 4. 

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)). 

Photodegradation of Poly(Ethylene Terephthalate) and Poly(Ethylene/1,4-Cyclohexylenedimethylene Terephthalate)... 

Figure 6. Trapping experiments for poly silane photodegradation.

A few reports of pyrazine monomers have appeared in the literature (70Millloo). The most extensive study of pyrazine monomers involves their use to prepare photodegradable polymers <76MI11104). 2-Vinylpyrazine (145) copolymers and poly(2,5-distyrylpyrazine)... 

The lanthanides find some use as stabilizers for polymers. The coating of polycarbonate with a poly(vinyl alcohol) film containing CeCl3 inhibits photodegradation of the polycarbonate.151 The naphthenates of cerium, lanthanum and yttrium act as thermal stabilizers for polyorgano-siloxanes.152... 

The thermal and photochemical dehydrochlorination of the vinyl chloride—CO copolymer have been studied by two different groups56,57). The decomposition rate for the copolymer was significantly higher than that for poly(vinyl chloride), the rate increasing with increasing CO content of the copolymer. In addition, the thermal decomposition of the copolymer was accelerated in the presence of molecular 02 while the photodegradation was slowed down 57). As with poly(vinyl chloride), the dehydrochlorination of the copolymer resulted in the formation of polyene sequences. There was no appreciable decrease in molecular weight. 

In this connection Ishikawa and coworkers studied the photodegradation of poly(disilanylene)phenylenes 203126, and found that irradiation under the same conditions as in the photolysis of the aryldisilanes results in the formation of another type of nonrearranged silene 204 produced together with silane 205 from homolytic scission of a silicon-silicon bond, followed by disproportionation of the resulting silyl radicals 206 to 204 and 205 (equation 51). 

Hie dye-doped ORMOSIL materials exhibit much higher photostability than the reported polymer-doped materials. For example, optical gain was reported for several coumarin dyes in PMMA (13), It is significant to note that the best dyes reported could only be used to several hundred pulses and that most of the coumarin dyes could not even oscillate for 100 pulses. The ORMOSIL gels thus represent an improvement of at least 1-2 orders of magnitude in photostability. Optical gain was also reported for R6G doped into modified poly(methyl methacrylate) (14L These materials exhibited loss of 20% output after 180 pump pulses (1 J/cm ) at 532 nm. The reported plots indicate that these materials would have dropped by 90% after 275-300 pulses due to rapid steady state photodegradation once the pulse count exceeded the critical pulse number. In this case the R6G doped ORMOSIL gel laser offers a useful lifetime improvement by a factor of more than 15 over the reported polymer material. 

UV irradiation causes photodegradation of poly[methylcyclohexyl-co-methyl((3-tri-methylsilyl)ethyl]silane and PMPS solutions.104 It was found that branching of PMPS is induced by light exposure. The photochemistry of both pure solids and their toluene solutions has been studied. The UV absorption of the copolymer in solution has a maximum at 308 nm and at 303 nm for the... 

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