Norrish type-2 mechanism

When the polymers are exposed to ultraviolet radiation, the activated ketone functionahties can fragment by two different mechanisms, known as Norrish types I and II. The degradation of polymers with the carbonyl functionahty in the backbone of the polymer results in chain cleavage by both mechanisms, but when the carbonyl is in the polymer side chain, only Norrish type II degradation produces main-chain scission (37,49). A Norrish type I reaction for backbone carbonyl functionahty is shown by equation 5, and a Norrish type II reaction for backbone carbonyl functionahty is equation 6. 

Attaching the ketone groups to the polymer backbone is more efficient on a chain scission/ketone basis because some of the light energy that the pendent ketone absorbs leads direcdy to chain scission via the Norrish type II mechanism, as well as photooxidation via the Norrish type I mechanism (see... 

As a side reaction, the Norrish type I reaction is often observed. The stability of the radical species formed by a-cleavage determines the Norrish type 1/Norrish type II ratio. For example aliphatic methyl ketones 10 react by a Norrish type II-mechanism, while aliphatic tcrt-butyl ketones 11 react preferentially by a Norrish type I-mechanism. 

Majeti11 has studied the photochemistry of simple /I-ketosulfoxides, PhCOCH2SOCH3, and found cleavage of the sulfur-carbon bond, especially in polar solvents, and the Norrish Type II process to be the predominant pathways, leading to both 1,2-dibenzoylethane and methyl methanethiolsulfonate by radical dimerization, as well as acetophenone (equation 3). Nozaki and coworkers12 independently revealed similar results and reported in addition a pH-dependent distribution of products. Miyamoto and Nozaki13 have shown the incorporation of protic solvents into methyl styryl sulfoxide, by a polar addition mechanism. 

The mechanism probably involves a Norrish type I cleavage (p. 318), loss of CO from the resulting radical, and recombination of the radical fragments. 

Another mechanism for alkanone-sensitized photodehydrochlorination comprises Norrish type I scission of the ketone, followed by ground-state reactions of radicals (19). However, the evidence for such a mechanism is based on experiments that were carried out in the vapor phase (19). Initiation of the photodegradation of PVC by hexachloroacetone has been suggested to involve the abstraction of hydrogen from the polymer by radicals resulting from the photolysis of the ketone s carbon-chlorine bonds (22). 

Norrish type II mechanism for photo-oxidation of polyolefins. 

Since the photochemistry of many compounds that have been used as triplet sensitizers has been well studied, we will not attempt to cover these reactions in detail. Unless the investigator is unaware of them, common photochemical processes such as the Norrish Type II cleavage are not ordinarily a complication and as will be mentioned later, they can actually serve as mechanistic probes. A discussion of the mechanisms of triplet energy transfer1,3,9 is beyond the scope of this review as are other specific reactions which have been recently covered elsewhere. 

The dimethyl ester of this acid in solution shows a quantum efficiency photochemical products. On the other hand, when the same acid is copolymerized with a glycol to form a polymeric compound with molecular weight 10,000 the quantum yield drops by about two orders of magnitude, 0.012. The reason for this behavior appears to be that when the chromophore is in the backbone of a long polymer chain the mobility of the two fragments formed in the photochemical process is severely restricted and as a result the photochemical reactions are much reduced. If radicals are formed the chances are very good that they will recombine within the solvent cage before they can escape and form further products. Presumably the Norrish type II process also is restricted by a mechanism which will be discussed below. 

There are two basic methods for making polymer materials photo-chemically degradable.1,2 One method is to chemically incorporate a chromo-phore into the polymer chains. One commercially successful chromophore is the carbonyl group.1,2,7 Absorption of UV radiation leads to degradation by the Norrish type I and II processes or by an atom abstraction process (Scheme 1). Note that once radicals are introduced into the system, chain degradation occurs by the autoxidation mechanism (Scheme 2). 

There are at least three types of mechanisms discussed in order to explain the ODPM rearrangement. The first mechanism (Sch. 6) is radicaloid in nature in involves a Norrish type I cleavage leading to the formation of acyl and allyl radical and recombination of these radicaloid species to the ODPM rearrangement product in two ways. 

Still another reaction which is readily susceptible to our n-7r model is the Norrish Type II with concomitant cyclobutanol formation (i.e. the Yang reaction 33)). This mechanism was described in detail by the author 1,3,12), again in those early papers. Here the two dimensional circle-dot-y notation suffices and is convenient. Note Equation 8. 

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