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Norrish mechanism

Degradation of polyolefins such as polyethylene, polypropylene, polybutylene, and polybutadiene promoted by metals and other oxidants occurs via an oxidation and a photo-oxidative mechanism, the two being difficult to separate in environmental degradation. The general mechanism common to all these reactions is that shown in equation 9. The reactant radical may be produced by any suitable mechanism from the interaction of air or oxygen with polyolefins (42) to form peroxides, which are subsequentiy decomposed by ultraviolet radiation. These reaction intermediates abstract more hydrogen atoms from the polymer backbone, which is ultimately converted into a polymer with ketone functionahties and degraded by the Norrish mechanisms (eq. [Pg.476]

Nornicotine, 2 83. See also Nicotine ( j-AT-Norprotosinomenine, 2 90 Norrish mechanisms, 23 376 Norsk Hydro, magnesium manufacturing by, 15 332-334 Norsorex, 22 363-364 North America... [Pg.635]

Further support for the Husain and Norrish mechanism comes from the work of Bradley et They studied the shock oxidation of NH3 at total pressures... [Pg.100]

Problem 5.9. The 2-nitrobenzyl group is used as a base- and acid-stable but photolabile protecting group for alcohols. Draw a Norrish mechanism for the release of an alcohol from a 2-nitrobenzyl ether upon photolysis. [Pg.253]

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. [Pg.476]

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... [Pg.512]

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. [Pg.216]

Chain transfer to polymer is reported as a major complication and is thought to be unavoidable in the polymerization of alkyl acrylates.200 202 The mechanism is believed to involve abstraction of a tertiary backbone hydrogen (Scheme 6.32). It has been proposed that this process and the consequent formation of branches may contribute to the early onset of the gel or Norrish-Trommsdorff effect in the polymerization of these monomers. At high temperatures the radicals formed may undergo fragmentation. [Pg.322]

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. [Pg.874]

The mechanism probably involves a Norrish type I cleavage (p. 318), loss of CO from the resulting radical, and recombination of the radical fragments. [Pg.1354]

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). [Pg.200]

Norrish type II mechanism for photo-oxidation of polyolefins. [Pg.698]

Recent experiments have demonstrated the operation of the hole hopping mechanism between G bases in DNA.145,481 In these experiments, Norrish I photocleavage of an acylated nucleoside in a syn-... [Pg.288]

Vesely [2b] concluded that since the value of 1/DP obtained (by extrapolation) at [A1C13] = 0, was approximately the same as that obtained from Norrish and Russell s results with stannic chloride [5], the fundamental mechanism of polymerisation by both catalysts must be the same. Whilst this may be so, it does not follow from this evidence, because the extrapolations are afflicted by considerable uncertainty and, moreover, it is now known that the transfer coefficients which determine the intercept depend on the nature of the catalyst. [Pg.404]


See other pages where Norrish mechanism is mentioned: [Pg.688]    [Pg.688]    [Pg.579]    [Pg.688]    [Pg.688]    [Pg.579]    [Pg.62]    [Pg.124]    [Pg.236]    [Pg.244]    [Pg.628]    [Pg.325]    [Pg.1299]    [Pg.224]    [Pg.200]    [Pg.201]    [Pg.209]    [Pg.427]    [Pg.288]    [Pg.138]    [Pg.108]    [Pg.117]    [Pg.58]    [Pg.32]    [Pg.303]    [Pg.265]    [Pg.24]    [Pg.28]    [Pg.65]    [Pg.140]    [Pg.256]    [Pg.260]   
See also in sourсe #XX -- [ Pg.750 , Pg.855 ]




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