ROOH

Kharasch called this the peroxide effect and demonstrated that it could occur even if peroxides were not deliberately added to the reaction mixture Unless alkenes are pro tected from atmospheric oxygen they become contaminated with small amounts of alkyl hydroperoxides compounds of the type ROOH These alkyl hydroperoxides act m the same way as deliberately added peroxides promoting addition m the direction opposite to that predicted by Markovmkov s rule... 

The reaction follows a free radical mechanism and gives a hydroperoxide a compound of the type ROOH Hydroperoxides tend to be unstable and shock sensitive On stand mg they form related peroxidic derivatives which are also prone to violent decomposi tion Air oxidation leads to peroxides within a few days if ethers are even briefly exposed to atmospheric oxygen For this reason one should never use old bottles of dialkyl ethers and extreme care must be exercised m their disposal... 

If a self-sustained oxidation is carried out under limiting rate conditions, the hydroperoxide provides the new radicals to the system (by reaction 4 or analogues) and is maintained at a low concentration (decomposition rate = generation rate). For these circumstances, the rate equation 9 holds, where n = average number of initiating radicals produced (by any means) per molecule of ROOH decomposed and / = fraction of RH consumed which disappears by ROO attack (25). 

There are two main subclasses ofhydroperoxid.es organic (alkyl) hydroperoxides, ie, ROOH, and organomineral hydroperoxides, ie, Q(OOH), where Q is sihcon (43), germanium, tin, or antimony. The alkyl group in ROOH can be primary, secondary, or tertiary. Except for ethylbenzene hydroperoxide, only alkyl hydroperoxides are commercially important. 

Many random copolymers have found commercial use as elastomers and plastics. For example, SBR (62), poly(butadiene- (9-styrene) [9003-55-8] has become the largest volume synthetic mbber. It can be prepared ia emulsion by use of free-radical initiators, such as K2S20g or Fe /ROOH (eq. 18), or in solution by use of alkyl lithium initiators. Emulsion SBR copolymers are produced under trade names by such companies as American Synthetic Rubber (ASPC), Armtek, B. F. Goodrich (Ameripool), and Goodyear (PHoflex) solution SBR is manufactured by Firestone (Stereon). The total U.S. production of SBR in 1990 was 581,000 t (63). 

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