80037-93-0Relevant articles and documents
Initiation mechanisms for radical polymerization of methyl methacrylate with tert-butyl peroxypivalate
Nakamura, Tomoyuki,Busfield, W. Ken,Jenkins, Ian D.,Rizzardo, Ezio,Thang, San H.,Suyama, Shuji
, p. 10824 - 10828 (2007/10/03)
The reaction of tert-butyl peroxypivalate (2) with methyl methacrylate (3) has been studied by the radical trapping technique employing 1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindol-2-yloxyl (1) as a scavenger. Thermolysis of 2 generated tert-butoxyl, tert-butyl, and methyl radicals in the ratios of 48:50:2 at 60 °C in 3. Both alkyl radicals underwent selective tail addition to 3. tert-Butyl radicals reacted about twice as fast as methyl radicals with 3. The absolute rate constant for addition of tert-butyl radicals to 3 was estimated to be 2.3 x 106 M-1 s-1 at 60 °C. The overall ratio of addition to H abstraction in the reaction of 2 with 3 was 5:1.
On the Regioselectivity of Free Radical Processes; Reactions of Benzoyloxy, Phenyl and t-Butoxy Radicals with Some α,β-Unsaturated Esters
Moad, Graeme,Rizzardo, Ezio,Solomon, David H.
, p. 1573 - 1588 (2007/10/02)
The reactions of three electrophilic radicals, benzoyloxy, and t-butoxy, have been examined with a series of α,β-unsaturated esters; methyl acrylate, methyl methacrylate, and methyl crotonate.For the three monomers the ratio of hydrogen abstraction to double bond addition was found to increase and the ratio of head against tail addition to decrease in the series: benzoyloxy; phenyl; t-butoxy.Relative rates for these reactions have been determined and the factors influencing the mode of reaction are discussed.
