"Initiators, Free-Radical". In: Encyclopedia of Polymer Science and ...

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580 INITIATORS, FREE-RADICAL Vol. 6
Table 8. Commercial tert-Alkyl Hydroperoxides
CAS registry
Name number Structure
tert-Butyl hydroperoxide [75-91-2] t-C4H9OOH
tert-Amyl hydroperoxide [3425-61-4] t-C5H11OOH
α-Cumyl hydroperoxide [80-15-9]
2,5-Dihydroperoxy-2,5-dimethylhexane [3025-88-5]
para-Menthane hydroperoxide a [26762-92-5]
m/p-Isopropyl-α-cumyl hydroperoxide [98-49-7]
a The OOH group may be attached to any of the three positions indicated.
in TCE where radicals are scavenged before they can induce the decomposition of
peroxydicarbonate molecules.
Peroxydicarbonates are efficient polymerization initiators for most vinyl
monomer polymerizations, especially for monomers such as acrylates, ethylene,
and vinyl chloride. They are particularly good initiators for less reactive monomers
such as those containing allyl groups. They are also effective for curing of unsaturated
polyester molding resins. In order to increase the shipping and handling
safety of peroxydicarbonates, stabilized formulations have been developed and
commercialized (115–120).
tert-Alkyl Hydroperoxides. Some commercially available tert-alkyl hydroperoxides
(121) are listed in Table 8. Hydroperoxides can decompose thermally
to initially form alkoxy and hydroxy radicals:
However, because of the high temperature nature of this class of peroxides
(10-h half-life temperatures of 133–172 ◦ C) and their extreme sensitivities to
radical-induced decompositions and transition-metal activation, hydroperoxides
have very limited utility as thermal initiators. The acid-promoted decomposition
to produce radicals has been reported (122). The oxygen–hydrogen bond in
(31)