Polyamine-Activated Polymerization Amine Structure and Activation

Inhibition of the Autoxidation of Organic Substances in the Liquid Phase.

“…Polyethylene and polypropylene polyamines must give radicals on reaction with a tertiary hydroperoxide (cumene hydroperoxide), since this reaction initiates the emulsion polymerization of styrene ( 333), but they may not give radicals with secondary hydroperoxides (see Section IV). A representative selection of primary, secondary, and tertiary amines do not, however, initiate the polymerization of styrene on reaction with tertiary hydroperoxides (333). The hydroperoxides are instead converted in high yield to the corresponding carbinols, the rate of reaction following the order tertiary amines > secondary amines > primary amines (64,85).…”

“…The generally deleterious effects of metals on organic oxidations can be most readily overcome both by deactivating dissolved metals by the addition of chelating (complex-forming) agents such as ethylenediamine tetraacetic acid or A^M'-disalicylidene-l^-propanediamine (65,255,330,333), and, when metal surfaces are present, by the addition of metal passivators as described above. The antioxidant activity of these compounds naturally only appears in the presence of metals.…”

“…The occurrence of this synergism between alkylamines and inhibitors of free radicals (66,97,167,251,294) provides further proof that, in autoxidations, alkyl amine-hydroperoxide reactions leading to the production of free radicals are comparatively unimportant (see Section II,D). For example, polyalkylene polyamines enhance the activity of phenolic antioxidants for the stabilization of edible fats and oils (68), whereas they rapidly decompose tertiary hydroperoxides to give free radicals (333). The difference in their behavior would seem to be due to the formation of a different type of hydroperoxide (i.e., nontertiary) in the fats and oils.…”

A new stepwise synthesis of a family of propylamines derived from diatom silaffins and their activity in silicification

“…Other non-methylated polyamines containing four and six nitrogen atoms have been obtained by reaction of trimethylene dibromide with trimethylendiamine or dipropylenetriamine. 7,8 The reaction is complicated and a mixture of polymeric and branched products are synthesised requiring complicated separations. As the amine chain is increased, the likelihood of branching also increases as the relative concentration of end amino-groups decreases.…”

GR-S Aging in Solution

“…A partial answer to this seeming paradox appears to be in the discoveries connected with redox systems of polymerization. The use of aliphatic amines, for example, to initiate cold polymerization (9, 11) gives confirmation of the view' (7) that the induced decomposition of a peroxide gives a free radical as a by-product. This free radical may be the cause of subsequent polymerization or autoxidation steps before it, too, interacts with the amine and presumably dehydrogenates the amine to form a nitrogen radical.…”