自由基非支链加成C=C、C=O和O=O分子键的新动力学模型

M. M. Silaev
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引用次数: 0

摘要

如果一个自由基的未配对的对电子可能离域,如烯丙基自由基CH2=CHĊH2在共轭键上,或甲酰基自由基HĊ=O在从碳到更具电子仿射性的氧的双键上,那么它可能是低反应性的。注意自由基的活性也与它所参与的反应热有关。在非支链反应自由基(加成)加入分子双键的过程中,反应中较低活性自由基的形成,与反应自由基的传播平行或竞争,导致链终止。因为这些低活性自由基不参与进一步的链传播,因为它们在相互碰撞或与链载体活性自由基碰撞时会衰变,从而导致后者的低效消耗和过程抑制。
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New Kinetic Models of Free-Radical Nonbranched-Chain Addition to C=C, C=O, and O=O Molecular Bonds
A free radical may be low-reactive if its unpaired p-electron may be delocalized, e.g., over conjugated bonds as in the case of allyl radical CH2=CHĊH2 or along a double bond from carbon to the more electron-affine oxygen as in the case of formyl radical HĊ=O. Note that the activity of a free radical is also connected to the reaction heat in which it participates. In nonbranched-chain processes of reactive free radical (addend) addition to double bonds of molecules, the formation of rather low-reactive free radicals in reactions, which are parallel to or competing with propagation via a reactive radicals, lead to chain termination, because these low-reactive radicals do not participate in further chain propagation and because they decay when colliding with each other or with chain-carrier reactive radicals thus resulting in inefficient expenditure of the latter and process inhibition.
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