A Consideration of the Q-e Scheme. IV. A Theoretical Approach to Price-Alfrey's Polarity Term
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概要
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Previously, we pointed out the correlations of the <I>P</I>-, <I>Q</I>- and <I>e</I>-terms with the components of the conjugation-stabilization energy between monomers and attacking radicals. In the present paper, the effect of heteroatoms on the components of the stabilization energy was investigated. For each series of isoelectronic monomers, in which a fixed carbon atom of a reference monomer (ethylene, styrene, butadiene or another neutral monomer) is replaced by a heteroatom (oxygen, nitrogen, etc.), we obtained the relations: ln<I>Q</I>－ln<I>Q</I><SUB>0</SUB>=(<I>C<SUB>m</SUB></I>⁄<B>RT</B>)(δ<I>X</I>)<SUP>2</SUP>, <I>P</I>∞exp(<I>C<SUB>r</SUB></I>⁄<B>RT</B>)(δ<I>Y</I>)<SUP>2</SUP>, <I>e</I><SUB>R</SUB>=－\sqrt<I>C</I>′<I><SUB>rm</SUB></I>⁄<B>RT</B>(δ<I>Y</I>) and <I>e</I><SUB>M</SUB>=－\sqrt<I>C</I>′<I><SUB>rm</SUB></I>⁄<B>RT</B>(δ<I>X</I>). Here, <I>C<SUB>m</SUB></I>, <I>C<SUB>r</SUB></I> and <I>C</I>′<I><SUB>rm</SUB></I> are positive constants characteristic of the monomer series, while δ<I>X</I> and δ<I>Y</I> are the Coulomb integral increments of the heteroatoms (relative to a carbon atom) in the monomer X and the radical Y respectively. <I>Q</I><SUB>0</SUB> is the <I>Q</I>-value of the reference monomer of the series. The <I>e</I>-values of the reference monomers were all assumed to be zero. The opinions of Price and Alfrey that the polarity term is the product of <I>e</I><SUB>R</SUB> and <I>e</I><SUB>M</SUB> and that <I>e</I><SUB>R<SUB>1</SUB></SUB>=<I>e</I><SUB>M<SUB>1</SUB></SUB> for the radical and the monomer of type 1 seem to be not only convenient but also reasonable for a series of monomers having a same skeletal structure. The π-electronic charges, <I>q</I><SUB>R</SUB> and <I>q</I><SUB>M</SUB>, on the end groups of the radical and the monomer seem to be correlated with <I>e</I><SUB>R</SUB> and <I>e</I><SUB>M</SUB> in such a manner that <I>e</I><SUB>R</SUB>=－(\sqrt<I>C</I>′<I><SUB>rm</SUB></I>⁄<B>RT</B>⁄<I>C</I><SUB>R</SUB>)<I>q</I><SUB>R</SUB> and <I>e</I><SUB>M</SUB>=－(\sqrt<I>C</I>′<I><SUB>rm</SUB></I>⁄<B>RT</B>⁄<I>C</I><SUB>M</SUB>)<I>q</I><SUB>M</SUB> Here, <I>C</I><SUB>R</SUB> and <I>C</I><SUB>M</SUB> are negative constants characteristic of the series of monomers. The correlation of the polarity term with the electrostatic interaction between the charges of the radical and the monomer seems to be ascribable to these relations.
- 社団法人 日本化学会の論文
著者
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Furukawa Junji
Department Of Applied Chemistry Aichi Institute Of Technology
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TSURUTA Teiji
Department of Industrial Chemistry, Science University of Tokyo
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Fueno Takayuki
Department of Synthetic Chemistry Kyoto University
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Kawabata N.
Department of Synthetic Chemistry Kyoto University
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