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N- and C-diallyl monomers of new structural types in radical polymerization: theoretical study on the mechanism of reaction

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Abstract

The cyclization and competing reactions for growing radical chains based on N-and C-diallyl monomers of new structural types have been investigated with density functional theory with B3LYP/6-311G(d) computations. The study of these reactions of five diallyl monomers, N,N-diallyl-N′-acetylhydrazine (DAAH) (I), 1,1-diallyl-3-methyl-2-(4-nitrofurazan-3-yl)guanidine (AMNG) (II), tris(diethylamino)diallylaminophosphonium chloride (DAAP-Cl) (III), 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride (AGC) (IV), 2-[(diallyl)hydroxymethyl]pyrrolidine (AGMP) (V), was carried out. The probability of homopolymerization is the highest in C-diallyl monomers. In neutral N-diallyl monomers, the reaction of intramolecular hydrogen abstraction proceeds more easily, whereas in the case of guanidinium salt, the availability of a charged guanidinium fragment leads to high efficiency of cyclopolymerization. These results are in good agreement with experimental data on the polymerization of N- and C-diallyl monomers of new structural types.

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Funding

The study of AGC was financially supported by the Russian Science Foundation (research project No. 23-23-00073). The investigation of DAAH, AMNG, DAAP and AGMP were carried out within the framework of the state task (No. 122012400109-8). Analytical and spectroscopic studies were carried out using the equipment of the Core Facilities Center "Research of materials and matter" at the PFRC UB RAS.

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Authors and Affiliations

  1. Institute of Technical Chemistry of Ural Branch of Russian Academy of Sciences, Korolev Str., 3, Perm, Russia, 614013

    Marina Gorbunova & Vladimir Strelnikov

  2. Perm State University, Bukirev Str., 15, Perm, Russia, 614090

    Marina Gorbunova, Sergey Shurov & Aleksandr Vasyanin

Authors
  1. Marina Gorbunova
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  2. Sergey Shurov
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  3. Aleksandr Vasyanin
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  4. Vladimir Strelnikov
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Contributions

M.G. and V.S. proposed the concept and determined the methodology. S.Sh. and A.V. made the calculations. M.N. wrote the main manuscript text and S.Sh. and A.V. prepared figures 3, 7. All authors reviewed the manuscript.

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Correspondence to Marina Gorbunova.

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Gorbunova, M., Shurov, S., Vasyanin, A. et al. N- and C-diallyl monomers of new structural types in radical polymerization: theoretical study on the mechanism of reaction. Theor Chem Acc 142, 121 (2023). https://doi.org/10.1007/s00214-023-03067-9

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