A Quantum-Chemical Study of the Structure of the Complex of Dibenzo-18-Crown-6 Ether with CaCl2 and Its Reactivity in the Oxidation of Ethylbenzene

IF 0.58 Q4 Materials Science

Polymer Science, Series D Pub Date : 2025-03-16 DOI:10.1134/S1995421224701454

I. S. Rodionov, V. I. Anisimova, N. V. Ulitin, A. A. Baldinov, I. A. Suvorova, N. M. Nurullina, D. A. Shiyan, K. A. Tereshchenko, S N. Tuntseva, T. L. Puchkova, Kh. E. Kharlampidi, O. V. Stoyanov

引用次数: 0

Abstract

Ethylbenzene hydroperoxide (EBOOH) is used as an initiator of polymerization of anaerobic adhesives. It was experimentally established that the complex of dibenzo-18-crown-6 ether with CaCl₂ (Ca²⁺∙DBC) accelerates the ethylbenzene oxidation. Based on quantum-chemical modeling by the PBEPBE-GD3/def2TZVP method, it was revealed that the formation of the catalyst’s intermediate adducts with the reaction system’s components is possible and energetically favorable. The O–O bond strength decreases both in α-EBOOH and in β-EBOOH in the adduct EBOOH∙Ca²⁺∙DBC. However, the adduct α-EBOOH∙Ca²⁺∙DBC promotes a more rapid decomposition of ethylbenzene hydroperoxide into radicals.

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乙苯过氧化氢（EBOOH）被用作厌氧粘合剂的聚合引发剂。实验证明，二苯并-18-冠醚与 CaCl2 的复合物（Ca2+∙DBC）可加速乙苯氧化。根据 PBEPBE-GD3/def2TZVP 方法建立的量子化学模型显示，催化剂的中间加合物与反应体系的组分有可能形成，并且在能量上是有利的。在加合物 EBOOH∙Ca2+∙DBC 中，α-EBOOH 和 β-EBOOH 中的 O-O 键强度都会降低。然而，加合物 α-EBOOH∙Ca2+∙DBC 能更快地将过氧化氢乙苯分解成自由基。

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来源期刊

Polymer Science, Series D Materials Science-Polymers and Plastics

CiteScore

0.80

自引率

0.00%

发文量

期刊介绍： Polymer Science, Series D publishes useful description of engineering developments that are related to the preparation and application of glues, compounds, sealing materials, and binding agents, articles on the adhesion theory, prediction of the strength of adhesive joints, methods for the control of their properties, synthesis, and methods of structural modeling of glued joints and constructions, original articles with new scientific results, analytical reviews of the modern state in the field.