Features of Polymerization of Methyl Methacrylate in the Presence of New Ruthenium(II) and Ruthenium(III) Carborane Complexes with Chelate P‒O‒P Ligands

IF 1 4区化学 Q4 POLYMER SCIENCE Polymer Science, Series B Pub Date : 2024-05-31 DOI:10.1134/s1560090424600219

N. A. Knyazeva, I. D. Grishin

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Abstract

The radical polymerization of methyl methacrylate by the atom transfer radical polymerization (ATRP) mechanism under the action of systems based on ruthenium(II) and ruthenium(III) carborane complexes containing chelate P‒O‒P ligands of various structures has been studied. It has been shown that systems based on these metal complexes, carbon tetrachloride, and isopropylamine as a reducing agent are capable of initiating the radical polymerization of methyl methacrylate. The most effective among those studied are systems based on ruthenacarboranes containing 9,9-dimethyl-4,5-bis-(diphenylphosphino)xanthene as a ligand. These compounds are capable of carrying out the process in a controlled manner, as evidenced by a linear increase in the molecular weight of the polymer and a decrease in dispersity values with increasing conversion. The controlled process according to the ATRP mechanism is confirmed by the presence of chlorine atoms at the ends of the polymer chains, as it has been detected by MALDI mass spectrometry. It has been shown that the possibility of coordination of the ruthenium atom with the oxygen atom of the ligand reduces the rate of the polymerization process and the degree of control over it.

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具有 P-O-P 螯合配体的新型钌（II）和钌（III）硼烷配合物在甲基丙烯酸甲酯聚合过程中的特征

摘要研究了在含有不同结构的 P-O-P 螯合配体的钌(II)和钌(III)硼烷配合物体系作用下，甲基丙烯酸甲酯通过原子转移自由基聚合（ATRP）机理进行自由基聚合的情况。研究表明，以这些金属络合物、四氯化碳和作为还原剂的异丙胺为基础的体系能够引发甲基丙烯酸甲酯的自由基聚合反应。在所研究的体系中，最有效的是以含有 9,9-二甲基-4,5-双（二苯基膦）呫吨的钌硼烷为配体的体系。这些化合物能够以受控的方式进行加工，聚合物分子量的线性增加和分散度值随转化率的增加而降低就是证明。MALDI 质谱法检测到聚合物链末端存在氯原子，这证实了 ATRP 机制的受控过程。研究表明，钌原子与配体氧原子配位的可能性降低了聚合过程的速率和控制程度。

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来源期刊

Polymer Science, Series B 化学-高分子科学

CiteScore

1.80

自引率

8.30%

发文量

审稿时长

>0 weeks

期刊介绍： Polymer Science, Series B is a journal published in collaboration with the Russian Academy of Sciences. Series B experimental and theoretical papers and reviews dealing with the synthesis, kinetics, catalysis, and chemical transformations of macromolecules, supramolecular structures, and polymer matrix-based composites (6 issues a year). All journal series present original papers and reviews covering all fundamental aspects of macromolecular science. Contributions should be of marked novelty and interest for a broad readership. Articles may be written in English or Russian regardless of country and nationality of authors. All manuscripts are peer reviewed