Spin Labels as the Instrument for Analysis of Topochemistry of Polymer-Immobilized Ziegler Catalytic Systems View Full Text


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Article Info

DATE

2000-03

AUTHORS

N. M. Bravaya, A. D. Pomogailo

ABSTRACT

A spin labeling technique was used to investigate the topochemical characteristics of polymer carriers and immobilized metal complexes. Functionalized polyethylenes (PE) such as PE–grafted-polyallylamine (1), PE–grafted-polydiallyl-amine (2), and PE–grafted-poly-4-vinylpyridine (3), obtained by grafting polymerization of the corresponding monomers, were used as polymer carriers. Metal-containing polymers were obtained by immobilization to 2 with either TiCl4 (2/Ti) or Al(C2H5)2 Cl (2/Al). The stable nitroxyl radical 2,2,6,6-tetramethyl-4-(2′-oxy-4′,6′-dichlorotriazine)piperidine-1-oxyl \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document} $$(\dot R_1 )$$ \end{document} was used for spin labeling 2 to give \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document} $$2/\dot R_1 $$ \end{document}, while 2,2,5,5,tetramethyl-3-(N-acetoamidiiodine)-pyrrollidine-1-oxyl \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document} $$(\dot R_2 )$$ \end{document} was used for spin labeling 3 to give \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document} $$3/\dot R_2 $$ \end{document}. Radical 2,2,6,6-tetramethyl-4-hydroxy-pyperidine-1-oxyl \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document} $$(\dot R_3 )$$ \end{document} was bonded to 2/Ti and 2/Al to give \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document} $$2/Ti/\dot R_3 $$ \end{document} and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document} $$2/Al/\dot R_3 $$ \end{document}, respectively. The accessibility of the functionalized polymers 1–3 to interact with the spin labels and the immobilized metal complexes was examined. Estimation of the effective distances between the spin labels and the dynamic behavior of nitroxyl radicals in the functionalized polymer matrixes and metal-containing polymers revealed several important features of spin-labeled systems. Metallation of a functional covering makes the polymer more accessible for spin labeling and has a considerable effect on the dynamic characteristics of polymer matrix. A change of the rotational activation energy of the spin labels from 15 kcal/mol in \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document} $$2/\dot R_1 $$ \end{document} to 44 kcal/mol for \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document} $$2/Ti(Al)/\dot R_3 $$ \end{document} in the temperature range 100–150°C was observed. More... »

PAGES

1-22

Identifiers

URI

http://scigraph.springernature.com/pub.10.1023/a:1009494915016

DOI

http://dx.doi.org/10.1023/a:1009494915016

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1015667848


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