Functionalization of Polystyrene Resins by Chemical Modification: Characterization of Halogenated Polystyrenes by Carbon-13 Nuclear Magnetic Resonance Spectroscopy

M. Jean Farrall; Jean M.J. Fréchet

doi:10.1021/ma60069a016

Functionalization of Polystyrene Resins by Chemical Modification: Characterization of Halogenated Polystyrenes by Carbon-13 Nuclear Magnetic Resonance Spectroscopy

M. Jean Farrall, Jean M.J. Fréchet

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26 Scopus citations

Abstract

The halogenation of polystyrene using ferric chloride and thallic acetate as catalysts for the bromination, and thallic trifluoroacetate with iodine in stoichiometric amounts for the iodination, has been studied by ¹³C-NMR spectroscopy using standard polymers obtained by polymerization of o-, m-, and p-bromostyrene. In all cases, the halogenated polymers were found to be substituted exclusively in the para position. Similarly, a brominated polymer prepared by reaction of polystyrene with n-butyllithium-TMEDA complex followed by bromine quenching was found to be substituted exclusively in the para position, while a similar lithiation followed by quenching with methyl iodide gave a methylated polymer substituted both in the meta and para positions in a 2:1 ratio. Lithiations carried out with tert-butyllithium-TMEDA resulted in higher degrees of functionalization than those carried out with n-butyllithium-TMEDA.

Original language	English (US)
Pages (from-to)	426-428
Number of pages	3
Journal	Macromolecules
Volume	12
Issue number	3
DOIs	https://doi.org/10.1021/ma60069a016
State	Published - 1979
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "Functionalization of Polystyrene Resins by Chemical Modification: Characterization of Halogenated Polystyrenes by Carbon-13 Nuclear Magnetic Resonance Spectroscopy",

abstract = "The halogenation of polystyrene using ferric chloride and thallic acetate as catalysts for the bromination, and thallic trifluoroacetate with iodine in stoichiometric amounts for the iodination, has been studied by 13C-NMR spectroscopy using standard polymers obtained by polymerization of o-, m-, and p-bromostyrene. In all cases, the halogenated polymers were found to be substituted exclusively in the para position. Similarly, a brominated polymer prepared by reaction of polystyrene with n-butyllithium-TMEDA complex followed by bromine quenching was found to be substituted exclusively in the para position, while a similar lithiation followed by quenching with methyl iodide gave a methylated polymer substituted both in the meta and para positions in a 2:1 ratio. Lithiations carried out with tert-butyllithium-TMEDA resulted in higher degrees of functionalization than those carried out with n-butyllithium-TMEDA.",

author = "{Jean Farrall}, M. and Fr{\'e}chet, {Jean M.J.}",

year = "1979",

doi = "10.1021/ma60069a016",

language = "English (US)",

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T1 - Functionalization of Polystyrene Resins by Chemical Modification

T2 - Characterization of Halogenated Polystyrenes by Carbon-13 Nuclear Magnetic Resonance Spectroscopy

AU - Jean Farrall, M.

AU - Fréchet, Jean M.J.

PY - 1979

Y1 - 1979

N2 - The halogenation of polystyrene using ferric chloride and thallic acetate as catalysts for the bromination, and thallic trifluoroacetate with iodine in stoichiometric amounts for the iodination, has been studied by 13C-NMR spectroscopy using standard polymers obtained by polymerization of o-, m-, and p-bromostyrene. In all cases, the halogenated polymers were found to be substituted exclusively in the para position. Similarly, a brominated polymer prepared by reaction of polystyrene with n-butyllithium-TMEDA complex followed by bromine quenching was found to be substituted exclusively in the para position, while a similar lithiation followed by quenching with methyl iodide gave a methylated polymer substituted both in the meta and para positions in a 2:1 ratio. Lithiations carried out with tert-butyllithium-TMEDA resulted in higher degrees of functionalization than those carried out with n-butyllithium-TMEDA.

AB - The halogenation of polystyrene using ferric chloride and thallic acetate as catalysts for the bromination, and thallic trifluoroacetate with iodine in stoichiometric amounts for the iodination, has been studied by 13C-NMR spectroscopy using standard polymers obtained by polymerization of o-, m-, and p-bromostyrene. In all cases, the halogenated polymers were found to be substituted exclusively in the para position. Similarly, a brominated polymer prepared by reaction of polystyrene with n-butyllithium-TMEDA complex followed by bromine quenching was found to be substituted exclusively in the para position, while a similar lithiation followed by quenching with methyl iodide gave a methylated polymer substituted both in the meta and para positions in a 2:1 ratio. Lithiations carried out with tert-butyllithium-TMEDA resulted in higher degrees of functionalization than those carried out with n-butyllithium-TMEDA.

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Functionalization of Polystyrene Resins by Chemical Modification: Characterization of Halogenated Polystyrenes by Carbon-13 Nuclear Magnetic Resonance Spectroscopy

Abstract

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