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An X‐ray photoelectron spectroscopic investigation of the selectivity of hydroxyl derivatization reactions
Author(s) -
Chilkoti Ashutosh,
Ratner Buddy D.
Publication year - 1991
Publication title -
surface and interface analysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.52
H-Index - 90
eISSN - 1096-9918
pISSN - 0142-2421
DOI - 10.1002/sia.740170805
Subject(s) - chemistry , trifluoroacetic anhydride , derivatization , reactivity (psychology) , selectivity , reagent , organic chemistry , benzaldehyde , chloride , context (archaeology) , polymer chemistry , catalysis , high performance liquid chromatography , medicine , paleontology , alternative medicine , pathology , biology
The Selectivity of trifluoroacetic anhydride (TFAA), used for the vapor‐phase derivatization of hydroxyl groups in multifunctional oxygen‐containing polymeric surfaces, has been investigated by XPS studies on model epoxides systems. The reactivity of TFAA towards epoxides observed here is discussed in the context of the large amount of published literature implying high selectivity of this reaction towards hydroxyl groups. Acetyl chloride (AcCl) and heptafluorobutyryl chloride (HFBuCl), used to derivatize hydroxyl groups in the literature, were also examined, with regard to cross‐reaction with epoxides. Both AcCl and HFBuCl react with epoxides, forming chloroacetates and perfluorinated chloroacetates, respectively. Moreover, HFBuCl is shown to react with double bonds forming perfluorinated chloroacetates, while AcCl is unreactive towards them. The reactivity of HFBuCl to wards epoxides and unsaturation compromises its use as a derivatization reagent of hydroxyl groups. However, the unique reaction products formed by exposure of hydroxyls and epoxides to AcCl vapor may allow hydroxyl species to be distinguished from epoxides in multifunctional carbon‐oxygen polymeric surfaces.