Contact-angle, ellipsometric, and spin-diffusion solid-state nuclear magnetic resonance spectroscopic investigations of copolymeric stationary phases immobilized on SiO2 surfaces.

Abstract

SiO2 surfaces-silica gel particles and silica wafers-were modified by covalently immobilizing three poly(ethylene-co-acrylic acid) copolymers, (-CH2CH2-)x[CH2CH/(CO2H)-]y, with different chain lengths and mass fractions of acrylic acid. 13C solid-state NMR spectroscopy on the modified silica gel particles revealed both mobile gauche and rigid trans aligned alkyl chains in the copolymers. For copolymers attached to silica wafers via a 3-aminopropyltriethoxysilane spacer molecule, ellipsometric measurements revealed a mean value of the layer thickness distribution of 6.5 and 4.3 nm, respectively, for the more acidic and the shorter copolymers with mobile alkyl chains mostly in the gauche conformation. For the longest and least acidic copolymer with more rigid trans ordered alkyl chains, however, a mean phase thickness of 10.6 nm was found. When this copolymer was immobilized via a 3-glycidoxypropyltrimethoxysilane spacer molecule we measured a mean layer thickness of 9.9 nm. A model of the surface morphology of this immobilization strategy was derived using spin-diffusion 13C NMR measurements on the corresponding modified silica. It was thereby proven that the trans and gauche-aligned alkyl chains occur in distinct domains of certain sizes on the silica surface. The surface polarity of all modified silica wafers was also investigated by measurement of contact-angle.