Journal Article

A 29Si, 1H, and 13C Solid-State NMR Study on the Surface Species of Various Depolymerized Organosiloxanes at Silica Surface

Le, Zichun, Zhang, Dong, Dong, Wen, Henderson, Ian M., Morozov, Yevhenii M., Protsak, Iryna S.

2019

Overview

Three poly(organosiloxanes) (hydromethyl-, dimethyl-, and epoxymethylsiloxane) of different chain lengths and pendant groups and their mixtures of dimethyl (DMC) or diethyl carbonates (DEC) were applied in the modification of fumed silica nanoparticles (FSNs). The resulting modified silicas were studied in depth using 29 Si, 1 H, and 13 C solid-state NMR spectroscopy, elemental analysis, and nitrogen adsorption-desorption (BET) analysis. The obtained results reveal that the type of grafting, grafting density, and structure of the grafted species at the silica surface depend strongly on the length of organosiloxane polymer and on the nature of the “green” additive, DMC or DEC. The spectral changes observed by solid-state NMR spectroscopy suggest that the major products of the reaction of various organosiloxanes and their DMC or DEC mixtures with the surface are D (RR’Si(O 0.5 ) 2 ) and T (RSi(O 0.5 ) 3 ) organosiloxane units. It was found that shorter methylhydro (PMHS) and dimethylsiloxane (PDMS) and their mixtures with DMC or DEC form a denser coverage at the silica surface since S BET diminution is larger and grafting density is higher than the longest epoxymethylsiloxane (CPDMS) used for FSNs modification. Additionally, for FSNs modified with short organosiloxane PMHS/DEC and also medium organosiloxane PDMS/DMC, the dense coverage formation is accompanied by a greater reduction of isolated silanols, as shown by solid-state 29 Si NMR spectroscopy, in contrast to reactions with neat organosiloxanes. The surface coverage at FSNs with the longest siloxane (CPDMS) greatly improves with the addition of DMC or DEC. The data on grafting density suggest that molecules in the attached layers of FSNs modified with short PMHS and its mixture of DMC or DEC and medium PDMS and its mixture of DMC form a “vertical” orientation of the grafted methylhydrosiloxane and dimethylsiloxane chains, in contrast to the reaction with PDMS/DEC and epoxide methylsiloxane in the presence of DMC or DEC, which indicates a “horizontal” chain orientation of the grafted methyl and epoxysiloxane molecules. This study highlights the major role of solid-state NMR spectroscopy for comprehensive characterization of solid surfaces. Graphical abstract

• Publisher: Springer US,Springer Nature B.V,Springer,SpringerOpen
• Subject: 13C solid-state NMR spectroscopy / 1H solid-state NMR spectroscopy / 29Si solid-state NMR spectroscopy / Bonding density / Carbonates / Chemistry and Materials Science / Density / Depolymerization / Dialkyl carbonates / Fumed nanosilica / Grafting / Horizontal orientation / INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY / Magnetic resonance spectroscopy / Materials Science / Mixtures / Molecular Medicine / Nano Express / Nanochemistry / Nanoparticles / Nanoscale Science and Technology / Nanotechnology / Nanotechnology and Microengineering / NMR / NMR spectroscopy / Nuclear magnetic resonance / Physics / Polydimethylsiloxane / Polymers / Science & Technology - Other Topics / Silica / Silica fume / Silicon / Silicon dioxide / Silicone resins / Silicones / Silicones, Dialkyl carbonates / Siloxanes / Solid state / Solid surfaces / Spectroscopy / Spectrum analysis / Surface modification / Vertical orientation