Effects of Hydrophobic Modification of Linear- and Branch- Structured Fluorinated and Nonfluorinated Silanes on Mesoporous Silica Particles

This work reports a comparison of hydrophobic surface modification on mesoporous silica particles (MSPs) obtained by large-scale production using a batch reactor with linear and branched fluorinated and nonfluorinated silanes. Fluorinated silanes were used with TDF-TMOS and TFP-TMOS as a linear and branched structure, respectively. Nonfluorinated silanes were used with OD-TEOS and HMDS as a linear and branched structure, respectively. These four silanes were grafted on the surface of the MSPs as the function of the concentrations, and then, the water contact angles (WCAs) were measured. The WCA of the four silane-grafted MSPs was higher in the branch-structured silanes, namely, TFP-TMOS@MSPs and HMDS@MSPs than in linear-structured silanes, namely, TDF-TMOS and OD-TEOS due to the higher hydrophobicity by a lot of -F and -CH3 groups. Furthermore, the relationship between the WCA and BET parameters was demonstrated using the surface areas, pore volumes, and grafted amounts of the four silane-grafted MSPs. The structural characterization was demonstrated by solid-state Si-29 MAS NMR to determine the bonding environment of Si atoms between the grafted silane and the surfaces of MSPs using the T-3/T-2 and Q(3)/Q(4) ratios of the fluorinated and nonfluorinated silane-grafted MSPs. Among the four silanes, nonfluorinated HMDS@MSPs had a high contact angle of 135 degrees as fluorinated TFP-TMOS@MSPs. When 5 wt % of HMDS@MSPs mixed with gravure ink was coated on a biodegradable polylactic acid (PLA) film, the contact angle was improved to 131.8 from 83.3 degrees of the natural PLA film.