Tailoring pore size of mesoporous silica and organosilica using biodegradable pentablock copolymer templates via EISA process

Abstract

In this work, we have designed unique poly(lactic acid-co-glycolic acid)-b-poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)-b-poly(lactic acid-co-glycolic acid) pentablock copolymers using Pluronic F68 and F108 triblock copolymers as macroinitiators. The poly(lactic acid-co-glycolic acid) (PLGA) blocks were attached as glycolide and lactide monomers at the both ends of each F68 and F108 triblock copolymer. The molecular weights and the block fractions were confirmed by gel permeation chromatography (GPC) and proton nuclear magnetic resonance (1H NMR) for the four kinds of pentablock copolymers. Using these pentablock copolymers as templates, we synthesized mesoporous ethane-silicas as well as silicas by the evaporation-induced self-assembly (EISA) method. 1,2-bis(triethoxysily)ethane (BTEE) were used as an organosilica precursor. The mesoporous ethane-silica samples were characterized using synchrotron small angle X-ray scattering (SAXS), nitrogen sorption experiments, transmission electron microscopy (TEM), and solid-state 29Si CP-MAS NMR. Based on the experimental results, it was confirmed that the porosity and pore diameter can be varied with the PLGA weight fraction of the pentablock copolymer. It is due to the PLGA block in polymer forming the hydrophobic domain in micelles, which leads to the formation of increased pore size over 20 nm without any additive pore expander. In addition, it seems that as the organosilica precursor increases, the association number of block copolymers forming one micelle decreases, resulting in a decrease in pore size. In summary, the polymer template plays a vital part in tuning the structure of the mesoporous ethane-silica samples. Thus, the development of synthetic method of mesoporous organosilica materials using polymer templates with different topology is still challenging and can endow the unique structure and property for mesoporous organosilica for future applications.