Quantifying Solvent Effects on Polymer Surface Grafting

When grafting polymers onto surfaces, the reaction conditions critically influence the resulting interface properties, including the grafting density and molar mass distribution (MMD) on the surface. Herein, we show theoretically and experimentally that the application of poor solvents is beneficial for the "grafting-to" approach. We demonstrate the effect by grafting poly(methyl methacrylate) chains on silica nanoparticles in different solvents and compare the MMD of the polymer in solution before and after grafting via size exclusion chromatography (SEC). The shorter polymer chains are preferentially grafted onto the surface, leading to a distortion effect between the MMD in solution and on surfaces. The molecular weight distortion effect is significantly higher for ethyl acetate (good solvent quality, difference in M_w surface to solution 14%) than for N,N-dimethylacetamide (poor solvent quality, 6%). The difference in MMD on the surface to the solution significantly affects both the surface properties (e.g. the grafting densities) and their determination.