Title

On-Demand Degrafting and the Study of Molecular Weight and Grafting Density of Poly(Methyl Methacrylate) Brushes on Flat Silica Substrates

Document Type

Article

Publication Date

3-3-2015

Publication Title

Langmuir

Abstract

We report on degrafting of surface-anchored poly(methyl methacrylate) (PMMA) brushes from flat silica-based substrates using tetrabutylammonium fluoride (TBAF) and determining their molecular weight distribution (MWD) using size exclusion chromatography (SEC). The grafted PMMA layer was synthesized using surface-initiated atom transfer radical polymerization (SI-ATRP) of MMA for polymerization times ranging from 6 to 24 h. X-ray photoelectron spectroscopy, ellipsometry, and time-of-flight secondary ion mass spectrometry were employed in tandem to characterize the degrafting process. The SEC eluograms were fit to various polymer distributions, namely Zimm–Schulz, ATRP in continuous stirred tank reactor, Wesslau, Schulz–Flory, and Smith et al. The ATRP model gives the best fit to the experimental data. The dry PMMA brush thickness and the number-average molecular weight (obtained from the MWD) suggest that the grafting density of the PMMA grafts is independent of polymerization time, indicating well-controlled/living growth of MMA. The observed polydispersity index (PDI) was higher than that generally observed in bulk grown polymers under similar conditions, indicating an effect due to chain confinement and crowding. We detect small but noticeable dependence of the polymer brush grafting density on the inhibitor/catalyst ratio. Higher inhibitor/catalyst ratio offers better control with lower early terminations, which results in a small increase in the apparent grafting density of the chains.

Volume

31

Issue

8

First Page

2372

Last Page

2381

DOI

10.1021/la5044766

ISSN

ISSN: 0743-7463, ESSN: 1520-5827

Rights

Copyright © 2015 American Chemical Society

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