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Robust Thick Polymer Brushes Grafted From Gold Surfaces Using Bidentate Thiol-Based Atom-Transfer Radical Polymerization Initiators

Robust Thick Polymer Brushes Grafted From Gold Surfaces Using Bidentate Thiol-Based Atom-Transfer Radical Polymerization Initiators

Chul Soon Park, Han Ju Lee, Andrew C Jamison, T Randall Lee

ACS Appl Mater Interfaces. 2016 Mar 2;8(8):5586-94.

PMID: 26841087

Abstract:

A new bromoisobutyrate-terminated alkanethiol, 16-(3,5-bis(mercaptomethyl)phenoxy)hexadecyl 2-bromo-2-methylpropanoate (BMTBM), was designed as a bidentate adsorbate to form thermally stable bromoisobutyrate-terminated self-assembled monolayers (SAMs) on flat gold surfaces to conduct atom-transfer radical polymerizations (ATRPs). The monolayers derived from BMTBM were characterized by ellipsometry, X-ray photoelectron spectroscopy (XPS), and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and compared to the monolayers formed from 16-mercaptohexadecyl 2-bromo-2-methylpropanoate (MBM), 16-(3-(mercaptomethyl)phenoxy)hexadecyl 2-bromo-2-methyl-propanoate (MTBM), and octadecanethiol (C18SH). In this study, although the monolayer derived from BMTBM was less densely packed than those derived from MBM and MTBM, the bidentate adsorbates demonstrated much higher thermal stability in solution-phase thermal desorption tests, owing to the "chelate effect". The enhanced stability of the BMTBM SAMs ensured the development of thick brushes of poly(methyl methacrylate) and polystyrene at elevated temperatures (60, 90, 105, and 120 °C). In contrast, SAMs derived from MBM and MTBM failed to grow polymer brushes at temperatures above 100 °C.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP25986805	Poly(hexadecyl methacrylate) solution		25986-80-5	Price

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