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. 2023 Jun 6;39(22):7613-7622.
doi: 10.1021/acs.langmuir.3c00280. Epub 2023 May 22.

Modular and Substrate-Independent Grafting-To Procedure for Functional Polymer Coatings

Lucas W Teunissen  1 , Maarten M J Smulders  1 , Han Zuilhof  1   2
Affiliations

Modular and Substrate-Independent Grafting-To Procedure for Functional Polymer Coatings

Lucas W Teunissen et al. Langmuir. .

Abstract

The ability to tailor polymer brush coatings to the last nanometer has arguably placed them among the most powerful surface modification techniques currently available. Generally, the synthesis procedures for polymer brushes are designed for a specific surface type and monomer functionality and cannot be easily employed otherwise. Herein, we describe a modular and straightforward two-step grafting-to approach that allows introduction of polymer brushes of a desired functionality onto a large range of chemically different substrates. To illustrate the modularity of the procedure, gold, silicon oxide (SiO2), and polyester-coated glass substrates were modified with five different block copolymers. In short, the substrates were first modified with a universally applicable poly(dopamine) primer layer. Subsequently, a grafting-to reaction was performed on the poly(dopamine) films using five distinct block copolymers, all of which contained a short poly(glycidyl methacrylate) segment and longer segment of varying chemical functionality. Ellipsometry, X-ray photoelectron spectroscopy, and static water contact angle measurements confirmed successful grafting of all five block copolymers to the poly(dopamine)-modified gold, SiO2, and polyester-coated glass substrates. In addition, our method was used to provide direct access to binary brush coatings, by simultaneous grafting of two different polymer materials. The ability to synthesize binary brush coatings further adds to the versatility of our approach and paves the way toward production of novel multifunctional and responsive polymer coatings.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Illustration of the Grafting-To Reaction Employed in This Study
A range of block copolymers (shown in red) of various compositions are grafted to poly(dopamine)-modified SiO2, gold, and PE substrates.
Scheme 2
Scheme 2. Molecular Structure of the Block Copolymers That Were Synthesized Using RAFT Polymerization and Employed in the Grafting-To Reactions in This Study
Figure 1
Figure 1
Layer thickness of poly(dopamine) film (gray bars) and block copolymers grafted to the poly(dopamine)-modified gold (A) and SiO2 (B) substrates determined by spectroscopic ellipsometry. (C) XPS wide scan spectra for pristine and poly(dopamine)-modified PE, SiO2, and gold samples. Note the appearance of the characteristic N 1s signal for the modified surfaces. (D) Static water contact angles for pristine substrates, poly(dopamine)-modified substrates, and poly(dopamine)-modified substrates after grafting of block copolymers.
Figure 2
Figure 2
XPS C1s narrow scan spectra of gold (A), SiO2 (B), and PE (C) after modification with poly(dopamine) and after subsequent grafting of poly(GMA)-b-poly(TFEMA), poly(GMA)-b-poly(MeOEGMA), poly(GMA)-b-poly(NMEP), poly(GMA)-b-poly(MMA), and poly(GMA)-b-poly(NIPAM).
Scheme 3
Scheme 3. Illustration of the Synthesis of Binary Brush Systems
Poly(GMA)-b-poly(TFEMA) and poly(GMA)-b-poly(MeOEGMA) copolymers, displayed as blue and red chains, respectively, were grafted to poly(dopamine)-modified SiO2 substrates.
Figure 3
Figure 3
(A) Layer thickness of poly(dopamine) film (gray bars) and poly(GMA)-b-poly(MeOEGMA)/poly(GMA)-b-poly(TFEMA) binary brush systems on SiO2. (B) XPS carbon narrow scan spectra of poly(GMA)-b-poly(MeOEGMA)/poly(GMA)-b-poly(TFEMA) binary brushes grafted on poly(dopamine)-modified SiO2.
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