Surface Polymerization from Planar Surfaces by Atom Transfer Radical Polymerization Using Polyelectrolytic Macroinitiators

Abstract

The one-pot synthesis of a new anionic polyelectrolytic macroinitiator based on esterification of a poly(glycerol monomethacrylate) precursor is described. Electrostatic adsorption of this macroinitiator onto an aminated (cationic) planar substrate is monitored by dual polarization interferometry. Controlled surface-initiated polymerization of five hydrophilic methacrylic monomers from this macroinitiator adsorbed onto aminated silicon wafer surfaces is achieved by atom transfer radical polymerization (ATRP) in protic media. The thickness, uniformity, and hydrophilicity of the resulting polymer brushes are characterized by ellipsometry, atomic force microscopy and contact angle studies, and the hydrophilic surface polymerization kinetics is modeled. Microcontact printing is used to produce patterned surfaces with micrometer-sized features. In summary, polyelectrolytic macroinitiators allow the facile synthesis of well-defined polymer brushes on commercially relevant metal oxide surfaces.

Controlled Cell Adhesion on PEG‐Based Switchable Surfaces

“…In strategy C, pristine gold surfaces were first modified by layer-by-layer polyelectrolyte deposition and subsequently functionalized by the polyanionic ATRP macroinitiator 3 (macroinitiator "grafting-from" approach). [14] Poly(OEGMA-co-MEO 2 MA) brushes were then grown from the surfaces using either standard-ATRP or AGET-ATRP methods. [15] All surface-modification strategies efficiently produced poly(OEGMA-co-MEO 2 MA) brushes on gold substrates.…”

Challenges and developments of self-assembled monolayers and polymer brushes as a green lubrication solution for tribological applications

“…210,211 Although this method is relatively easy to carry out as it works much like a SAM, there is steric hindrance that impedes the density of the nal lm that is formed. 71,212,213 In addition to this, the adsorption techniques are reversible so that the layers may be susceptible to high shear forces.…”

“…The commercial success of ATRP has been well reported, in part due to the polymerisations ability to be completed in commercially available equipment. 210,213,221,227,238 ATRP can form well-dened polymer brushes from easily synthesised initiators and is well known as a successful controllable polymerisation.…”

Functionalization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) films via surface‐initiated atom transfer radical polymerization: Comparison with the conventional free‐radical grafting procedure

“…34 The addition of CuBr 2 to the polymerization mixture is usually required to quickly promote equilibrium between the dormant and active chains during Si-ATRP and to limit the polydispersity of the polymer grown on the surface. 19,35,36 Many reports have shown the importance of water in polymerization to accelerate the rate of ATRP of HEMA compared to that conduced in methanol. 35,37,38 The monomer mixture (HEMA in water) did not swell in hydrophobic PHBHV; this ensured that the polymer chains propagated from the initiator sites on the PHA film surface.…”