Atmospheric pulsed plasma copolymerization of acrylic monomers: Kinetics, chemistry, and applications

Abstract

In this study, dimethylacrylamide (DMA) homopolymer and DMA/ethylene glycol dimethacrylate (DMA/EGDMA) copolymers are produced by an atmospheric pulsed plasma deposition technique. Such a mild deposition method is used to limit monomer fragmentations and favor cross‐linked structures formed through the unsaturated carbon double bond polymerization. The kinetics of deposition, and the dependence of the chemical and physical properties of the films on the comonomer ratio are investigated by combining surface and volume‐sensitive techniques. In addition, water‐stable catechol‐bearing terpolymer films are easily produced from a precursor mixture composed of dopamine methacrylamide dissolved in a 50 mol% DMA/EGDMA solution. Finally, it is demonstrated that the developed coatings can be exploited for efficient one‐step bioconjugation reaction for potential biological applications.

Ultrathin Film Hydrogels with Controlled Swelling and Viscoelastic Properties Deposited by Nanosecond Pulsed Plasma Induced‐Polymerization

“…Moreover, a shift to higher wavelength numbers of the C═O band can be observed for polymerized samples, supporting the free‐radical polymerization mechanism proposed. [ 17 ] Both samples exhibit most of the characteristic MAA and EGDMA absorption bands (as highlighted in Figure 2) proving that the structural integrity of the monomers is mainly preserved. However, fragmentation/recombination phenomena cannot be neglected in AP plasma‐induced polymerization, as observed by the widening, splitting and shifting of some MAA peaks, like the C─O stretching in ─COOH at 1186 cm −1 , the triplet centered at 1389 cm −1 (attributed to CH 3 symmetric/antisymmetric deformations and skeletal vibrations) [ 20 ] or the new doublet at 1246 and 1271 cm −1 attributed to EGDMA (see FTIR spectra obtained for P(EGDMA) in Figure S1, Supporting Information).…”

“…Lots of efforts have been put to elucidate the optimum experimental conditions for controlled polymerization, as the kinetics are very sensible to a wide range of parameters, such as the atmosphere composition (presence of oxygen and reactive oxygen species), [ 13a ] the initial set‐up (precursor is injected in plasma in‐discharge or post‐discharge, distance of the plasma discharge to the substrate…) [ 11 ] or plasma power, [ 15 ] among much others. [ 16 ] In this context, our group has recently published a work [ 17 ] reporting the successful plasma polymerization copolymerization of different acrylic monomers in the liquid state. Interestingly, we also demonstrate that plasma exposure time can be effectively used to control the kinetics of polymerization.…”

Plasma polymerization of biogenic precursors

“…Functional group preservation has been obtained, for instance, by maintaining a low substrate temperature, using low plasma powers, or pulsing the plasma discharges. [ 64 ]…”

Atmospheric plasma deposition of bioinspired catechol-rich polymers: a promising route for the simple construction of redox-active thin films

“…Recently, we reported on the abilities of a one-step atmospheric aerosol-assisted plasma polymerization method ensuring high deposition rates of high purity and pinhole-free extremely adherent and tunable catechol-bearing films in terms of morphology, thickness and catechol content. 12,13 In particular, the developed approach offers an interesting alternative to the production of catechol-films from liquid-assisted plasma routes, 14,15 known to suffer from non-wetting phenomena. Compared to the work of Mun et al exploiting dopamine, 16 the method relies on injecting a liquid precursor consisting of a catechol-based vinyl monomer (dopamine (meth)acrylamide) dissolved in (di)methacrylate acting as co-monomer and solvent directly into the plasma discharge zone.…”

“…Compared to the work of Mun et al exploiting dopamine, 16 the method relies on injecting a liquid precursor consisting of a catechol-based vinyl monomer (dopamine (meth)acrylamide) dissolved in (di)methacrylate acting as co-monomer and solvent directly into the plasma discharge zone. Although the catechol-functionalized thin films were successfully exploited for the covalent immobilization of biomolecules, 13 such a precursor formulation was irrelevant for energy storage applications due to the low catechol density diluted in the methacrylate-based film matrix.…”