Insights on the Atmospheric-Pressure Plasma-Induced Free-Radical Polymerization of Allyl Ether Cyclic Carbonate Liquid Layers.

Edyta M Niemczyk,Gilles Frache,Jean R N Haler,Alvaro Gomez-Lopez,Haritz Sardon,Robert Quintana

doi:10.3390/polym13172856

Abstract

Plasma-induced free-radical polymerizations rely on the formation of radical species to initiate polymerization, leading to some extent of monomer fragmentation. In this work, the plasma-induced polymerization of an allyl ether-substituted six-membered cyclic carbonate (A6CC) is demonstrated and emphasizes the retention of the cyclic carbonate moieties. Taking advantage of the low polymerization tendency of allyl monomers, the characterization of the oligomeric species is studied to obtain insights into the effect of plasma exposure on inducing free-radical polymerization. In less than 5 min of plasma exposure, a monomer conversion close to 90% is obtained. The molecular analysis of the oligomers by gel permeation chromatography coupled with high-resolution mass spectrometry (GPC-HRMS) further confirms the high preservation of the cyclic structure and, based on the detected end groups, points to hydrogen abstraction as the main contributor to the initiation and termination of polymer chain growth. These results demonstrate that the elaboration of surfaces functionalized with cyclic carbonates could be readily elaborated by atmospheric-pressure plasmas, for instance, by copolymerization.

Highlights

The synthesis and direct deposition of polymeric thin films by atmospheric-pressure plasma-induced polymerization is an appealing approach for the elaboration of functional surfaces [1]
The monomer is a clear liquid at room conditions and has a very low vapor pressure, both properties facilitated the formation by the spin coating of very thin liquid layers over the silicon substrates
Even even if if this this secondary secondary polymerization polymerization mechanism mechanism could could be be further supported with additional work, the results reported here clearly further supported with additional work, the high-resolution mass spectrometry (HRMS) results reported here clearly indicate indicate that that the the plasma-induced plasma-induced polymerization polymerization of of the the A6CC

Summary

Introduction

The synthesis and direct deposition of polymeric thin films by atmospheric-pressure plasma-induced polymerization is an appealing approach for the elaboration of functional surfaces [1]. Vinyl functional monomers are readily polymerized by plasma-induced free-radical polymerization leading to the deposition of thin films with a large variety of functional groups, including cyclic groups, such as epoxide [4,5], lactam [6] and catechol/quinone [7]. These groups are of interest because they can improve adhesion between the thin film and the treated surface. Their reactivity allows post-polymerization modifications of the surface, for instance, for biomolecule immobilization for practical applications in biomedical [7]

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Results

Conclusion