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Special Issue Editor

Dr. Benoit Lessard

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Guest Editor

Department of Chemical and Biological Engineering, University of Ottawa, Ottawa, ON, Canada
Interests: organic electronics; OLEDs; OPVs; OTFTs; SWNT; polymer synthesis; organic chemistry; surface engineering; interface engineering; crystal engineering; phthalocyanies
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Reversible-deactivation radical polymerization (RDRP), also known as controlled radical polymerization (CRP), is emerging as a robust and versatile choice for functional material development. Since the mid-1980s, CRP has been utilized to engineer controlled polymers architectures with tunable material properties both in academia and industry. CRP facilitates the incorporation of functional monomers, controls polymer microstructure and in some cases does not require excessive purification steps prior to use in a variety of delicate electronic and biological applications.

This Special Issue will focus on the development of new materials and applications that benefit from the use of CRP. Advancement of novel material applications, such as nanoporous membranes, drug delivery, biological imaging, tissue engineering, nanofeatured templates, proton exchange membranes, and electron donor–acceptor polymers for organic photovoltaics, organic light emitting diodes and electrical memory applications, to name but a few. Current applications which benefit from the use of CRP or novel applications as a result of the use of CRP will both be explored.

As the fields of functional materials by CRP is rapidly advancing, it is our pleasure to invite you to submit a manuscript for this Special Issue. Full papers, and communications are welcome. The main theme can either be the polymer chemistry or the application of the polymers where CRP was employed, or (ideally) the manuscript can cover both aspects simultaneously.

Prof. Benoit Lessard
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

controlled radical polymerization (CRP)
reversible-deactivation radical polymerization (RDRP)
functional materials
controlled Polymer
tuneable properties
next generation applications
block copolymers
polymer thin film

Published Papers (2 papers)

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Research

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20 pages, 4856 KiB

Open AccessArticle

Ethylene Glycol Dicyclopentenyl (Meth)Acrylate Homo and Block Copolymers via Nitroxide Mediated Polymerization

by Alexandre Maupu, Yara Kanawati, Adrien Métafiot and Milan Maric

Materials 2019, 12(9), 1547; https://doi.org/10.3390/ma12091547 - 11 May 2019

Cited by 3 | Viewed by 3903

Abstract

Nitroxide-mediated polymerization (NMP), (homo and block copolymerization with styrene (S) and butyl methacrylate/S) of ethylene glycol dicyclopentenyl ether (meth)acrylates (EGDEA and EGDEMA) was studied using BlocBuilder alkoxyamines. EGDEA homopolymerization was not well-controlled, independent of temperature (90–120 °C), or additional free nitroxide (0–10 mol%) used. Number average molecular weights (M_n) achieved for poly(EGDEA) were 4.0–9.5 kg mol⁻¹ and were accompanied by high dispersity (Ð = M_w/M_n = 1.62–2.09). Re-initiation and chain extension of the poly(EGDEA) chains with styrene (S) indicated some block copolymer formation, but a high fraction of chains were terminated irreversibly. EGDEA-stat-S statistical copolymerizations with a low mol fraction S in initial feed, f_S_,0 = 0.05, were slightly better controlled compared to poly(EGDEA) homopolymerizations (Ð was reduced to 1.44 compared to 1.62 at similar conditions). EGDEMA, in contrast, was successfully polymerized using a small fraction of S (f_S_,0 ~ 10 mol%) to high conversion (72%) to form well-defined EGDEMA-rich random copolymer (molar composition = F_EGDEMA = 0.87) of M_n = 14.3 kg mol⁻¹ and Ð = 1.38. EGDEMA-rich compositions were also polymerized with the unimolecular succinimidyl ester form of BlocBuilder initiator, NHS-BlocBuilder with similar results, although Ðs were higher ~1.6. Chain extensions resulted in monomodal shifts to higher molecular weights, indicating good chain end fidelity. Full article

(This article belongs to the Special Issue Novel Materials and Applicaitons by Controlled Radical Polymerization)

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Review

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20 pages, 4345 KiB

Open AccessReview

Smart Control of Nitroxide-Mediated Polymerization Initiators’ Reactivity by pH, Complexation with Metals, and Chemical Transformations

by Mariya Edeleva, Gerard Audran, Sylvain Marque and Elena Bagryanskaya

Materials 2019, 12(5), 688; https://doi.org/10.3390/ma12050688 - 26 Feb 2019

Cited by 20 | Viewed by 3497

Abstract

Because alkoxyamines are employed in a number of important applications, such as nitroxide-mediated polymerization, radical chemistry, redox chemistry, and catalysis, research into their reactivity is especially important. Typically, the rate of alkoxyamine homolysis is strongly dependent on temperature. Nonetheless, thermal regulation of such reactions is not always optimal. This review describes various ways to reversibly change the rate of C–ON bond homolysis of alkoxyamines at constant temperature. The major methods influencing C–ON bond homolysis without alteration of temperature are protonation of functional groups in an alkoxyamine, formation of metal–alkoxyamine complexes, and chemical transformation of alkoxyamines. Depending on the structure of an alkoxyamine, these approaches can have a significant effect on the homolysis rate constant, by a factor of up to 30, and can shorten the half-lifetime from days to seconds. These methods open new prospects for the application of alkoxyamines in biology and increase the safety of (and control over) the nitroxide-mediated polymerization method. Full article

(This article belongs to the Special Issue Novel Materials and Applicaitons by Controlled Radical Polymerization)

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