Photoinduced Cross‐Linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling

Feillée, Noémi; Chemtob, Abraham; Ley, Christian; Croutxé‐Barghorn, Céline; Allonas, Xavier; Ponche, Arnaud; Nouën, Didier Le; Majjad, Hicham; Jacomine, Léandro

doi:10.1002/marc.201500459

Cited by 19 publications

(15 citation statements)

References 27 publications

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“…The oxidative coupling reaction utilized to deliver polydisulfides (Scheme B) has been recognized since the 1940s, and takes usually place in the presence of oxidation reagents such as oxygen, iodine, hydrogen peroxides, and dimethyl sulfoxide among others, or can be induced electrochemically. In fact, the catalyst‐free oxygen oxidative polymerization was not efficient to produce polymers with more than eight repeat units in average .…”

Section: Chemistrymentioning

confidence: 99%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

254

220

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/marc.201800650. ChemistryBefore moving to the recent advances within the last 5 years in the diverse applications of sulfur chemistry in polymer and Sulfur-Containing PolymersSulfur and its functional groups are major players in an area of exciting research taking place in modern polymer and materials science, both in academia and industry. In fact, manifold sulfur-based reactions that are both exceptionally versatile as well as tremendously useful have been implemented, and further utilized for the design and preparation of polymeric materials that lead to a plethora of applications ranging from medicine to optics and nanotechnology to separation science. Hence, within this review, an overview of strategies and developments used over the last 5 years to reinforce the importance of the sulfur functional group in modern polymer and materials science is presented. In particular, many important references in the primary literature of sulfur chemistry are referred to, including thiol-ene, thiol-yne, thiol-Michael addition, disulfide cross-linking, and thiol-disulfide exchange, among others, by explaining and illustrating the important principles. Last but not least, the grand aim to underpin the importance of sulfur in modern polymer and materials science is achieved by presenting selected examples in diverse fields and postulating the respective potential for real-world applications. he is now a full professor at KIT.sulfur atoms, and tetraphenylethene-bearing di(alkyl bromide) (Scheme 3). The yield of the polymerization was dependent on the di(alkyl bromide) monomer; the longer spacer between the aromatic moiety and the reactive bromide end groups Scheme 1. The discussion henceforth focuses on the synthesis of polymers possessing the depicted sulfur functional groups. Scheme 2.Representative examples of polythioethers prepared via A) the nucleophilic substitution reaction between an electrophilic dihalide with nucleophilic derivatives of dithiols under alkaline conditions; B) the thiol-ene/yne addition reaction between AA and BB type monomers (i.e., dithiols and dienes/diynes); and C) radical or ionic ring-opening of sulfurcontaining strained rings.Scheme 3. The thiol-bromo polymerization of conformationally fixed monomers to provide multifunctional polymers. [19] Macromol. Rapid Commun. 2019, 40, 1800650 Scheme 4. The regioselective selective nucleophilic aromatic substitution between thiol and fluorinated aromatic compounds, the para-fluorothiol reaction (PFTR).Scheme 5. Synthesis of a linear polymer via PFTR-reaction. [21]

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Section: Chemistrymentioning

confidence: 99%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

254

220

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“…The approachd escribed herein has found applicationsi n other materials, such as gels [10] and films, [11] and hasthe benefit of offering materials resistant to many environmental aspects, including heat, salt concentration, UV radiation, shear force, and pH value. The methodi nvolves applying techniques from thiol-disulfide exchange processesu sing commerciallya vailable epoxy resins and hardeners.…”

Section: Introductionmentioning

confidence: 99%

Epoxy Matrices Modified by Green Additives for Recyclable Materials

Henriksen

Ravnsbæk²,

Bjerring

et al. 2017

ChemSusChem

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Epoxy-based thermosets are one of the most popular matrix materials in many industries, and significant environmental benefits can be obtained by developing a recyclable variant of this widely utilized material. Incorporation of a bio-based disulfide additive within a commercial epoxy system leads to a cross-linked material that can be fractionated under mild and environmentally benign conditions. The material has been analyzed by FTIR and solid-state NMR. Furthermore, modified epoxy matrices with low additive concentrations are demonstrated to have similar mechanical and thermal properties compared to commercially available benchmarks. Thus, additive formulation and fractionation based on green chemistry principles have been demonstrated, and a recyclable epoxy matrix has been developed.

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“…Radiation control of polymerization relies on the photogeneration of a superbase catalyst (1,5,7-triazabicyclo[4.4.0]dec-5-ene: TBD) through a photobase generator (xanthone propionic acid-protected TBD, PBG, see Table 1) [17]. Using this PBG, we have recently demonstrated the feasibility of multiple thiol air oxidation of polyfunctional thiol monomers to yield disulfide cross-linked films [18,19], but the photooxidative polymerization of PdS resin is unprecedented. In terms of mechanism, given that thiols are more acidic than alcohols by an average of about 5 pK a units (pK a = 5-11), TBD (pK a ≈ 13.5) can readily react with a thiol to form a thiolate anions RS − acting as a much better electron donor [20].…”

Section: Introductionmentioning

confidence: 99%

Oxidative photopolymerization of thiol-terminated polysulfide resins. Application in antibacterial coatings

Chemtob

Feillée

Ley

et al. 2018

Progress in Organic Coatings

Self Cite

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A UV photoinduced cross-linking of non-modified commercial poly(disulfide) resins (Thioplast) is reported via the air oxidative photocoupling of terminal thiol functions. Catalyzed by a photogenerated guanidine base (TBD), this step-growth photopolymerization is useful to maximize disulfide functions content. The mechanism proceeds through thiol deprotonation into thiolate anions, further oxidized into thiyl radicals, eventually dimerizing into disulfide cross-links. Starting with a detailed structural characterization of the thiol-terminated resin, photooxidative kinetics are studied under exposure to a polychromatic medium-pressure Hg arc using Raman and infrared spectroscopy. The effects of irradiance, film thickness, photobase concentration, resin molar mass, and content of an additional polythiol monomer (reactive diluent) have been investigated. In an effort of upscaling, irradiation under a 365 nm LED panel has enabled the fast preparation of 1.5 µm thick cross-linked poly(disulfide) coatings in a matter of minutes. Capitalizing on the ability of residual thiol groups to react with silver cations, a post-functionalization has been successfully performed, leading to films exhibiting at their surface stable thiolate-silver bonds as proved by X-ray photoelectron spectroscopy. Despite the well-established biocide action of silver ions, no antibacterial action has been evidenced by confocal fluorescence microscopy because of insufficient release.

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Photoinduced Cross‐Linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling

Cited by 19 publications

References 27 publications

Sulfur Chemistry in Polymer and Materials Science

Sulfur Chemistry in Polymer and Materials Science

Epoxy Matrices Modified by Green Additives for Recyclable Materials

Oxidative photopolymerization of thiol-terminated polysulfide resins. Application in antibacterial coatings

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