Room temperature sonochemical initiation of thiol-ene reactions

Skinner, Emily K.; Whiffin, Fraeya; Price, Gareth J.

doi:10.1039/c2cc32457a

Cited by 34 publications

(29 citation statements)

References 26 publications

(30 reference statements)

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“…These results provide evidence that the uninhibited sample undergoes polymerization through the sonochemical cavitation process, and that MEHQ is required to prevent premature polymerization. These observations are supported by the work of Skinner et al, 23 which quantified room temperature sonochemical initiation in thiol-ene systems using a radical trap (2,2-diphenyl-1-picryhydrazyl), and showed a radical generation at a rate of 0.62 × 10 -4 mol dm -3 s -1 led to successful thiol-ene reactions even in the absence of a radical initiator. Therefore, MEHQ plays a critical role in the current thiol-ene miniemulsion system to prevent simultaneous occurrence of monomer droplet formation and polymerizationa process that could lead to broad particle size distributions and uncontrolled process parameters.…”

Section: Resultssupporting

confidence: 68%

Functional, sub-100 nm polymer nanoparticles via thiol–ene miniemulsion photopolymerization

Amato

Flynt

et al. 2015

Polym. Chem.

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ARTICLE This journal isIn this work, sub-100 nm crosslinked polythioether nanoparticles were synthesized via thiol-ene photopolymerization in miniemulsion using high-energy homogenization. The effects of the miniemulsion formulation and homogenization parameters -including inhibitor concentration, surfactant concentration, organic weight fraction, ultrasonication time and amplitude -on nanoparticle size and size distribution were investigated. Thiol-ene nanoparticles with a mean particle diameter of 46 nm were obtained under optimized conditions for the current system at 2.5 wt. % organic fraction and 20 mM surfactant concentration. In an effort to demonstrate potential utility of thiol-ene nanoparticles, we exploit the step-growth radical mechanism of thiol-ene photopolymerization under non-stoichiometric conditions to fabricate functional nanoparticles that express excess thiol or alkene at the particle surface. We show that these excess functional groups can be utilized as reactive handles in thiol-Michael and radicalmediated thiol-ene reactions for immobilization of fluorescent moieties via postpolymerization modification.

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Section: Resultssupporting

confidence: 68%

Functional, sub-100 nm polymer nanoparticles via thiol–ene miniemulsion photopolymerization

Amato

Flynt

et al. 2015

Polym. Chem.

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“…Hence, the thiol‐ene coupling of cysteamine and diallyl isosorbide could be finished in the aqueous condition. As described in the Experimental Section (Section ), the commonly used mircowave was also employed here to accelerate this reaction5 and a small amount of Tween‐80 was taken to enhance the solubility of diallyl isosorbide …”

Section: Resultsmentioning

confidence: 99%

“…This indicated good shape memory performance. In addition, we should pay attention to that all curves representing the three thermomechanical cycles were almost overlapped in Figure , which meant that the shape memory behaviors were remained quite constant and repeatable after several cycles …”

Section: Resultsmentioning

confidence: 99%

Green Synthesis of a Bio‐Based Epoxy Curing Agent from Isosorbide in Aqueous Condition and Shape Memory Properties Investigation of the Cured Resin

Dai

Liu

et al. 2016

Macro Chemistry & Physics

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The bio‐based diamine and epoxy monomer derived from isosorbide are synthesized. Especially, the diamine is obtained using microwave assistant thiol‐ene coupling reaction in the aqueous media and the influence of reaction parameters, such as initiator content and reaction time, are investigated. After curing the synthesized epoxy monomer together with the diamine, properties of the cured resins are studied by differential sscanning calorimetry, dynamic mechanical analysis, and thermogravimetric analyzer. Results demonstrate that the cured resin has good shape fixity, good shape recovery, and satisfied thermal stability despite the presence of heteroatoms. This bio‐based epoxy resin shows great potential to be used as a candidate for shape memory material. Considering the bio‐based feedstock and environmental friendly synthetic process, a “green + green” strategy to prepare thermosetting resins with advanced properties is provided in this paper.

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“…Recently, new pathways for initiating/catalyzing the thiol‐ene reaction have been explored. For example, Skinner and co‐workers discussed the use of ultrasound for the initiation of the thiol‐ene reaction using toluene and water as solvent. High conversions were obtained using air saturated water.…”

Section: Introductionmentioning

confidence: 99%

TEMPO Driven Mild and Modular Route to Functionalized Microparticles

Hafeez

Barner

Nebhani

2018

Macromol. Rapid Commun.

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The synthesis of crosslinked polymeric microspheres (3.8-15.0 µm) via (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) initiated thiol-ene dispersion polymerization under ambient conditions is reported for the first time. The initiating ability of TEMPO for the thiol-ene reaction is validated by electron paramagnetic resonance (EPR) and H nuclear magnetic resonance (NMR) spectroscopy on model reactions between 1-octadecanethiol and two electron deficient enes, n-butylacrylate and divinyl sulfone. Critically, the TEMPO resonance observed in the EPR spectra decreases with time when TEMPO is mixed with thiol and an electron deficient ene. The H NMR spectra demonstrate formation of up to 90% of thioether under ambient conditions. Based on these model reactions, a variety of crosslinked polymeric microspheres are synthesized with excellent morphological stability using poly(vinyl pyrrolidone) as surfactant. The ability of the microspheres for a second TEMPO initiated thiol-ene reaction is demonstrated by the ligation of fluorescein-5-maleimide (an ene) to the microspheres' surface containing excess of thiol functionality and by ligation of cysteine (containing a thiol group) to the microspheres' surface containing an excess of ene functionality. The synthesized polymeric microspheres are characterized using scanning electron microscopy, differential scanning calorimetry, Fourier-transform infrared spectroscopy, zeta potential, and X-ray photoelectron spectroscopy.

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Room temperature sonochemical initiation of thiol-ene reactions

Abstract: Thiol-ene 'click' reactions have been initiated for a range of primary alkenes using ultrasound in both toluene and water. The method is particularly effective in aqueous solutions in the presence of air.

Cited by 34 publications

References 26 publications

Functional, sub-100 nm polymer nanoparticles via thiol–ene miniemulsion photopolymerization

Functional, sub-100 nm polymer nanoparticles via thiol–ene miniemulsion photopolymerization

Green Synthesis of a Bio‐Based Epoxy Curing Agent from Isosorbide in Aqueous Condition and Shape Memory Properties Investigation of the Cured Resin

TEMPO Driven Mild and Modular Route to Functionalized Microparticles

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