Thiol–Ene Linear Step-Growth Photopolymerization in Miniemulsion: Fast Rates, Redox-Responsive Particles, and Semicrystalline Films

Jasinski, Florent; Rannée, Agnès; Schweitzer, Julie; Fischer, Diane; Lobry, Emeline; Croutxé‐Barghorn, Céline; Schmutz, Marc; Nouën, Didier Le; Criqui, Adrien; Chemtob, Abraham

doi:10.1021/acs.macromol.5b02512

Cited by 47 publications

(71 citation statements)

References 58 publications

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“…[13] Apart from the advantages already mentioned, thiol-ene reactions allow the synthesis of high molecular weight polyesters in aqueous dispersed medium and are thus suitable for the production of polymeric nanoparticles containing ester groups in the main chain, which can undergo hydrolysis, enabling their degradation in physiological environment, which is of great importance for biomedical applications or material disposal. [14][15][16] Besides avoiding the use of organic solvents, miniemulsion polymerization offers advantages over other types of polymerization, such as bulk and solution polymerizations, because it yields products with low viscosity and therefore mass, heat, and momentum transfer is improved. Additionally, the miniemulsion process enables the production of polymeric nanoparticles with unique characteristics and vast commercial interest.…”

Section: Introductionmentioning

confidence: 99%

“…[16][17][18][19][20][21] Thiol-ene step-growth polymerization in miniemulsion is currently being investigated and only a handful of articles have been published in the literature. [14][15][16][22][23][24] Furthermore, works portraying the polymerization of renewable monomers through thiol-ene polymerization in aqueous dispersed medium are still uncommon. [16] In this work, we present the synthesis and characterization of poly(thioether-ester) nanoparticles via thiol-ene polymerization in miniemulsion using a fully renewable α,ω-diene monomer obtained from 10-undecenoic acid and 1,3-propanediol, both derived from castor oil.…”

Section: Introductionmentioning

confidence: 99%

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Biocompatible Polymeric Nanoparticles From Castor Oil Derivatives via Thiol‐Ene Miniemulsion Polymerization

Cardoso

Machado²,

Feuser³

et al. 2017

Euro J Lipid Sci & Tech

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Biocompatible polymeric nanoparticles are obtained via thiol-ene polymerization of a biobased monomer in miniemulsion. The α,ω-diene-diester monomer is synthesized through esterification reaction of a glycerol derivative, namely 1,3-propanediol, with 10-undecenoic acid, a long-chain diene carboxylic acid. In order to investigate how different monomeric structures behave toward thiolene polymerization in miniemulsion, two types of thiols are investigated: 1,4-butanedithiol and 2-mercaptoethyl ether. Poly(thioether-ester)s with weight average molecular weight up to 15 kDa (M n ) are obtained, depending on initiator concentration and types of surfactant and dithiol employed. Finally, biobased poly(thioether-ester) nanoparticles are submitted to cytotoxicity and hemolysis analyses. High cell viability and no significant changes in cell morphology are observed after the incubation on murine fibroblast (L929) and human cervical cancer cells (HeLa). Last, hemolysis assays revealed blood compatibility and therefore polymeric nanoparticles have been shown to be a potential alternative drug delivery vector for intravenous administration. Practical Applications: There is a great demand for polymeric systems that fulfill a number of requirements, such as biodegradability and biocompatibility, for biomedical applications. In this context, biobased polymers obtained from vegetable oils are a very attractive sustainable alternative to fossil-derived polymeric materials, presenting potential biodegradability and low toxicity. By thiol-ene reactions, polymeric materials containing ester groups in the main chain -which can undergo hydrolysis-can be prepared in miniemulsion, enabling their degradation in physiological environment and, therefore, being interesting for biomedical applications and material disposal. Such novel materials could be used in temporary implants, tissue engineering, and drug delivery systems.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Biocompatible Polymeric Nanoparticles From Castor Oil Derivatives via Thiol‐Ene Miniemulsion Polymerization

Cardoso

Machado²,

Feuser³

et al. 2017

Euro J Lipid Sci & Tech

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“…Thiol–ene chemistry has become an increasingly useful technique the past decade for a wide range of applications due to its “click” characteristic . Thiol–ene and its sister reaction thiol–yne are extremely efficient reactions, quickly reacting in a clean manner that produces little to no side product .…”

Section: Introductionmentioning

confidence: 99%

“…Thiol–ene processes have become important tools for the polymer chemist due to the high yield, speed, and selectivity of this reaction, making it ideal for use in many aspects of polymer synthesis. Thiol–ene and thiol–yne reactions have been used for step‐growth polymerization, postpolymerization functionalization, polymer crosslinking, hyperbranched polymer synthesis, and protein‐polymer conjugation . Photochemical thiol–ene involves the photochemical initiation of the radical thiol–ene process, typically through excitation of a photoinitiator, which is then abstracts a hydrogen giving rise to thiyl radicals .…”

Section: Introductionmentioning

confidence: 99%

Photocatalyzed thiol–alkene coupling: Mechanistic study and polymer synthesis

Allegrezza

Thompson

Kloster

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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Due to the “click” chemistry characteristics of the thiol–ene reaction, these transformations have been gaining an increasing amount of attention in current chemical research. The high efficiency and selectivity of these transformations have been useful for many areas of study, from small molecule organic synthesis, to polymer synthesis and functionalization, to bio‐conjugation reactions. In this work, a study of a novel method of photochemical thiol–ene reactions using alkyl halides and an tris[2‐phenylpyridinato‐C2,N]iridium(III) (Ir(ppy)3) photocatalyst is investigated. This process is shown to progress rapidly and has the benefit of low catalyst and initiator concentrations relative to reagents as well as mild conditions associated with photochemical processes. To understand the mechanism of this process, catalyst and initiator concentrations and other reaction conditions are varied. To demonstrate the utility of this process, a step‐growth thiol–ene polymer is synthesized using dithiol and diene monomers and a crosslinked polymer network is synthesized as well. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1931–1937

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“…Previously, we and others developed radical‐mediated thiol‐ene and thiol‐yne polymerizations for the production of colloidal polymer particles . Synthesis of colloidal polymers have been shown to work in different dispersed polymerization modes, such as emulsions, dispersions, miniemulsions and suspensions .…”

Section: Introductionmentioning

confidence: 99%

Composite Particles From Pickering‐Stabilized Radical Mediated Thiol‐Ene Suspension Polymerizations

Cassidy

Durham

Shipp

2019

Macro Reaction Engineering

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Pickering stabilization is a facile method to create composite colloidal particles. Inorganic colloidal SiO2 nanoparticles are often used as the stabilizer for particles instead of the more common amphiphilic surfactants. Here the use of this approach in radical‐mediated thiol‐ene suspension polymerizations using monomers 1,3,5‐triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione (TTT) and pentaerythritol tetrakis (3‐mercaptopropionate) (PETMP) is described. The resulting micron‐sized crosslinked poly(thioether) colloidal particles are coated with 80 nm silica nanoparticles. The addition of a small amount of various costabilizers is examined (hexadecane, cetyl alcohol and toluene), and while all yielded particles, cetyl alcohol provide more consistent results. Scanning electron microscopy and thermal analysis of the composite particles demonstrate morphologies that are consistent with a raspberry‐like structure. No significant changes to the glass transition temperature are observed, which is consistent with the silica nanoparticles being located at the surface of the polymer particles.

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Thiol–Ene Linear Step-Growth Photopolymerization in Miniemulsion: Fast Rates, Redox-Responsive Particles, and Semicrystalline Films

Cited by 47 publications

References 58 publications

Biocompatible Polymeric Nanoparticles From Castor Oil Derivatives via Thiol‐Ene Miniemulsion Polymerization

Biocompatible Polymeric Nanoparticles From Castor Oil Derivatives via Thiol‐Ene Miniemulsion Polymerization

Photocatalyzed thiol–alkene coupling: Mechanistic study and polymer synthesis

Composite Particles From Pickering‐Stabilized Radical Mediated Thiol‐Ene Suspension Polymerizations

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