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133 results on '"Daniel Taton"'

1. Gold Nanoclusters Synthesized within Single-Chain Nanoparticles as Catalytic Nanoreactors in Water

Author: Jokin Pinacho-Olaciregui, Ester Verde-Sesto, Daniel Taton, and José A. Pomposo
Subjects: single-chain nanoparticles, gold nanoclusters, catalytic nanoreactors, Organic chemistry, QD241-441
Abstract: Metalloenzymes are able to catalyze complex biochemical reactions in cellular (aqueous) media with high efficiency. In recent years, a variety of metal-containing single-chain nanoparticles (SCNPs) have been synthesized as simplified metalloenzyme-mimetic nano-objects. However, most of the metal-containing SCNPs reported so far contained complexed metal ions but not metal nanoclusters (NCs) with diameter
Published: 2024
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2. The promise of N-heterocyclic carbenes to capture and valorize carbon dioxide

Author: Pierre Stiernet, Bo Pang, Daniel Taton, and Jiayin Yuan
Subjects: Carbene, N-heterocyclic carbene, CO2 capture, CO2 valorization, Catalysis, Chemistry, QD1-999, Environmental protection, TD169-171.8
Abstract: With increasing environmental concerns due to the anthropologic emissions of greenhouse gasses, especially carbon dioxide (CO2), the development of new technologies to capture the latter is of great public value. While amino-containing materials excel in capturing CO2, they generally suffer from a few limitations, namely, the high energy penalty for desorption and the obstacle to directly convert CO2 into valuable resources. In this context, molecular or polymeric compounds based on N-heterocyclic carbenes (NHCs) have emerged as versatile alternatives to efficiently sequester CO2. NHCs are among the most investigated reactive species in chemistry: not only have they been intensively used as ligands for transition metal catalysts but also they exhibit a rich chemistry, either as true reagents or as organic catalysts. However, their air- and moisture-sensitivity represents a limitation to their use in synthesis. As reviewed thereafter, NHCs can selectively react with CO2 forming stable adducts, in the form of zwitterionic betaine-type species, providing CO2 directly-on-site for further fixation. Advances in the use of NHCs in this field are illustrated in this paper with a special emphasis on integration of NHCs in materials enabling heterogeneous utilizations in capture and catalysis.
Published: 2023
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3. Direct and selective access to amino-poly(phenylene vinylenes)s with switchable properties by dimerizing polymerization of aminoaryl carbenes

Author: Quentin Sobczak, Aravindu Kunche, Damien Magis, Daiann Sosa Carrizo, Karinne Miqueu, Jean-Marc Sotiropoulos, Eric Cloutet, Cyril Brochon, Yannick Landais, Daniel Taton, and Joan Vignolle
Subjects: Science
Abstract: Despite the ubiquity of singlet carbenes in chemistry, their utility as true monomeric building blocks for the synthesis of functional organic polymers has been underexplored. Here the authors show mono- and bis-acyclic amino(aryl)carbenes selectively dimerize to form diaminoalkenes and hitherto unknown amino-containing poly(p-phenylene vinylene)s.
Published: 2021
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4. Stereoselective ROP of rac- and meso-Lactides Using Achiral TBD as Catalyst

Author: Sébastien Moins, Sébastien Hoyas, Vincent Lemaur, Beste Orhan, Kayla Delle Chiaie, Roberto Lazzaroni, Daniel Taton, Andrew P. Dove, and Olivier Coulembier
Subjects: organocatalyst, stereocontrol, lactide, ring-opening polymerization, TBD, Chemical technology, TP1-1185, Chemistry, QD1-999
Abstract: 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) polymerizes rac-lactide (rac-LA) to form highly isotactic polylactide (PLA) with a Pm = 0.88, while meso-LA yields heterotactic PLA (Pm ~ 0.8) at −75 °C. The stereocontrol of the cryogenic-based ring-opening polymerization comes from a perfect imbrication of both chiral LA and the propagating chiral end-group interacting with the achiral TBD catalyst.
Published: 2020
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5. Nanocomposites Based on Luminescent Colloidal Nanocrystals and Polymeric Ionic Liquids towards Optoelectronic Applications

Author: Annamaria Panniello, Chiara Ingrosso, Paul Coupillaud, Michela Tamborra, Enrico Binetti, Maria Lucia Curri, Angela Agostiano, Daniel Taton, and Marinella Striccoli
Subjects: colloidal nanocrystals, polymeric ionic liquids, nanocomposites, surface functionalization, time-resolved spectroscopy, Technology, Electrical engineering. Electronics. Nuclear engineering, TK1-9971, Engineering (General). Civil engineering (General), TA1-2040, Microscopy, QH201-278.5, Descriptive and experimental mechanics, QC120-168.85
Abstract: Polymeric ionic liquids (PILs) are an interesting class of polyelectrolytes, merging peculiar physical-chemical features of ionic liquids with the flexibility, mechanical stability and processability typical of polymers. The combination of PILs with colloidal semiconducting nanocrystals leads to novel nanocomposite materials with high potential for batteries and solar cells. We report the synthesis and properties of a hybrid nanocomposite made of colloidal luminescent CdSe nanocrystals incorporated in a novel ex situ synthesized imidazolium-based PIL, namely, either a poly(N-vinyl-3-butylimidazolium hexafluorophosphate) or a homologous PIL functionalized with a thiol end-group exhibiting a chemical affinity with the nanocrystal surface. A capping exchange procedure has been implemented for replacing the pristine organic capping molecules of the colloidal CdSe nanocrystals with inorganic chalcogenide ions, aiming to disperse the nano-objects in the PILs, by using a common polar solvent. The as-prepared nanocomposites have been studied by TEM investigation, UV-Vis, steady-state and time resolved photoluminescence spectroscopy for elucidating the effects of the PIL functionalization on the morphological and optical properties of the nanocomposites.
Published: 2014
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6. Block Copolymer Synthesis by a Sequential Addition Strategy from the Organocatalytic Group Transfer Polymerization of Methyl Methacrylate to the Ring-Opening Polymerization of Lactide

Author: Mohamed Samir Zaky, Gilles Guichard, and Daniel Taton
Subjects: Acetals, Polymers and Plastics, Polymers, Organic Chemistry, Materials Chemistry, Polymethyl Methacrylate, Methacrylates, Methylmethacrylate, Polymerization
Abstract: Sequential block copolymerization involving comonomers belonging to different classes, e.g., a vinyl-type monomer and a heterocycle, is a challenging task in macromolecular chemistry, as corresponding propagating species do not interconvert easily from one to the other by crossover reactions. Here, it is first evidenced that 1-methoxy 2-methyl 1-trimethylsilyloxypropene (MTS), i.e., a silyl ketene acetal (SKA)-containing initiator, can be used in presence of the P
Published: 2022

7. Functional nanostructures by NiCCo-PISA of helical poly(aryl isocyanide) copolymers

Author: Andrew P. Dove, Sètuhn Jimaja, Yujie Xie, Rachel K. O'Reilly, Jeffrey C. Foster, Daniel Taton, Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), University of Warwick [Coventry], School of Chemistry [Birmingham], and University of Birmingham [Birmingham]
Subjects: Circular dichroism, Materials science, Polymers and Plastics, Aryl, Isocyanide, Organic Chemistry, Bioengineering, Pentafluorophenyl esters, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Micelle, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Amphiphile, Polymer chemistry, Copolymer, 0210 nano-technology, Maleimide
Abstract: International audience; Herein, we present a straightforward and versatile methodology to achieve functional polymeric nano-objects that contain helical cores. Nickel-catalysed coordination polymerisation-induced self-assembly (NiCCo-PISA) of helical poly(aryl isocyanide) amphiphilic diblock copolymers was conducted, affording micelles containing controllable quantities of activated ester groups (i.e. pentafluorophenyl esters) in the core that were subsequently modified using post-polymerisation modification (PPM) with amine nucleophiles. Three amines bearing different functionalities (alcohol, trifluoro and a maleimide dye) were successfully introduced into the nano-object cores as verified via NMR and FT-IR spectroscopy, while the retention of helicity within the resulting diblock copolymers was confirmed by circular dichroism (CD) spectroscopy. Changes in nanostructure morphology following modification were monitored by dynamic light-scattering (DLS), confirming the disassembly of the nano-objects when the core hydrophilicity was increased through the introduction of polar functionalities. These readily-synthesised and modified nanostructures containing helical cores are valuable scaffolds for use in applications such as circularly polarised luminescence, enantioselective chemistry or chiral separation.
Published: 2021

8. A chiral thiourea and a phosphazene for fast and stereoselective organocatalytic ring-opening-polymerization of racemic lactide

Author: Mohamed Samir Zaky, Olivier Coulembier, Anne-Laure Wirotius, Daniel Taton, Gilles Guichard, Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Centre d'Innovation et de Recherche en Matériaux Polymères (CIRMAP), Université de Mons (UMons), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), and École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lactide, 010405 organic chemistry, Metals and Alloys, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Ring-opening polymerization, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, chemistry, Thiourea, Polymerization, Organocatalysis, Tacticity, Materials Chemistry, Ceramics and Composites, Phosphazene
Abstract: International audience; Control of stereoregularity is inherent to precision polymerization chemistry for the development of functional materials. A prototypal example of this strategy is the ring-opening polymerization (ROP) of racemic lactide (rac-LA), a bio-sourced monomer. Despite significant advances in organocatalysis, stereoselective ROP of rac-LA employing chiral organocatalysts remains unexplored. Here we tackle that challenge by resorting to Takemoto's catalyst, a chiral aminothiourea, in the presence of a phosphazene base. This chiral binary organocatalytic system allows for fast, chemo- and stereoselective ROP of rac-LA at room temperature, yielding highly isotactic, semi-crystalline and metal-free polylactide, with a melting temperature as high as 187 °C.
Published: 2021

9. Stimuli-responsive and core cross-linked micelles developed by NiCCo-PISA of helical poly(aryl isocyanide)s

Author: Sètuhn Jimaja, Spyridon Varlas, Jeffrey C. Foster, Daniel Taton, Andrew P. Dove, Rachel K. O'Reilly, School of Chemistry [Birmingham], University of Birmingham [Birmingham], University of Warwick [Coventry], Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and European Project: 642671,H2020,H2020-MSCA-ITN-2014,SUSPOL(2015)
Subjects: [CHIM.POLY]Chemical Sciences/Polymers, Polymers and Plastics, Organic Chemistry, Bioengineering, Biochemistry
Abstract: International audience; We report the synthesis of redox- and pH-sensitive block copolymer micelles that contain chiral cores composed of helical poly(aryl isocyanide)s. Pentafluorophenyl (PFP) ester-containing micelles synthesised via nickel-catalysed coordination polymerisation-induced self-assembly (NiCCo-PISA) of helical poly(aryl isocyanide) amphiphilic diblock copolymers are modified post-polymerisation with various diamines to introduce cross-links and/or achieve stimulus-sensitive nanostructures. The successful introduction of the diamines is confirmed by Fourier-transform infrared spectroscopy (FT-IR), while the stabilisation effect of the cross-linking is explored by dynamic light scattering (DLS). The retention of the helicity of the core-forming polymer block is verified by circular dichroism (CD) spectroscopy and the stimuli-responsiveness of the nanoparticles towards a reducing agent (L-glutathione, GSH) and pH is evaluated by following the change in the size of the nanoparticles by DLS. These stimuli-responsive nanoparticles could find use in applications such as drug delivery, nanosensors or biological imaging.
Published: 2022

10. Direct and selective access to amino-poly(phenylene vinylenes)s with switchable properties by dimerizing polymerization of aminoaryl carbenes

Author: Daniel Taton, Karinne Miqueu, Jean-Marc Sotiropoulos, Quentin Sobczak, Aravindu Kunche, Joan Vignolle, Damien Magis, Yannick Landais, Eric Cloutet, Daiann Sosa Carrizo, Cyril Brochon, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Team 4 LCPO : Polymer Materials for Electronic, Energy, Information and Communication Technologies, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, ANR-19-CE06-0015,CARBENOPOL,Plateformes Polymères Modulaires par Synthèse Macromoléculaire Impliquant la Polymérisation de Bis-carbènes Comme Briques de Base(2019), and ANR-10-LABX-0042,AMADEus,Advanced Materials by Design(2010)
Subjects: Double bond, Polymers, Science, General Physics and Astronomy, Protonation, 010402 general chemistry, 01 natural sciences, Article, General Biochemistry, Genetics and Molecular Biology, chemistry.chemical_compound, Phenylene, Singlet state, chemistry.chemical_classification, Multidisciplinary, 010405 organic chemistry, Aryl, General Chemistry, Combinatorial chemistry, 0104 chemical sciences, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Polymer synthesis, Piperidine
Abstract: Despite the ubiquity of singlet carbenes in chemistry, their utility as true monomeric building blocks for the synthesis of functional organic polymers has been underexplored. In this work, we exploit the capability of purposely designed mono- and bis-acyclic amino(aryl)carbenes to selectively dimerize as a general strategy to access diaminoalkenes and hitherto unknown amino-containing poly(p-phenylene vinylene)s (N-PPV’s). The unique selectivity of the dimerization of singlet amino(aryl)carbenes, relative to putative C-H insertion pathways, is rationalized by DFT calculations. Of particular interest, unlike classical PPV’s, the presence of amino groups in α-position of C=C double bonds in N-PPV’s allows their physico-chemical properties to be manipulated in different ways by a simple protonation reaction. Hence, depending on the nature of the amino group (iPr2N vs. piperidine), either a complete loss of conjugation or a blue-shift of the maximum of absorption is observed, as a result of the protonation at different sites (nitrogen vs. carbon). Overall, this study highlights that singlet bis-amino(aryl)carbenes hold great promise to access functional polymeric materials with switchable properties, through a proper selection of their substitution pattern., Despite the ubiquity of singlet carbenes in chemistry, their utility as true monomeric building blocks for the synthesis of functional organic polymers has been underexplored. Here the authors show mono- and bis-acyclic amino(aryl)carbenes selectively dimerize to form diaminoalkenes and hitherto unknown amino-containing poly(p-phenylene vinylene)s.
Published: 2021

11. Benzoic Acid as an Efficient Organocatalyst for the Statistical Ring-Opening Copolymerization of ε-Caprolactone and <scp>L</scp>-Lactide: A Computational Investigation

Author: Haritz Sardon, Daniel Taton, Coralie Jehanno, Fernando Ruipérez, Olivier Coulembier, Leila Mezzasalma, University of Mons [Belgium] (UMONS), Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Departamento de Ciencia y Tecnologıa de Polımeros e Instituto de Materiales Polimericos (POLYMAT), Universidad del Pais Vasco / Euskal Herriko Unibertsitatea [Espagne] (UPV/EHU), Institute of Physics, Stockholm University-Albanova University Center, Center of innovation and research in materials and polymers (CIRMAP), and Laboratory of polymeric and composite materials
Subjects: Polymers and Plastics, Organic Chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Ring (chemistry), 01 natural sciences, 0104 chemical sciences, 3. Good health, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymer chemistry, Materials Chemistry, Copolymer, L lactide, 0210 nano-technology, Caprolactone, ComputingMilieux_MISCELLANEOUS, Benzoic acid
Abstract: Statistical copolymers of l-lactide (L-LA) and e-caprolactone (CL) are of major interest as a result of the desired combination of properties they exhibit for high-added-value applications, includi...
Published: 2019

12. Nickel-Catalyzed Coordination Polymerization-Induced Self-Assembly of Helical Poly(aryl isocyanide)s

Author: Daniel Taton, Jeffrey C. Foster, Yujie Xie, Spyridon Varlas, Andrew P. Dove, Sètuhn Jimaja, Rachel K. O'Reilly, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and University of Birmingham [Birmingham]
Subjects: Materials science, Polymers and Plastics, Aryl, Isocyanide, Organic Chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Nanomaterials, Inorganic Chemistry, chemistry.chemical_compound, Nickel, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Materials Chemistry, Coordination polymerization, Nanomedicine, Self-assembly, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: The interest in helix-containing nanostructures is currently growing as a consequence of their potential applications in areas such as nanomedicine, nanomaterial design, chiral recognition, and asymmetric catalysis. Herein, we present a facile and tunable one-pot methodology to achieve chiral nano-objects. The nickel-catalyzed coordination polymerization-induced self-assembly (NiCCo-PISA) of helical poly(aryl isocyanide) amphiphilic diblock copolymers was realized and allowed access to various nano-object morphologies (spheres, worm-like micelles, and polymersomes). The helicity of the core block was confirmed via circular dichroism (CD) spectroscopy for all morphologies, proving their chiral nature. Small-molecule uptake by the spherical nanoparticles was investigated by encapsulating Nile Red into the core of the spheres and subsequent transfer into aqueous media. The presence of a CD signal for the otherwise CD-inactive dye proved the chiral induction effect of the nano-objects' helical core. This demonstrates the potential of NiCCo-PISA to prepare nanoparticles for applications in nanomaterials, catalysis, and recognition.
Published: 2020

13. N-Heterocyclic carbene/Lewis acid-mediated ring-opening polymerization of propylene oxide. Part 1: Triisobutylaluminum as an efficient controlling agent

Author: Junpeng Zhao, Qilei Song, Guangzhao Zhang, Stéphane Carlotti, Daniel Taton, Frédéric Peruch, South China University of Technology [Guangzhou] (SCUT), Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Polymers and Plastics, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Ring-opening polymerization, Catalysis, chemistry.chemical_compound, Nucleophile, Polymer chemistry, Materials Chemistry, Propylene oxide, Lewis acids and bases, bicomponent catalyst, Organic Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, substituted epoxides, block copolymers, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, 0210 nano-technology, anionic ring-opening polymerization, Carbene, N-heterocyclic carbene
Abstract: International audience; Ring-opening polymerization (ROP) of propylene oxide (PO) is achieved at 25 °C either in bulk or in solution, using N-heterocyclic carbenes (NHCs) and triisobutylaluminum (i-Bu3Al) as a bicomponent catalytic system. Transfer to monomer was not observed and poly(propylene oxide)s with predictable molar masses up to 60 000 g·mol−1 and low dispersities were obtained. In presence/absence of an alcohol as the initiator, the polymerization of PO follows anionic or zwitterionic ROP mechanisms, respectively. The addition of the Lewis acid strongly improves the efficiency of NHCs for the polymerization of substituted epoxides. It is established that i-Bu3Al is involved both in the formation of an initiating/propagating complex of moderate basicity/nucleophilicity and in the coordination of PO, enabling the activation of the monomer towards the complexed nucleophilic active species. Block copolyethers are also prepared by PPO chain extension experiments. All (co)polyethers were thoroughly characterized by 1H NMR spectroscopy, SEC and MALDI-TOF mass spectrometry as means to prove the control and benefit of this NHC approach for epoxides ROP.
Published: 2020

14. N-Heterocyclic carbene/Lewis acid-mediated ring-opening polymerization of propylene oxide. Part 2: Toward dihydroxytelechelic polyethers using triethylborane

Author: Qilei Song, Guangzhao Zhang, Frédéric Peruch, Stéphane Carlotti, Junpeng Zhao, Daniel Taton, South China University of Technology [Guangzhou] (SCUT), Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Molar mass, Polymers and Plastics, Organic Chemistry, Triethylborane, Dispersity, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Ring-opening polymerization, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Polymer chemistry, Materials Chemistry, Propylene oxide, Lewis acids and bases, 0210 nano-technology, Carbene
Abstract: International audience; Propylene oxide (PO) is polymerized by metal-free ring-opening 11 polymerization (ROP) at 25 °C using N-heterocyclic carbenes (NHCs) and 12 triethylborane (Et 3 B) as a bicomponent catalytic system. Poly(propylene oxide)s with 13 predictable molar mass up to 60 000 g.mol-1 and low dispersity (Ð < 1.10) were 14 obtained without the occurrence of undesirable transfer reaction to the monomer. In 15 presence of an alcohol as the initiator, the ROP of PO follows an anionic mechanism 16 assisted by monomer activation improving the efficiency of NHCs for the 17 polymerization of substituted epoxides. Et 3 B is involved both in the formation of a 18 complexed active center and in the activation of PO. Interestingly, 19 dihydroxytelechelic PPOs can be readily synthesized not only using 1,4-20 benzenedimethanol but also water, both serving as difunctional initiators. Block
Published: 2020

15. Isoselective Ring-Opening Polymerization of rac-Lactide from Chiral Takemoto’s Organocatalysts: Elucidation of Stereocontrol

Author: Olivier Coulembier, Beste Orhan, Anne-Laure Wirotius, Daniel Taton, Mathieu Jean-Luc Joseph Tschan, Andrew P. Dove, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), University of Birmingham [Birmingham], Laboratoire de Chimie des Matériaux et Polymères (SMPC), and Université de Mons-Hainaut
Subjects: Lactide, Polymers and Plastics, Stereochemistry, Organic Chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Ring-opening polymerization, 0104 chemical sciences, Kinetic resolution, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Organocatalysis, Tacticity, Materials Chemistry, Epimer, Stereoselectivity, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: Despite significant advances in organocatalysis, stereoselective polymerization reactions utilizing chiral organocatalysts have received very little attention, and much about the underlying mechanisms remains unknown. Here, we report that both commercially available (R,R)- and (S,S)-enantiomers of chiral thiourea-amine Takemoto’s organocatalysts promote efficient control and high isoselectivity at room temperature of the ring-opening polymerization (ROP) of racemic lactide by kinetic resolution, yielding highly isotactic, semicrystalline and metal-free polylactide (PLA). Kinetic investigations and combined analyses of the resulting PLAs have allowed the stereocontrol mechanism, which eventually involves both enantiomorphic site control and chain-end control, to be determined. Moreover, epimerization of rac-LA to meso-LA is identified as being responsible for the introduction of some stereoerrors during the ROP process.
Published: 2018

16. Partially Biosourced Poly(1,2,3-triazolium)-Based Diblock Copolymers Derived from Levulinic Acid

Author: Karim Aissou, Anatoli Serghei, Eric Drockenmuller, Daniel Taton, Imen Miladi, Amira Kallel Elloumi, Hatem Ben Romdhane, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Laboratoire de Chimie Organique Structurale et Macromoléculaire (LR99ES14), Université de Tunis El Manar (UTM), Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Polymères et des Biomatériaux (IMP-LMPB), Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut de Chimie du CNRS (INC), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie des polymères organiques (LCPO), Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Centre National de la Recherche Scientifique (CNRS), MIT, Dept Mat Sci & Engn, Cambridge, Massachusetts Institute of Technology (MIT), and Université Tunis El Manar (UTM)
Subjects: TRANSFER RAFT POLYMERIZATION, Polymers and Plastics, SOLID ELECTROLYTES, 02 engineering and technology, TRIBLOCK COPOLYMERS, 010402 general chemistry, ANION-EXCHANGE MEMBRANES, 01 natural sciences, Styrene, Inorganic Chemistry, chemistry.chemical_compound, Polymer chemistry, Materials Chemistry, Levulinic acid, Copolymer, [CHIM]Chemical Sciences, Reversible addition−fragmentation chain-transfer polymerization, Imide, ComputingMilieux_MISCELLANEOUS, POLYMERIZED IONIC LIQUID, Acrylate, MEDIATED RADICAL POLYMERIZATION, Organic Chemistry, Chain transfer, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, BLOCK-COPOLYMERS, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, POLY(IONIC LIQUID)S, SENSITIZED SOLAR-CELLS, 0210 nano-technology, VINYL LEVULINATE
Abstract: International audience; Partially biobased poly(1,2,3-triazolium)s are synthesized by reversible additionfragmentation chain transfer (RAFT) polymerization of tailor-made 1,2,3-triazole-functionalized (meth)acrylate monomers derived from levulinic acid, followed by N-alkylation of the 1,2,3-triazole moieties by methyl iodide (CH3I) and subsequent anion exchange with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI). Chain extension of a 1,2,3-triazole-functionalized polymethacrylate by RAFT polymerization of styrene followed by N-alkylation with CH3I and anion exchange with LiTFSI affords two poly(1,2,3-triazole)- and two poly(1,2,3-triazolium)-based diblock copolymers (BCPs) with different weight fractions of each block. Discussion of the structure/properties relationships of all obtained materials is based on NMR spectroscopy, size exclusion chromatography, differential scanning calorimetry, thermogravimetric analysis, and broadband dielectric spectroscopy. The morphological and self-assembling properties of neutral and charged BCPs in bulk and in thin films are investigated by small-angle X-ray scattering and atomic force microscopy experiments, respectively.
Published: 2018

17. Alcohol- and Water-Tolerant Living Anionic Polymerization of Aziridines

Author: Frederik R. Wurm, Elisabeth Rieger, Daniel Taton, Camille Bakkali-Hassani, Stéphane Carlotti, Denis Andrienko, Manfred Wagner, Lei Liu, Tassilo Gleede, Max-Planck-Institut für Polymerforschung (MPI-P), Max-Planck-Gesellschaft, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: chemistry.chemical_classification, Polymers and Plastics, Chemistry, Organic Chemistry, Alcohol, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Anionic addition polymerization, Nucleophile, Polymerization, Tosyl, Polymer chemistry, Materials Chemistry, Living polymerization, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Living anionic polymerization
Abstract: Living anionic polymerization gives access to well-defined polymers, but it demands strict purification of reagents and solvents. This work presents the azaanionic polymerization (AAROP) of aziridines as a robust living polymerization technique, with the ease of controlled radical polymerizations. AAROP does not require inert atmosphere and remains living in the presence of large amounts of water or alcohols. Mesyl-, tosyl-, or brosyl-activated aziridines were polymerized with up to 100-fold excess of a protic impurity with respect to the initiator and still being active for chain extension. This allowed the preparation of polyols by anionic polymerization without protective groups, as only minor initiation occurred from the alcohols. The tolerance toward protic additives lies in the electron-withdrawing effect of the activating groups, decreasing the basicity of the propagating species, while maintaining a strong nucleophilic character. In this way, competing alcohols and water are only slightly involved...
Published: 2018

18. Benzoic acid-organocatalyzed ring-opening (co)polymerization (ORO(c)P) of <scp>l</scp>-lactide and ε-caprolactone under solvent-free conditions: from simplicity to recyclability

Author: Olivier Coulembier, Julien De Winter, Daniel Taton, Leila Mezzasalma, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Mass Spectrometry Research Group, Université de Mons (UMons), Laboratoire de Chimie des Matériaux et Polymères (SMPC), and Université de Mons-Hainaut
Subjects: 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Pollution, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, chemistry, Polymerization, Polymer chemistry, Copolymer, Environmental Chemistry, Sublimation (phase transition), 0210 nano-technology, Bifunctional, Caprolactone, ComputingMilieux_MISCELLANEOUS, Benzoic acid
Abstract: The development of sustainable synthetic approaches to biodegradable and biocompatible polymeric materials represents a key challenge in polymer chemistry. A novel solvent-free and organocatalyzed ring-opening (co)polymerization (ORO(c)P) method utilizing benzoic acid(BA) as simple thermostable carboxylic acid-type catalyst is proposed to not only produce structurally well-defined aliphatic homopolyesters derived from L-lactide (L-LA) and e-caprolactone (CL), but also and, unexpectedly, statistical copolyesters based on the two monomer units. RO(c)P reactions were conducted in bulk in a temperature range of 155–180 °C, in presence of alcohols as initiators. A triblock copolymer, namely, PLLA-b-PCL-b-PLLA, was also synthesized, attesting to the “controlled/living” character of this BA-OROP process. A bifunctional mechanism is proposed to operate, involving activation of both the monomer and the propagating hydroxyl by H-bonding. Very importantly, the BA organocatalyst could be readily recycled by simple sublimation and could be reused in further organocatalytic cycles.
Published: 2018

19. Synthesis of self-healable waterborne isocyanate-free poly(hydroxyurethane)-based supramolecular networks by ionic interactions

Author: Lourdes Irusta, Haritz Sardon, Robert H. Aguirresarobe, Jaime Martín, Amaury Bossion, Ion Olazabal, Daniel Taton, Sara Marina, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Departamento de Ciencia y Tecnologıa de Polımeros e Instituto de Materiales Polimericos (POLYMAT), and Universidad del Pais Vasco / Euskal Herriko Unibertsitatea [Espagne] (UPV/EHU)
Subjects: Adipic acid, Polymers and Plastics, Organic Chemistry, Supramolecular chemistry, Ionic bonding, Bioengineering, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Isocyanate, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Chemical engineering, Dicarbonate, 0210 nano-technology, Citric acid, Phase inversion, ComputingMilieux_MISCELLANEOUS
Abstract: A novel synthetic strategy to isocyanate-free supramolecular polyhydroxyurethanes based on ionic interactions is described. Water-dispersible non-isocyanate polyhydroxyurethanes (WPHUs) dispersions were first prepared from aminoalkyl-terminated poly(dimethylsiloxane), diglycerol dicarbonate and a 8-membered cyclic carbonate (bis-N-8-C) via phase inversion polymerization. Taking advantage of the tertiary amino-groups present in bis-N-8-C, which acted as an internal emulsifier in presence of acetic acid, WPHUs dispersions could thus be achieved. After optimizing the internal surfactant concentration, namely at 30 mol% of bis-N-8-C, stable waterborne PHU dispersions with particle size around 200 nm were obtained. Supramolecular PHU assemblies based on ionic interactions were generated by mixing carboxylic acids of different functionalities, including adipic acid or citric acid, with the optimal dispersion, in absence of any organic solvents. This simple post-chemical modification step enabled to improve the film properties. Formation of the supramolecular network was evidenced by FTIR and 1H NMR spectroscopies. Use of citric acid was found to greatly improve the mechanical properties of the resulting films, as characterized by a transition solid/liquid, which varied from 60 °C. Supramolecular interactions impart healing abilities to the films, as determined by optical microscopy. Altogether, this study demonstrates for the first time the potential of combining water-dispersible non-isocyanate polyhydroxyurethanes with simple carboxylic acid-containing reagents, providing a straightforward and sustainable approach to novel reprocessable PHU-type materials.
Published: 2019

20. Opportunities for organocatalysis in polymer synthesis via step-growth methods

Author: Haritz Sardon, Nicolas Zivic, Katherine V. Heifferon, James L. Hedrick, Amaury Bossion, Daniel Taton, Timothy Edward Long, Leire Meabe, European Commission, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Team 1 LCPO : Polymerization Catalyses & Engineering, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Departamento de Ciencia y Tecnologıa de Polımeros e Instituto de Materiales Polimericos (POLYMAT), Universidad del Pais Vasco / Euskal Herriko Unibertsitatea [Espagne] (UPV/EHU), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Materials science, Polymers and Plastics, Large array, polyurethanes, Nanotechnology, 02 engineering and technology, 010402 general chemistry, step-growth, 01 natural sciences, Materials Chemistry, organocatalysis, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Organic Chemistry, Surfaces and Interfaces, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Step-growth polymerization, Polyester, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, chemistry, Organocatalysis, Ceramics and Composites, 0210 nano-technology
Abstract: Organocatalysis has emerged as an invaluable tool for polymer synthesis and has already demonstrated versatility for replacing organometallic catalysts in many polymerization reactions. The overall ease of removal and lower toxicity of organocatalysts relative to their common metal counterparts has also nurtured development especially in chain growth polymerizations to achieve precision macromolecular architectures for application in the biomedical space. The application of organocatalysts in step-growth polymerizations of polymers, including polyesters, polycarbonates, and polyurethanes, has garnered fewer studies in spite of the large array of benefits that could be achieved. Step-growth polymers account for nearly 20 wt. % of the Word Plastic Production and play a vital role in many technologies as engineering plastics and high performance polymeric materials with outstanding thermomechanical performance. Step-growth polymerizations are achieved using monomers with a diversity of chemical functionality. Consequently, a vast array of polymeric structures are attainable and will impact diverse applications in energy, aerospace, medicine, transportation, and construction. This review article will highlight the recent advances in organocatalysis in step growth polymerizations. We will primarily focus our review on the synthesis of commercially important polyesters and polyurethanes using organocatalysis, however, the review will also emphasize recent literature describing less explored polymers, such as polyethers, polycarbonates, and polybenzoins, which have recently employed organocatalysts. Moreover, the article will draw attention to recent efforts in the use of carbon dioxide as a monomer for the preparation of step-growth polymers in the presence of organocatalysis. The authors thank the European Commission for its financial support through the projects SUSPOL-EJD 642671. Haritz Sardon gratefully acknowledges financial support from MINECO through project MAT2017-83373-R.
Published: 2019

21. Self-catalysed folding of single chain nanoparticles (SCNPs) by NHC-mediated intramolecular benzoin condensation

Author: Rachel K. O'Reilly, Sofiem Garmendia, Daniel Taton, Andrew P. Dove, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and University of Birmingham [Birmingham]
Subjects: Polymers and Plastics, Organic Chemistry, Bioengineering, Chain transfer, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 3. Good health, 0104 chemical sciences, Catalysis, Benzaldehyde, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Benzyl alcohol, Intramolecular force, Polymer chemistry, Vinyl acetate, Copolymer, [CHIM]Chemical Sciences, Benzoin condensation, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: A self-catalysed folding strategy to form single chain nanoparticles (SCNPs) was developed via an intramolecular N-heterocyclic carbene (NHC)-mediated benzoin condensation. Benzaldehyde, styrene and benzimidazolium chloride units were randomly incorporated into a poly(ionic liquid)-based (PIL) copolymer precursor by reversible addition–fragmentation chain transfer (RAFT) copolymerisation. Post-chemical modification of this linear precursor by insertion of a non-innocent acetate counter-anion into the benzimidazolium moieties conferred thermolatent catalytic behaviour owing to the equilibrium between benzimidazolium acetate units and corresponding NHC ones. Upon heating, catalytically active NHCs allowed the formation of benzoin-type intramolecular cross-links, thus folding linear chains into SCNPs. NHC moieties became deactivated after cooling to room temperature, which enabled easy isolation and purification of the covalently and intramolecularly cross-linked SCNPs. Importantly, the latent NHC moieties were proven to retain their catalytic activity when arranged into SCNPs as evidenced through their reactivation by simple heating. The catalytic activity of these SCNPs was further confirmed by implementing another NHC-organocatalysed reaction, namely, transesterification reaction between vinyl acetate and benzyl alcohol. This work represents the first example of catalysis by a parent linear precursor which drives its own folding and remains catalytically active.
Published: 2019

22. Catalytically Active N ‐Heterocyclic Carbene Release from Single‐Chain Nanoparticles Following a Thermolysis‐Driven Unfolding Strategy

Author: Rachel K. O'Reilly, Andrew P. Dove, Stefan B. Lawrenson, Sofiem Garmendia, Maria C. Arno, Daniel Taton, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and University of Birmingham [Birmingham]
Subjects: Silver, Polymers and Plastics, Metalation, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Heterocyclic Compounds, Materials Chemistry, Copolymer, Benzoin condensation, ComputingMilieux_MISCELLANEOUS, Molecular Structure, Chemistry, Organic Chemistry, Temperature, Nuclear magnetic resonance spectroscopy, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, Cross-Linking Reagents, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, Organocatalysis, Nanoparticles, 0210 nano-technology, Methane, Carbene, Macromolecule
Abstract: The need for efficient, tailor-made catalysts has inspired chemists to design synthetic macromolecular architectures for selective catalysis. To this purpose, herein the synthesis and in-depth characterization of Ag(I)-crosslinked single-chain nanoparticles (SCNPs) is reported and their application as catalysts is demonstrated. Specifically, a copolymer of styrenic benzimidazolium chloride is synthesized as a linear precursor via reversible addition-fragmentation chain-transfer polymerization. Metalation of the benzimidazolium moieties by Ag(I) resulted in the intramolecular cross-linking of single chains via the formation of silver-N-heterocyclic carbene (Ag-NHC) linkages under dilute conditions. The successful formation of well-defined, robust SCNPs is evidenced by size-exclusion chromatography, dynamic light scattering, nuclear magnetic resonance spectroscopy, and transmission electron microscopy. Finally, it is demonstrated that the Ag-SCNPs can be used as NHC pre-catalysts, by first indirectly evidencing the formation of the corresponding unfolded NHC-CS2 polybetaine and then organocatalysing a benzoin condensation reaction.
Published: 2019

23. Bulk Organocatalytic Synthetic Access to Statistical Copolyesters from l-Lactide and ε-Caprolactone Using Benzoic Acid

Author: Olivier Coulembier, Simon Harrisson, Saad Saba, Pascal Loyer, Leila Mezzasalma, Daniel Taton, University of Mons [Belgium] (UMONS), Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Team 1 LCPO : Polymerization Catalyses & Engineering, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Nutrition, Métabolismes et Cancer (NuMeCan), Institut National de la Recherche Agronomique (INRA)-Université de Rennes (UR)-Institut National de la Santé et de la Recherche Médicale (INSERM), Fonds De La Recherche Scientifique - FNRS, European Commission, Institut National de la Santé et de la Recherche Médicale, European Regional Development Fund, Belgian Federal Science Policy Office, European Project: 642671,H2020,H2020-MSCA-ITN-2014,SUSPOL(2015), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)
Subjects: Polymers and Plastics, Polyesters, Diol, Bioengineering, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Polymerization, Biomaterials, Dioxanes, chemistry.chemical_compound, Lactones, Polymer chemistry, Materials Chemistry, Copolymer, Reactivity (chemistry), organocatalysis, bulk, Caproates, Benzoic acid, statistical copolymers, caprolactone, Lactide, Molar mass, Benzoic Acid, 021001 nanoscience & nanotechnology, 0104 chemical sciences, copolymerization, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, lactide, 0210 nano-technology, Caprolactone
Abstract: International audience; The development of synthetic strategies to produce statistical copolymers based on l-lactide (l-LA) and ε-caprolactone (CL), denoted as P(LA- stat-CL), remains highly challenging in polymer chemistry. This is due to the differing reactivity of the two monomers during their ring-opening copolymerization (ROcP). Yet, P(LA- stat-CL) materials are highly sought after as they combine the properties of both polylactide (PLA) and poly(ε-caprolactone) (PCL). Here, benzoic acid (BA), a naturally occurring, cheap, readily recyclable, and thermally stable weak acid, is shown to trigger the organocatalyzed ring-opening copolymerization (OROcP) of l-LA and CL under solvent-free conditions at 155 °C, in presence of various alcohols as initiators, with good control over molar masses and dispersities (1.11 < Đ < 1.35) of the resulting copolyesters. Various compositions can be achieved, and the formation of statistical compounds is shown through characterization by H, C, and diffusion ordered spectroscopy NMR spectroscopies and by differential scanning calorimetry, as well as through the determination of reactivity ratios ( r = 0.86, r = 0.86), using the visualization of the sum of squared residuals space method. Furthermore, this BA-OROcP process can be exploited to access metal-free PLA- b-P(LA- stat-CL)- b-PLA triblock copolymers, using a diol as an initiator. Finally, residual traces of BA remaining in P(LA- stat-CL) copolymers (
Published: 2019

24. Hyperbranched polyesters by polycondensation of fatty acid-based ABn-type monomers

Author: Daniel Taton, Didier Pintori, Etienne Grau, Henri Cramail, Blandine Testud, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Institut des Corps Gras (ITERG), ITERG, Team 2 LCPO : Biopolymers & Bio-sourced Polymers, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and Team 1 LCPO : Polymerization Catalyses & Engineering
Subjects: Condensation polymer, Double bond, FOS: Physical sciences, 02 engineering and technology, Applied Physics (physics.app-ph), Condensed Matter - Soft Condensed Matter, 010402 general chemistry, Branching (polymer chemistry), 01 natural sciences, Sodium methoxide, chemistry.chemical_compound, Polymer chemistry, Environmental Chemistry, [CHIM]Chemical Sciences, polyester, chemistry.chemical_classification, bio-sourced, Physics - Applied Physics, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Pollution, 0104 chemical sciences, 3. Good health, Polyester, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], HyperBranched polymers, Soft Condensed Matter (cond-mat.soft), 0210 nano-technology, Glass transition
Abstract: Widely available vegetable oils were readily derivatized into chemically pure ABn-type monomers (n = 2 or 3). Their polymerization led to unprecedented hyperbranched polyesters. Four different AB2/AB3-type monomers bearing one A-type methyl ester and two or three B-type alcohol functions were purposely synthesized via two elementary steps, i.e. epoxidation of the internal double bond of the vegetable oil precursors followed by ring-opening of the epoxy groups under acidic conditions. The polycondensation of these bio-sourced monomers was performed in bulk, in the presence of an appropriate catalyst, giving access to modular hyperbranched polyesters with tunable properties. Among the catalysts tested, zinc acetate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and sodium methoxide proved the most effective, allowing the achievement of molar masses in the range 3000--10 000 g mol--1 and dispersities varying from 2 to 15, depending on the initial conditions. The degree of branching, DB, as determined by 1H NMR spectroscopy, was found to be between 0.07 and 0.45. The as-devised hyperbranched polyesters displayed either amorphous or semi-crystalline properties, as a function of the selected AB2/AB3-type initial monomers, with a glass transition temperature, Tg, ranging from --33 to 9 {\textdegree}C and a decomposition temperature at 5 wt% of the sample, Td5%, varying from 204 to 340 {\textdegree}C., Comment: http://lcpo.fr/index.php/research-teams/2-biopolymers-and-bio-sourced-polymers, http://lcpo.fr/index.php/research-teams/1-polymerization-catalyses-and-engineering
Published: 2019
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25. The organocatalytic ring-opening polymerization of N-tosyl aziridines by an N-heterocyclic carbene

Author: Daniel Taton, Frederik R. Wurm, Camille Bakkali-Hassani, Joan Vignolle, Stéphane Carlotti, Elisabeth Rieger, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Max-Planck-Institut für Polymerforschung (MPI-P), Max-Planck-Gesellschaft, Team 1 LCPO : Polymerization Catalyses & Engineering, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), French Ministry of Education and Research, European Union’s Horizon 2020 research and innovation programme, MSCA-ITN action, SUSPOL project, grant agreement no 642671, European Project: 642671,H2020,H2020-MSCA-ITN-2014,SUSPOL(2015), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Stereochemistry, CATALYSTS, MONOMERS, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Ring-opening polymerization, Catalysis, LIVING ANIONIC-POLYMERIZATION, chemistry.chemical_compound, Tosyl, Polymer chemistry, Materials Chemistry, Copolymer, POLYESTERS, COPOLYMERIZATION, Living anionic polymerization, EPSILON-CAPROLACTONE, Metals and Alloys, PROTON-TRANSFER POLYMERIZATION, General Chemistry, Aziridine, 021001 nanoscience & nanotechnology, POLYAMINES, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Ceramics and Composites, POLYMERS, STABLE CARBENES, 0210 nano-technology, Carbene, Isopropyl
Abstract: International audience; The ring-opening polymerization of N-tosyl aziridines, in the presence of 1,3-bis(isopropyl)-4,5(dimethyflimidazol-2-ylidene as an organocatalyst and an N-tosyl secondary amine as initiator mimicking the growing chain, provides the first metal-free route to well defined poly(aziridine)s (PAz) and related PAz-based block copolymers.
Published: 2016

26. Direct one-pot synthesis of poly(ionic liquid) nanogels by cobalt-mediated radical cross-linking copolymerization in organic or aqueous media

Author: Daniel Taton, Daniela Cordella, Mathilde Weiss-Maurin, Christophe Detrembleur, Christine Jérôme, Univ Liege, Dept Chem, CERM, Université de Liège-CERM, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Kinetic chain length, Polymers and Plastics, Ethyl acetate, Bioengineering, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biochemistry, MOLECULAR-SIZE DISTRIBUTION, chemistry.chemical_compound, LIVING COPOLYMERIZATION, Bromide, Polymer chemistry, Copolymer, Vinyl acetate, POLY(VINYL ACETATE), DRUG-DELIVERY, VINYL-ACETATE, Aqueous solution, Organic Chemistry, RAFT POLYMERIZATION, THERMOSENSITIVE NANOGELS, 021001 nanoscience & nanotechnology, 0104 chemical sciences, BLOCK-COPOLYMERS, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, chemistry, Ionic liquid, CLICK CHEMISTRY, FUNCTIONAL MATERIALS, 0210 nano-technology
Abstract: International audience; Nanogels of controlled kinetic chain length were synthesized by cobalt-mediated radical cross-linking copolymerization (CMRccP) involving a vinyl monomer and a divinyl cross-linker. This strategy was first validated to achieve neutral poly(vinyl acetate) nanogels by CMRccP of vinyl acetate and divinyl adipate as a cross-linker at 40 degrees C in the presence of an alkyl-cobalt(III) serving both as an initiator and a controlling agent using ethyl acetate as a solvent. Poly(ionic liquid) nanogels were then directly obtained by CMRccP of N-vinyl-3-ethyl imidazolium bromide in the presence of 1,13-divinyl-3-decyl diimidazolium bromide as a cross-linker. CMRccP experiments could be conducted either in an organic solvent using dimethyl formamide or, more interestingly, in aqueous solution, demonstrating the robustness and versatility of this one-step process. Chain extensions of PIL nanogels were also carried out in water, forming core-shell structures, thus opening new avenues in the design of functional nanogels.
Published: 2016

27. Reversible ionically-crosslinked single chain nanoparticles as bioinspired and recyclable nanoreactors for N -heterocyclic carbene organocatalysis

Author: Rachel K. O'Reilly, Sofiem Garmendia, Daniel Taton, Andrew P. Dove, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Team 1 LCPO : Polymerization Catalyses & Engineering, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Birmingham [Birmingham], The research leading to these results has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement no. 642671, project 'SUSPOL-EJD'., European Project: 642671,H2020,H2020-MSCA-ITN-2014,SUSPOL(2015), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Polymers and Plastics, Organic Chemistry, Bioengineering, Chain transfer, 02 engineering and technology, Nanoreactor, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, chemistry.chemical_compound, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Benzoin, Organocatalysis, Amphiphile, Ionic liquid, Salt metathesis reaction, [CHIM]Chemical Sciences, 0210 nano-technology
Abstract: International audience; The intrinsic advantages of poly(ionic liquid)s (PILs), based on their high chemical activity and flexible structure, have been harnessed by exploring their applicability as catalytic single chain nanoparticles (SCNPs). A non-covalent bioinspired approach has been established to ionically crosslink an imidazolium-based poly(ionic liquid) to form folded SCNPs. An amphiphilic styrenic-type coPIL was synthesized by reversible addition fragmentation chain transfer (RAFT) to include hydrophilic stabilizer units, hydrophobic spacers and two antagonist functionalities randomly distributed through the polymer backbone. The antagonist functionalities were then intramolecularly and ionically crosslinked using a simple anion metathesis reaction, which resulted in folding to form the SCNPs under mild conditions. The folding process enabled the protection of the N-heterocyclic carbene (NHC) functionality, through the benzoate–imidazolium interaction between antagonist monomer units. Upon the application of heat, free NHCs could be generated within the confined SCNPs, which could be further utilized in benzoin catalysis. Most importantly, the reversible nature of the crosslinking and reversible generation of the active functionality allowed for the utilization of the SCNPs as a recyclable catalytic support.
Published: 2018

28. Poly(arylene vinylene) Synthesis via a Precursor Step-Growth Polymerization Route Involving the Ramberg–Bäcklund Reaction as a Key Post-Chemical Modification Step

Author: Georges Hadziioannou, Yannick Landais, Kunche Aravindu, Daniel Taton, Frédéric Robert, Cyril Brochon, Joan Vignolle, Eric Cloutet, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie des polymères organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Institut de Chimie du CNRS (INC), Team 4 LCPO : Polymer Materials for Electronic, Energy, Information and Communication Technologies, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and Team 1 LCPO : Polymerization Catalyses & Engineering
Subjects: Polymers and Plastics, 02 engineering and technology, Fluorene, Conjugated system, 010402 general chemistry, 01 natural sciences, Step-growth polymerization, Inorganic Chemistry, chemistry.chemical_compound, Polymer chemistry, Materials Chemistry, Copolymer, chemistry.chemical_classification, Ramberg–Bäcklund reaction, Ramberg-Bäcklund reaction, Organic Chemistry, Arylene, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, π-Conjugated polymers, Poly(fluorene vinylene-co-carbazole vinylene), [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Poly(fluorene vinylene), 0210 nano-technology
Abstract: International audience; The synthesis of conjugated copolymers based on poly(fluorene vinylene) [PFV] and poly(fluorene vinylene-co-carbazole vinylene) [PFVCV] was achieved via a previously unexplored precursor three-step synthetic route involving the Ramberg-Bäcklund reaction. The resulting -conjugated (co)polymers proved highly soluble in common organic solvents, such as DCM, THF, or CHCl3. The solution step-growth polymerization between 2,7-bis(bromomethyl)-9,9'-dihexyl-9H-fluorene [F-Br] and 2,7-bis(mercaptomethyl)-9,9'-dihexyl-9H-fluorene [F-SH] was carried out under basic conditions at 100 °C in a mixture of MeOH and THF. The resulting polysulfides were then subjected to an oxidation reaction using m-CPBA, which was followed by the Ramberg-Bäcklund reaction in the presence of CF2Br2/Al2O3-KOH, thus achieving the desired PFV. Similarly, PFVCV could be synthesized through the same three-step sequence employing, in this case, 2,7-bis(mercaptomethyl)-9-(tridecan-7-yl)-9H-carbazole (C-SH) and F-Br. Conjugated polymers with apparent molecular weights up to 15 kg.mol-1 and exhibiting promising optical features were obtained following this convenient synthetic strategy.
Published: 2018

29. Unexpected Synthesis of Segmented Poly(hydroxyurea−urethane)s from Dicyclic Carbonates and Diamines by Organocatalysis

Author: Daniel Taton, Etienne Grau, Henri Cramail, David Mecerreyes, Alejandro J. Müller, Amaury Bossion, Haritz Sardon, Lourdes Irusta, Guoming Liu, Roberto Hernández Aguirresarobe, Cui Su, European Commission, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Departamento de Ciencia y Tecnologıa de Polımeros e Instituto de Materiales Polimericos (POLYMAT), Universidad del Pais Vasco / Euskal Herriko Unibertsitatea [Espagne] (UPV/EHU), Team 2 LCPO : Biopolymers & Bio-sourced Polymers, and University of Chinese Academy of Sciences [Beijing] (UCAS)
Subjects: Polymers and Plastics, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Diamine, Polymer chemistry, Materials Chemistry, organocatalysis, Dicarbonate, Polyurethane, chemistry.chemical_classification, Organic Chemistry, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, polyurethane, Organocatalysis, Urea, 0210 nano-technology, Ethylene glycol, polyurea
Abstract: A complete study of the effect of different organocatalysts on the step-growth polyaddition of a five-membered dicyclic carbonate, namely diglycerol dicarbonate, with a poly(ethylene glycol)-based diamine in bulk at 120 °C was first carried out. The reaction was found to be dramatically catalyst-dependent, higher rates being observed in the presence of strong bases, such as phosphazenes (t-Bu-P4 or P4) and 5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). Unexpectedly, the as-formed urethane linkages entirely vanished with time, as evidenced by FTIR and 13C NMR spectroscopies, while signals due to urea bond formation progressively appeared. An advantage of the chemical transformation occurring from urethane to urea linkages was further taken by optimizing the polymerization conditions to access a range of poly(hydroxyurea−urethane)s (PHUUs) with precise urethane to urea ratio in a one-pot process. Characterization of the corresponding polymers by rheological measurements showed that the storage modulus reached a plateau at high temperatures and at high urea contents. The application temperature range of poly(hydroxyurea−urethane)s could thus be increased from 30 to 140 °C, as for regular polyurethanes. Furthermore, SAXS and phase-contrast microscopy images demonstrated that increasing the urea content improved the phase separation between soft and hard segments of these PHUUs. Altogether, this novel, straightforward, efficient, and environmentally friendly strategy enables the access to non-isocyanate poly(urea−urethane)s with tunable urethane-to-urea ratio from five-membered dicyclic carbonates following an organocatalytic pathway The authors thank the European Commission for its financial support through the projects SUSPOL-EJD 642671, Renaissance-ITN 289347, and OrgBIO-ITN 607896. Haritz Sardon gratefully acknowledges financial support from MINECO through project SUSPOL and FDI 16507. A. J. Müller, G. Liu, and H. Sardon also acknowledge European funding by the RISE BIODEST project (H2020-MSCA-RISE-2017-778092). G. Liu is grateful to the support from the Youth Innovation Promotion Association of CAS (2015026).
Published: 2018

30. Selective Initiation from Unprotected Aminoalcohols for the N -Heterocyclic Carbene-Organocatalyzed Ring-Opening Polymerization of 2-Methyl- N- tosyl Aziridine: Telechelic and Block Copolymer Synthesis

Author: Tassilo Gleede, Clément Coutouly, Frederik R. Wurm, Daniel Taton, Joan Vignolle, Camille Bakkali-Hassani, Stéphane Carlotti, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Max-Planck-Institut für Polymerforschung (MPI-P), and Max-Planck-Gesellschaft
Subjects: Diethanolamine, Polymers and Plastics, Organic Chemistry, 02 engineering and technology, Aziridine, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Ring-opening polymerization, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Tosyl, Polymerization, Polymer chemistry, Materials Chemistry, Copolymer, [CHIM]Chemical Sciences, 0210 nano-technology, Tetrahydrofuran, Isopropyl, ComputingMilieux_MISCELLANEOUS
Abstract: Commercial aminoalcohols, namely, 2-(methyl amino)ethanol (1) and diethanolamine (2), are investigated as direct initiators, i.e., with no need of protection of the hydroxyl groups, for the N-heterocyclic carbene-organocatalyzed ring-opening polymerization (NHC-OROP) of 2-methyl-N-p-toluenesulfonyl aziridine. NHC-OROP’s are performed at 50 °C in tetrahydrofuran, in the presence of 1,3-bis(isopropyl)-4,5(dimethyl)imidazol-2-ylidene (Me5-IPr) as organocatalyst. Thus, nonprotected and nonactivated aminoalcohol initiators 1 and 2 provide a direct access to metal-free α-hydroxy-ω-amino- and α,α′-bis-hydroxy-ω-amino telechelics on the basis of polyaziridine (PAz), respectively. Excellent control over molar masses, narrow dispersities (Đ ≤ 1.20), and high chain-end fidelity are evidenced by combined analyses, including NMR spectroscopy, size exclusion chromatography, and MALDI ToF mass spectrometry. The amino-initiated NHC-OROP is therefore tolerant to the presence of nonprotected hydroxyl group(s). The as-obtai...
Published: 2018

31. Facile Synthesis of Reversibly Crosslinked Poly(ionic liquid)-type Gels: Recyclable Supports for Organocatalysis by N-Heterocyclic Carbenes

Author: Daniel Taton, Sofiem Garmendia, Romain Lambert, Andrew P. Dove, Rachel K. O'Reilly, Anne-Laure Wirotius, Joan Vignolle, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry [University of Warwick], University of Warwick [Coventry], School of Chemistry University of Birmingham, University of Birmingham [Birmingham], Team 1 LCPO : Polymerization Catalyses & Engineering, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The research leading to these results has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement no. 642671, project 'SUSPOL-EJD'., European Project: 642671,H2020,H2020-MSCA-ITN-2014,SUSPOL(2015), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Polymers and Plastics, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Styrene, chemistry.chemical_compound, Polymer chemistry, N-Heterocyclic carbene, Materials Chemistry, Copolymer, Benzoin condensation, Poly(ionic liquid), Chemistry, Organocatalysis, Organic Chemistry, Masked-carbene, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Reagent, Ionic liquid, 0210 nano-technology, Carbene
Abstract: International audience; Owing to their broad modularity, polymeric versions of ionic liquids, referred to as poly(ionic liquids) (PILs), have attracted increasing attention as recyclable polymer-supported (pre)catalysts for various chemical transformations. Herein, an imidazolium-based statistical copolymer based on PIL (=coPIL) is specifically designed by free-radical copolymerization of styrene and 4-vinylbenzylethyl(benz)imidazolium chloride. A selective ion-exchange reaction can be subsequently achieved to incorporate bio-sourced difunctional sebacate-type counter-anions, causing the physical crosslinking of the coPIL precursor via electrostatic interactions between pendant imidazolium moieties and sebacate dianions. The as-obtained gel-type precursor exhibits a thermally latent behavior in THF, proving advantageous for a facile manipulation and practical use for organocatalysis. Upon heating, typically at 80 °C, interaction between the sebacate dianion and the proton in C2-position of the imidazolium moieties generates polymer-supported N-heterocyclic carbene units that act as catalytic active species towards NHC-organocatalyzed reactions, namely, benzoin condensation, transesterification and cyanosilylation. The PIL-based gel precursors can be restored, recycled and reused by simply cooling down, i.e. with no need of an external chemical reagent, due to the shift of the intramolecular equilibrium towards the formation of imidazolium sebacate-type units. Overall, this novel gel-type copolymeric platform shows a thermo-responsive behaviour, and proves particularly versatile for heterogeneous organocatalysis.
Published: 2018

32. Pd( ii )–NHC coordination-driven formation of water-soluble catalytically active single chain nanoparticles

Author: Daniel Taton, Joan Vignolle, Romain Lambert, Pierre Berto, Sofiem Garmendia, Anne-Laure Wirotius, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Polymers and Plastics, Ethylene oxide, Ligand, Organic Chemistry, Bioengineering, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 0104 chemical sciences, Styrene, Catalysis, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Suzuki reaction, chemistry, Intramolecular force, Polymer chemistry, Copolymer, 0210 nano-technology, Carbene, ComputingMilieux_MISCELLANEOUS
Abstract: A well-defined linear statistical copolymer precursor, made of styrene, grafted poly(ethylene oxide) and benzimidazolium chloride units serving as N-heterocyclic carbene (NHC) ligand precursors, is designed by random RAFT copolymerization. Intramolecular coordination forming Pd(II)–NHC2 crosslinks yields single chain nanoparticles (SCNPs). The formation of SCNPs is achieved by the insertion of Pd(OAc)2 into diluted solution, which is monitored by combined analyses, including NMR, SEC, DLS and TEM. When used for the Suzuki coupling in water, the catalytic activity of these Pd(II)–NHC2-containing SCNPs is greatly improved relative to Pd(OAc)2 as a benchmark molecular catalyst. When compared to a molecular catalyst of Pd–NHC2-type, i.e. with a structure similar to that of the SCNP-supported catalytic units, the conversion to a reaction product is again higher, owing to a beneficial SCNP effect, although an increase in catalytic efficiency is not spectacular.
Published: 2018

33. All Poly(ionic liquid)-Based Block Copolymers by Sequential Controlled Radical Copolymerization of Vinylimidazolium Monomers

Author: Daniel Taton, Daniela Cordella, Anthony Kermagoret, David Mecerreyes, Christophe Detrembleur, Mehmet Isik, Christine Jérôme, Antoine Debuigne, Univ Liege, Dept Chem, CERM, Université de Liège-CERM, Univ Basque Country UPV EHU, Joxe Mari Korta Ctr, POLYMAT, Univ Basque Country, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Polymers and Plastics, Radical polymerization, Ethyl acetate, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, METATHESIS, Inorganic Chemistry, chemistry.chemical_compound, Polymer chemistry, Materials Chemistry, Copolymer, Vinyl acetate, Reversible addition−fragmentation chain-transfer polymerization, CONDUCTIVITY, VINYL-ACETATE, Alkyl, chemistry.chemical_classification, FRAGMENTATION CHAIN TRANSFER, POLYMERIZED IONIC LIQUIDS, ELECTROLYTES, Organic Chemistry, RAFT POLYMERIZATION, PERFORMANCE, 021001 nanoscience & nanotechnology, ANION-EXCHANGE, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, chemistry, Ionic liquid, SEPARATION, 0210 nano-technology
Abstract: International audience; The organometallic-mediated radical polymerization (OMRP) of N-vinyl-3-alkylimidazolium-type monomers, featuring the bis(trifluoromethylsulfonyl)imide counter-anion (Tf2N-) in the presence of Co(acac)(2) as controlling agent, is reported. Polymerizations of monomers with methyl, ethyl, and butyl substituents are fast, reaching high monomer conversion in ethyl acetate as solvent at 30 degrees C, and afford structurally well-defined hydrophobic poly(ionic liquid)s (PILs) of N-vinyl type. Block copolymer synthesis is also achieved by sequential OMRP of N-vinyl-3-alkyldazolium salts carrying different alkyl chains and different counteranions (Tf2N- or Br-). These block copolymerizations are carried out at 30 degrees C, either under homogeneous solution in methanol or in a biphasic medium consisting of a mixture of ethyl acetate and water. Unprecedented PIL-b-PIL block copolymers are thus prepared under these conditions. However, anion exchange occurs at the early stage of the growth of the second block. Finally, diblock copolymers generated in the biphasic medium can be readily coupled by addition of isoprene, forming all PIL-based and symmetrical ABA-type triblock copolymers in a one-pot process. Such a direct block copolymerization method, involving vinylimidazolium monomers bearing different alkyl chains, thus opens new opportunities in the precision synthesis of all PIL-based block copolymers of tunable properties.
Published: 2015

34. Special Issue in: Organocatalyzed polymerizations

Author: Andrew P. Dove, Olivier Coulembier, Daniel Taton, Haritz Sardon, Alejandro J. Müller, Departamento de Ciencia y Tecnologıa de Polımeros e Instituto de Materiales Polimericos (POLYMAT), Universidad del Pais Vasco / Euskal Herriko Unibertsitatea [Espagne] (UPV/EHU), University of Warwick [Coventry], Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Center of innovation and research in materials and polymers (CIRMAP), and Laboratory of polymeric and composite materials
Subjects: [CHIM.POLY]Chemical Sciences/Polymers, Polymers and Plastics, Chemistry, Organic Chemistry, Materials Chemistry, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract: International audience
Published: 2017

35. Expanding the scope of N -heterocyclic carbene-organocatalyzed ring-opening polymerization of N -tosyl aziridines using functional and non-activated amine initiators

Author: Frederik R. Wurm, Joan Vignolle, Camille Bakkali-Hassani, Stéphane Carlotti, Daniel Taton, Elisabeth Rieger, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Max-Planck-Institut für Polymerforschung (MPI-P), and Max-Planck-Gesellschaft
Subjects: Sulfonyl, chemistry.chemical_classification, Polymers and Plastics, Alkene, Organic Chemistry, General Physics and Astronomy, 02 engineering and technology, Aziridine, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Ring-opening polymerization, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Tosyl, Polymer chemistry, Trimethylsilyl azide, Materials Chemistry, Amine gas treating, 0210 nano-technology, Isopropyl, ComputingMilieux_MISCELLANEOUS
Abstract: Polyaziridines (PAz) were synthesized for the first time by the 1,3-bis(isopropyl)-4,5(dimethyl)imidazol-2-ylidene-organocatalyzed ring-opening polymerization (OROP) of 2-alkyl- N - p -toluenesulfonyl aziridine (alkyl = methyl or phenyl), in the presence of both functional activated amine and non-functional non-activated amine initiators. Thus, not only an allyl-functionalized N -sulfonyl amine could serve as initiator, but also trimethylsilyl azide allowed introducing an allyl and an azido functionality in α-position of PAz chains, respectively. A non-activated and commercially available secondary amine, such as di- n -butylamine, also effectively initiated the OROP of N -tosylaziridines. Excellent control over molar masses, high chain-end fidelity and narrow dispersities ( Ð ≤ 1.20) were achieved, as attested by NMR spectroscopy, size exclusion chromatography and MALDI ToF mass spectrometry. PAz precursors consisting of the alkene or the azido functionality could further be derivatized, highlighting the accessibility of those functional groups. Overall, this N -heterocyclic carbene-OROP methodology offers a metal-free route to well-defined α-functionalized PAz.
Published: 2017

36. Fluorinated Poly(ionic liquid) Diblock Copolymers Obtained by Cobalt-Mediated Radical Polymerization-Induced Self-Assembly

Author: Abdelhafid Aqil, Farid Ouhib, Eric Drockenmuller, Daniela Cordella, Thomas Defize, Christine Jérôme, Anatoli Serghei, Daniel Taton, Karim Aissou, Christophe Detrembleur, Center for Education and Research on Macromolecules - CERM [Liège, Belgium], CESAM RU [Liège, Belgium]-Université de Liège, Centre d'Etude et de Recherche sur les Macromolécules (CERM), Université de Liège, CERM, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 4 LCPO : Polymer Materials for Electronic, Energy, Information and Communication Technologies, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon
Subjects: Materials science, Polymers and Plastics, Organic Chemistry, Radical polymerization, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Polyelectrolyte, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Cobalt-mediated radical polymerization, Polymer chemistry, Ionic liquid, Materials Chemistry, Copolymer, Ionic conductivity, Self-assembly, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: Poly(ionic liquid)s (PILs) have attracted considerable attention as innovative single-ion solid polyelectrolytes (SPEs) in substitution to the more conventional electrolytes for a variety of electrochemical devices. Herein, we report the precise synthesis, characterization, and use as single-ion SPEs of a novel double PIL-based amphiphilic diblock copolymer (BCP), i.e., where all monomer units are of N-vinyl-imidazolium type, with triethylene glycol pendant groups in the first block and a statistical distribution of N-vinyl-3-ethyl- and N-vinyl-3-perfluorooctyl-imidazolium bromides in the second block. BCP synthesis is achieved directly in water by a one-pot process, by cobalt-mediated radical polymerization-induced self-assembly (CMR-PISA). A subsequent anion exchange reaction substituting bis(trifluoromethylsulfonyl)imide (Tf2N–) for bromide (Br–) counter-anions leads to PIL BCPs with two different lengths of the first block. They demonstrate ionic conductivity σDC = 1–3 × 10–7 S cm–1, as determined by ...
Published: 2017

37. Non-Isocyanate Polyurethane Soft Nanoparticles Obtained by Surfactant-Assisted Interfacial Polymerization

Author: James L. Hedrick, Daniel Taton, Zhan Yuin Ong, Yi Yan Yang, Gavin O. Jones, Haritz Sardon, Amaury Bossion, David Mecerreyes, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Univ Basque Country UPV EHU, Joxe Mari Korta Ctr, POLYMAT, Univ Basque Country, IBM Almaden Research Center [San Jose], IBM, Departamento de Ciencia y Tecnologıa de Polımeros e Instituto de Materiales Polimericos (POLYMAT), Universidad del Pais Vasco / Euskal Herriko Unibertsitatea [Espagne] (UPV/EHU), and European Commission
Subjects: Materials science, polyurethanes, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, nanogels, Polymer chemistry, Electrochemistry, General Materials Science, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Polyurethane, isocyanate free, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Interfacial polymerization, Isocyanate, 0104 chemical sciences, Miniemulsion, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Drug delivery, 0210 nano-technology
Abstract: Polyurethanes (PUs) are considered ideal candidates for drug delivery applications due to their easy synthesis, excellent mechanical properties, and biodegradability. Unfortunately, methods for preparing well-defined PU nanoparticles required miniemulsion polymerization techniques with a nontrivial control of the polymerization conditions due to the inherent incompatibility of isocyanate-containing monomers and water. In this work, we report the preparation of soft PU nanoparticles in a one-pot process using interfacial polymerization that employs a non-isocyanate polymerization route that minimizes side reactions with water. Activated pentafluorophenyl dicarbonates were polymerized with diamines and/or triamines by interfacial polymerization in the presence of an anionic emulsifier, which afforded non-isocyanate polyurethane (NIPU) nanoparticles with sizes in the range of 200–300 nm. Notably, 5 wt % of emulsifier was required in combination with a trifunctional amine to achieve stable PU dispersions and avoid particle aggregation. The versatility of this polymerization process allows for incorporation of functional groups into the PU nanoparticles, such as carboxylic acids, which can encapsulate the chemotherapeutic doxorubicin through ionic interactions. Altogether, this waterborne synthetic method for functionalized NIPU soft nanoparticles holds great promise for the preparation of drug delivery nanocarriers. The authors thank the European Commission for their financial support through the project SUSPOL-EJD 642671 and the Gobierno Vasco/Eusko Jaurlaritza (IT 999-16). Haritz Sardon gratefully acknowledges financial support from MINECO through project SUSPOL and FDI 16507. Yi Yan Yang gratefully acknowledges financial support from the Institute of Bioengineering and Nanotechnology (Biomedical Research Council and Joint Council Office, Agency for Science, Technology and Research, Singapore).
Published: 2017

38. Intramolecular Quaternization as Folding Strategy for the Synthesis of Catalytically Active Imidazolium-Based Single Chain Nanoparticles

Author: Anne-Laure Wirotius, Romain Lambert, Daniel Taton, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Polymers and Plastics, Intramolecular reaction, Comonomer, Organic Chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Metathesis, 01 natural sciences, 0104 chemical sciences, Styrene, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Intramolecular force, Polymer chemistry, Materials Chemistry, Copolymer, Reversible addition−fragmentation chain-transfer polymerization, Benzoin condensation, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: A novel synthetic strategy to single chain nanoparticles (SCNP) based on a previously unexplored intramolecular reaction as a means to autonomously fold a parent copolymer precursor is reported. The latter is a statistical styrenic-type copolymer synthesized by RAFT polymerization and is composed of four different comonomer units, including styrene, grafted poly(ethylene oxide) chains, and antagonist benzimidazol- and chlorobenzyl-based units. The two latter functions are reacted together by a quaternization reaction to spark the folding process, creating imidazolium-based cross-link points. Formation of SCNP with a hydrodynamic diameter
Published: 2017

39. Organic Lewis Pairs Based on Phosphine and Electrophilic Silane for the Direct and Controlled Polymerization of Methyl Methacrylate: Experimental and Theoretical Investigations

Author: Frédéric Robert, Winnie Nzahou Ottou, Yannick Landais, Damien Bourichon, Anne-Laure Wirotius, Joan Vignolle, Egoitz Conde-Mendizabal, Karinne Miqueu, Daniel Taton, Jean-Marc Sotiropoulos, Ana Pascual, Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Caractérisation Physique Off-line (LCPO), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-11-BS08-0011,CATAPULT,POLYMERISATIONS ORGANOCATALYSEES PAR LES CARBENES : VERS UNE PLATEFORME CATALYTIQUE MULTI-TACHE(2011), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Pau et des Pays de l'Adour (UPPA)
Subjects: Sulfonyl, chemistry.chemical_classification, Polymers and Plastics, Trimethylsilyl, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, MESH: Phosphine, Silane, Lewis Pair, Metal-free polymerization, Methyl methacrylate, Density Functional Theory, 010402 general chemistry, 01 natural sciences, Frustrated Lewis pair, 0104 chemical sciences, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Polymerization, Polymer chemistry, Materials Chemistry, [CHIM]Chemical Sciences, Phosphonium, Lewis acids and bases, Methyl methacrylate, Phosphine
Abstract: International audience; Fully organic Lewis pairs, combining a phosphine such as tri-n-butylphosphine (PnBu3), tritert-butylphosphine (PtBu3) or tris(2,4,6-trimethoxyphenyl) phosphine (TTMPP) as a Lewis base, and N-(trimethylsilyl)bis(trifluoromethane sulfonyl)imide (Me3SiNTf2) as a Lewis acid, are shown to directly initiate the polymerization of methyl methacrylate (MMA) at room temperature in toluene. A dual reaction mechanism involving an optimal TTMPP:Me3SiNTf2 ratio of 1:2 accounts for the control of the polymerization. Molar masses of poly(methyl methacrylate)’s (PMMA’s) can be varied by the initial [MMA]0/[TTMPP]0 molar ratio. Chain extension experiments confirm that a majority of chains of a TTMPP/Me3SiNTf2-derived PMMA can be reactivated. Both density functional theory (DFT) calculations and stoichiometric studies reveal that TTMPP and Me3SiNTf2 form a P-silyl phosphonium intermediate that is in equilibrium with the corresponding frustrated Lewis pair (FLP). This FLP could correspond to the active form of the initiation step. Both computational and experimental data support the existence of a cooperative mechanism during the TTMPP/Me3SiNTf2 Lewis pair-mediated polymerization of MMA.
Published: 2017

40. One-Pot Synthesis and PEGylation of Hyperbranched Polyacetals with a Degree of Branching of 100%

Author: Na Liu, Frédéric Robert, Jean-Marc Vincent, Henri Cramail, Daniel Taton, Joan Vignolle, Yannick Landais, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), and Team 2 LCPO : Biopolymers & Bio-sourced Polymers
Subjects: COPOLYMER MICELLES, Polymers and Plastics, STAR POLYMERS, One-pot synthesis, Branching (polymer chemistry), Aldehyde, Inorganic Chemistry, CONTROLLED DRUG-DELIVERY, chemistry.chemical_compound, POLYGLYCEROLS, DESIGN, Polymer chemistry, NANOPARTICLES, Materials Chemistry, Organic chemistry, DENDRIMERS, DIETHYLSTILBESTROL, RELEASE, chemistry.chemical_classification, Chemistry, Organic Chemistry, Acetal, DEGRADATION, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, Hemiacetal, Pyridinium, Brønsted–Lowry acid–base theory
Abstract: International audience; The Bronsted acid-catalyzed polytransacetalization of hydroxymethylbenzaldehyde dimethylacetal (1), a commercially available AB(2)-type monomer, led to hyperbranched polyacetals (HBPA's) with a degree of branching (DB) around 0.5 by forming methanol as byproduct. In sharp contrast, the polyacetalization of the nonprotected homologue, namely, hydroxymethylbenzaldehyde (2), yielded HBPA's with DB = 1, by forming water as byproduct, under the same acidic conditions. This major difference arises from the instability of the initially formed hemiacetal intermediates, which react faster than aldehyde moieties, driving the polyacetalization toward the quantitative formation of dendritic acetal units. This represents a rare example of defect-free hyperbranched polymer synthesis utilizing a very simple AB(2)-type monomer. Bronsted acid catalysts included p-toluenesulfonic, camphorsulfonic, and pyridinium camphorsulfonic acids. Trapping of the water generated during polyacetalization of 2 was accomplished using molecular sieves regularly renewed, which allowed achieving polymers of relatively high molar masses. These HBPA's with DB = 1 featuring multiple aldehyde functions at their periphery were further derivatized into PEGylated HBPA's, using linear amino-terminated poly(ethylene oxide)s of different molar masses. This led to submicrometric sized HBPA's with a core shell architecture. Finally, HBPA derivatives could be readily hydrolyzed under acidic conditions (e.g., pH = 4), owing to the acid sensitivity of their constitutive acetal linkages.
Published: 2014

41. Catalytically Active N -Heterocyclic Carbene Release from Single-Chain Nanoparticles Following a Thermolysis-Driven Unfolding Strategy

Author: Sofiem Garmendia, Stefan B. Lawrenson, Maria C. Arno, Rachel K. O'Reilly, Daniel Taton, and Andrew P. Dove
Subjects: Polymers and Plastics, Organic Chemistry, Materials Chemistry
Published: 2019

42. Imidazolium-Based Poly(Ionic Liquid)s Featuring Acetate Counter Anions: Thermally Latent and Recyclable Precursors of Polymer-Supported N-Heterocyclic Carbenes for Organocatalysis

Author: Anne-Laure Wirotius, Romain Lambert, Paul Coupillaud, Joan Vignolle, Daniel Taton, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Anions, Polymers and Plastics, Polymers, NHCS, poly(ionic liquid)s, CATALYSTS, 02 engineering and technology, Acetates, 010402 general chemistry, 01 natural sciences, HYDROGEN CARBONATES, Catalysis, chemistry.chemical_compound, CARBON-DIOXIDE, Deprotonation, ADDUCTS, Heterocyclic Compounds, Polymer chemistry, Materials Chemistry, Organic chemistry, organocatalysis, N-heterocyclic carbenes, Benzoin condensation, Methyl acrylate, Tetrahydrofuran, Molecular Structure, Chemistry, Organic Chemistry, Imidazoles, Temperature, PRECATALYSTS, imidazolium, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, IONIC LIQUIDS, Reagent, Organocatalysis, Ionic liquid, METAL-COMPLEXES, 0210 nano-technology, Methane
Abstract: International audience; Statistical copoly(ionic liquid)s (coPILs), namely, poly(styrene)-co-poly(4-vinylbenzylethylimidazolium acetate) are synthesized by free-radical copolymerization in methanolic solution. These coPILs serve to in situ generate polymer-supported N-heterocyclic carbenes (NHCs), referred to as polyNHCs, due to the noninnocent role of the weakly basic acetate counteranion interacting with the proton in C2-position of pendant imidazolium rings. Formation of polyNHCs is first evidenced through the quantitative formation of NHC-CS2 units by chemical postmodification of acetate-containing coPILs, in the presence of CS 2 as electrophilic reagent (= stoichiometric functionalization of polyNHCs). The same coPILs are also employed as masked precursors of polyNHCs in organocatalyzed reactions, including a one-pot two-step sequential reaction involving benzoin condensation followed by addition of methyl acrylate, cyanosilylation, and transesterification reactions. The catalytic activity can be switched on and off successively upon thermal activation, thanks to the deprotonation/ reprotonation equilibrium in C2-position. NHC species are thus in situ released upon heating at 80 degrees C (deprotonation), while regeneration of the coPIL precursor occurs at room temperature (reprotonation), triggering its precipitation in tetrahydrofuran. This also allows recycling the coPIL precatalyst by simple filtration, and reusing it for further catalytic cycles. The different organocatalyzed reactions tested can thus be performed with excellent yields after several cycles.
Published: 2016

43. One-Pot Synthesis of Double Poly(Ionic Liquid) Block Copolymers by Cobalt-Mediated Radical Polymerization-Induced Self-Assembly (CMRPISA) in Water

Author: Zdravko Kochovski, Christophe Detrembleur, Christine Jérôme, Daniela Cordella, Daniel Taton, Antoine Debuigne, Univ Liege, Dept Chem, CERM, Université de Liège-CERM, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH (Helmholtz-Zentrum Berlin), Helmholtz-Zentrum Berlin, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: C (Detrembleur, Polymers and Plastics, Polymers, using an alkyl bis(acetylacetonate) cobalt(III) adduct as initiator and controlling agent. The as-obtained hydrophilic poly(N-vinyl-3ethyl imidazolium bromide) (PVEtImBr) is then used as a macroinitiator for the CMR-PISA of N-vinyl-3-octyl imidazolium bromide (VOcImBr). Self-assembly of the amphiphilic PVEtImBr-b-PVOcImBr block copolymer, 02 engineering and technology, cobalt-mediated radical polymerization, vinyl imidazolium, MONOMERS, Detrembleur, 01 natural sciences, Polymerization, chemistry.chemical_compound, Bromide, C (Jerome, ROUTE, Materials Chemistry, Copolymer, Jerome, POLYELECTROLYTE-STABILIZED NANOPARTICLES, Daniel)[ 3 ], Debuigne, Molecular Structure, RAFT POLYMERIZATION, Cobalt, 021001 nanoscience & nanotechnology, D (Cordella, block copolymers, Chemistry, Z (Kochovski, D (Taton, SEPARATION, Daniela)[ 1 ], Christine)[ 1 ], 0210 nano-technology, A (Debuigne, Materials science, Free Radicals, Radical polymerization, poly(ionic liquid)s, Taton, 010402 general chemistry, Antoine)[ 1 ], VESICLES, NANO-OBJECTS, i.e, Amphiphile, Polymer chemistry, AQUEOUS DISPERSION POLYMERIZATION, Reversible addition−fragmentation chain-transfer polymerization, Zdravko)[ 2 ], forming polymer nanoparticles consisting of a hydrophilic PVEtImBr corona and a hydrophobic PVOcImBr core. Preliminary investigation into the effect of the size of the hydrophobic block on the dimension of the nanoparticles is also described. Keywords Author Keywords:block copolymers, Organic Chemistry, technology, industry, and agriculture, Water, induced self assembly, Kochovski, rapidly takes place in water, 0104 chemical sciences, of PIL-b-PIL-type, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Cobalt-mediated radical polymerization, IONIC LIQUIDS, Ionic liquid, Christophe)[ 1 ] MACROMOLECULAR RAPID COMMUNICATIONS Volume: 37 Issue: 14 Pages: 1181-1187 Special Issue: SI DOI: 10.1002/marc.201600039 Published: JUL 2016 View Journal Information Abstract Amphiphilic double poly(ionic liquid) (PIL) block copolymers are directly prepared by cobaltmediated radical polymerization induced self-assembly (CMR-PISA) in water of N-vinyl imidazolium monomers carrying distinct alkyl chains. The cobalt-mediated radical polymerization of N-vinyl-3-ethyl imidazolium bromide (VEtImBr) is first carried out until high conversion in water at 30 degrees C, One-Pot Synthesis of Double Poly(Ionic Liquid) Block Copolymers by Cobalt-Mediated Radical Polymerization-Induced Self-Assembly (CMRPISA) in Water By:Cordella
Abstract: International audience; Amphiphilic double poly(ionic liquid) (PIL) block copolymers are directly prepared by cobaltmediated radical polymerization induced self-assembly (CMR-PISA) in water of N-vinyl imidazolium monomers carrying distinct alkyl chains. The cobalt-mediated radical polymerization of N-vinyl-3-ethyl imidazolium bromide (VEtImBr) is first carried out until high conversion in water at 30 degrees C, using an alkyl bis(acetylacetonate) cobalt(III) adduct as initiator and controlling agent. The as-obtained hydrophilic poly(N-vinyl-3ethyl imidazolium bromide) (PVEtImBr) is then used as a macroinitiator for the CMR-PISA of N-vinyl-3-octyl imidazolium bromide (VOcImBr). Self-assembly of the amphiphilic PVEtImBr-b-PVOcImBr block copolymer, i.e., of PIL-b-PIL-type, rapidly takes place in water, forming polymer nanoparticles consisting of a hydrophilic PVEtImBr corona and a hydrophobic PVOcImBr core. Preliminary investigation into the effect of the size of the hydrophobic block on the dimension of the nanoparticles is also described.
Published: 2016

44. Update and challenges in organo-mediated polymerization reactions

Author: Winnie Nzahou Ottou, Daniel Taton, Joan Vignolle, Haritz Sardon, David Mecerreyes, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institute for Polymer Materials (POLYMAT), Universidad del Pais Vasco / Euskal Herriko Unibertsitatea [Espagne] (UPV/EHU), Team 1 LCPO : Polymerization Catalyses & Engineering, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The research leading to these results has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement no. 642671, project 'SUSPOL-EJD'., ANR-11-BS08-0011,CATAPULT,POLYMERISATIONS ORGANOCATALYSEES PAR LES CARBENES : VERS UNE PLATEFORME CATALYTIQUE MULTI-TACHE(2011), European Project: 642671,H2020,H2020-MSCA-ITN-2014,SUSPOL(2015), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Direct initiation, Polymers and Plastics, Ring-opening polymerization, Bifunctional activation, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Step-growth polymerization, chemistry.chemical_compound, Materials Chemistry, Organic chemistry, Reversible addition−fragmentation chain-transfer polymerization, Lewis acids and bases, Group transfer polymerization, Organic catalyst, Chemistry, Basic catalysis, Organic Chemistry, Cationic polymerization, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Acid catalysis, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, Organocatalysis, Ceramics and Composites, 0210 nano-technology
Abstract: International audience; Organocatalysis has become a very powerful tool for precision macromolecular chemistry, as judged by the number of articles published in this field in the past decade. A variety of small organic molecules, including Bronsted/Lewis bases and acids, based on amines, phosphines or carbenes, but also on bi-component systems, have been employed as a means to catalyze the polymerization of miscellaneous monomers. Not only can organocatalysts be employed to promote the ring-opening polymerization of various heterocyclics (e.g. lactones, lactide, cyclic carbonates, epoxides, lactams, cyclocarbosiloxanes), but some of them also allow activating vinylic monomers such as (meth)acrylics, or triggering the step growth polymerization of monomers such as diisocyanates and diols for polyurethane synthesis. The reduced toxicity of organocatalysts in comparison to their metallic counterparts is also driving their development in some sensitive applications, such as biomedical or microelectronics. Overall, organocatalysts display specific monomer activation modes, thereby providing a unique opportunity to control the polymerization of various functional monomers, under mild conditions. This review article focuses on advances of the past 4 years (>150 publications) in polymerization reactions utilizing small organic molecules either as direct initiators or as true catalysts, with a special emphasis on monomer activation modes, as well as polymerization mechanism aspects.
Published: 2016

45. Poly(N-heterocyclic-carbene)s and their CO2 Adducts as Recyclable Polymer-Supported Organocatalysts for Benzoin Condensation and Transesterification Reactions

Author: Daniel Taton, Yves Gnanou, Joan Vignolle, Julien Pinaud, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Polymers and Plastics, 010402 general chemistry, 01 natural sciences, Ring-opening polymerization, LIVING POLYMERIZATION, Inorganic Chemistry, OLEFIN METATHESIS, chemistry.chemical_compound, Deprotonation, Bromide, PYRIDINE OLIGOMERS, N-HETEROCYCLIC CARBENES, Polymer chemistry, Materials Chemistry, Organic chemistry, CATALYTIC-ACTIVITY, Benzoin condensation, Imide, POLY(ETHYLENE OXIDE)S, 010405 organic chemistry, Organic Chemistry, ORGANOMETALLIC CATALYSIS, 0104 chemical sciences, RING-OPENING POLYMERIZATION, BLOCK-COPOLYMERS, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, IONIC LIQUIDS, Organocatalysis, Ionic liquid, Carbene
Abstract: International audience; The synthesis of poly(N-heterocyclic carbene)s, denoted poly-(NHC)s, and of their poly(NHC-CO(2)) adducts for a use in organocatalysis is described. Poly(NHC)s were readily obtained in a three-step sequence of reactions, involving i) the free-radical polymerization of ionic liquid monomers, that is, 1-vinyl-3-alkylimidazolium-type monomers with bromide (Br(-)) as counteranion, followed by ii) anion exchange of Br(-) for bis(trifluoromethanesulfonyl)imide ((-)NTf2), of the poly(1-vinyl-3-alkylimidazolium bromide) precursors, affording poly(1-vinyl-3-alkylimidazolium bis(trifluorornethanesulfonyl)imide) derivatives, and iii) deprotonation of the latter polymeric ionic liquids with a strong base. Carbon dioxide (CO(2)) was found to reversibly react with poly(NHC)s forming relatively air-stable and thermolabile poly(NHC-CO(2)) adducts. Both poly(NHC)s and their poly(NHC-CO(2)) adducts were used as polymer-supported organic catalysts and precatalysts, respectively, in transesterification and benzoin condensation reactions under homogeneous conditions. Both types of polymer-supported NHCs were recycled and used several times, but the manipulation of poly(NHC)s like their molecular NHC analogues-was more complicated owing to their air and moisture sensitivity. In this regard, zwitterionic poly(NHC-CO(2)) adducts like their molecular NHC-CO(2) analogues could be easier manipulated than their bare poly(NHC) counterparts, providing good to excellent yields even after several organocatalytic cycles, in particular toward the transesterification reaction.
Published: 2011

46. pH and Temperature Responsive Polymeric Micelles and Polymersomes by Self-Assembly of Poly[2-(dimethylamino)ethyl methacrylate]-b-Poly(glutamic acid) Double Hydrophilic Block Copolymers

Author: Daniel Taton, Willy Agut, Christophe Schatz, Annie Brûlet, Sébastien Lecommandoux, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Team 3 LCPO : Polymer Self-Assembly & Life Sciences, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), and Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: CROSS-LINKING, Polymers, Glutamic Acid, 02 engineering and technology, 010402 general chemistry, Methacrylate, 01 natural sciences, Micelle, Lower critical solution temperature, GENE DELIVERY, Microscopy, Electron, Transmission, AQUEOUS-SOLUTIONS, Polymer chemistry, Electrochemistry, Copolymer, Nanotechnology, Scattering, Radiation, General Materials Science, POLY(2-VINYLPYRIDINIUM)-BLOCK-POLY(ETHYLENE OXIDE), DRUG-DELIVERY, Micelles, Spectroscopy, Aqueous solution, Chemistry, Temperature, POLYPEPTIDE DIBLOCK COPOLYMERS, COACERVATE CORE MICELLES, Surfaces and Interfaces, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Nanostructures, 0104 chemical sciences, Nylons, [CHIM.POLY]Chemical Sciences/Polymers, Isoelectric point, NEUTRON-SCATTERING, Polymersome, Methacrylates, CLICK CHEMISTRY, Self-assembly, 0210 nano-technology, POLYION COMPLEX MICELLES
Abstract: International audience; The aqueous solution behavior of novel polypeptide-based double hydrophilic block copolymers (DHBCs), namely, poly[2-(dimethylamino)ethyl methacrylate]-b-poly(glutamic acid) (PDMAEMA-b-PGA), exhibiting pH- and temperature-responsiveness is presented using a combination of scattering techniques (light and neutron) and transmission electron microscopy. Close to the isoelectric point (IEP), direct or inverse electrostatic polymersomes are generated by electrostatic interactions developing between the two charged blocks and driving the formation of the hydrophobic membrane of the polymersomes, with the latter being stabilized in water by uncompensated charges. Under basic conditions, that is, when PDMAEMA is uncharged, the thermosensitivity of the DHBCs relates to the lower critical solution temperature (LCST) behavior of PDMAEMA around 40 degrees C. As a consequence, at pH = 11 and below this LCST, free chains of DHBC unimers are evidenced, while above the LCST the hydrophobicity of PDMAEMA drives the self-assembly of the DHBCs in a reversible manner. In this case, spherical polymeric micelles or polymersomes are obtained, depending on the PGA block length. These possibilities of variation in size and shape of morphologies that can be achieved as a function of temperature and/or pH variations open new routes in the development of multiresponsive nanocarriers for biomedical applications.
Published: 2010

47. N-Heterocyclic Carbene-Organocatalyzed Ring-Opening Polymerization of Ethylene Oxide in the Presence of Alcohols or Trimethylsilyl Nucleophiles as Chain Moderators for the Synthesis of α,ω-Heterodifunctionalized Poly(ethylene oxide)s

Author: Jean Raynaud, Yves Gnanou, Christelle Absalon, Daniel Taton, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Polymers and Plastics, Trimethylsilyl, FACILE SYNTHESIS, INTRAMOLECULAR STETTER REACTION, 010402 general chemistry, MATERIALS SCIENCE, 01 natural sciences, Ring-opening polymerization, 3-DIPOLAR CYCLOADDITIONS, Inorganic Chemistry, chemistry.chemical_compound, Nucleophile, Polymer chemistry, Materials Chemistry, CATALYTIC-ACTIVITY, GLYCOL) DERIVATIVES, Telechelic polymer, Ethylene oxide, 010405 organic chemistry, Organic Chemistry, CARBONYL-COMPOUNDS, Solution polymerization, ONE END, 0104 chemical sciences, BLOCK-COPOLYMERS, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, CLICK CHEMISTRY, Carbene
Abstract: International audience; The present study describes innovations in the ring-opening polymerization (ROP) of ethylene oxide (EO) using N-heterocyclic carbenes (NHCs) as organocatalysts, which enables the synthesis of alpha,omega-heterodifunctionalized poly(ethylene oxide)s (PEOs). Two representative NHC catalysts, namely, 1,3-bis(diisopropyl)imidazol-2-ylidene (1) and 1,3-bis(di-tert-butyl)imidazol-2-ylidene (2), were efficiently employed in conjunction with a variety of chain regulators of general structure NuE, where Nu and E are the nucleophilic and the electrophilic part, respectively, with E = H or SiMe3 (e.g., PhCH2OH, HC CCH2OH, N3SiMe3, and PhCH2OSiMe3). Catalytic amounts of the NHC (typically [NHC]/[NuE]/[EO] = 0.1/1/100 in moles) were indeed utilized to trigger the metal-free ROP of EO at 50 C in dimethyl sulfoxide, allowing the polymerization to proceed to completion. In this way, PEOs of dispersities lower than 1.2 and molar masses perfectly matching the [EO]/[NuE] ratio were obtained, attesting to the controlled/living character of these NHC-catalyzed polymerizations. Characterization of alpha,omega-difunetionalized PEOs by combined techniques such as H-1 NMR spectroscopy, MALDI-TOF mass spectrometry, and size exclusion chromatography confirmed the quantitative introduction of the nucleophilic moiety (Nu) and its electrophilic component (E = H Or SiMe3) in the alpha- and omega-position of the PEO chains, respectively, and the formation of polymers with narrowly distributed molar masses. These results are discussed in the light of the existence of two possible mechanisms. The first one involves a direct attack of the NHC catalyst onto EO and the formation of a zwitterionic intermediate (activated monomer mechanism). The second possibility is the activation by the NHC of the E moiety of the NuE chain regulator first and then of the alpha-Nu,omega-OE PEO chain (activated chain end mechanism).
Published: 2010

48. Micelles and Polymersomes Obtained by Self-Assembly of Dextran and Polystyrene Based Block Copolymers

Author: Daniel Taton, Joanna Giermanska, Sébastien Lecommandoux, Redouane Borsali, Jean-François Le Meins, Yves Gnanou, Clément Houga, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Centre de recherches Paul Pascal (CRPP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Team 3 LCPO : Polymer Self-Assembly & Life Sciences, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Centre de Recherches sur les Macromolécules Végétales (CERMAV), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF), Université Joseph Fourier - Grenoble 1 (UJF), Team 1 LCPO : Polymerization Catalyses & Engineering, inconnu, and Inconnu
Subjects: Polymers and Plastics, Surface Properties, micelles, Bioengineering, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Micelle, Biomaterials, chemistry.chemical_compound, Polymer chemistry, Materials Chemistry, Copolymer, Dimethyl Sulfoxide, Particle Size, Furans, Dissolution, ComputingMilieux_MISCELLANEOUS, vesicles, Molar mass, Water, Dextrans, self-assembly, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Molecular Weight, Solutions, block copolymers, [CHIM.POLY]Chemical Sciences/Polymers, Dextran, chemistry, dextran, polysaccharide, Polymersome, Nanoparticles, Polystyrenes, Polystyrene, Self-assembly, 0210 nano-technology, Hydrophobic and Hydrophilic Interactions
Abstract: International audience; The self-assembly of dextran-block-polystyrene (dex-b-PS) block copolymers was investigated in solution. The hydrophobic PS weight fraction in these block copolymers ranges from 7 to 92% w/w, whereas the average number molar mass of dextran was kept constant at 6600 gmol(-1). Self-assembly by direct dissolution in water could be performed only for block copolymers with a low hydrophobic content (7% w/w), whereas mixtures of tetrahydrofuran and dimethylsulfoxide were required for higher PS content, before transferring the structures into water. Core-shell micelles, ovoids, and vesicles could be identified upon characterization by light and neutrons scattering, atomic force microscopy, and transmission electron microscopy. Most of the morphologies observed were not expected considering the chemical composition of the block copolymers. Finally, the size and shape of these nanoparticles were fixed upon cross-linking the dextran block through reaction of the hydroxyl groups with divinylsulfone. The role of the dextran conformation on the self-assembly process is discussed.
Published: 2008

49. Synthesis by RAFT and Ionic Responsiveness of Double Hydrophilic Block Copolymers Based on Ionic Liquid Monomer Units

Author: David Mecerreyes, Yves Gnanou, Alaitz Ruiz, Kari Vijayakrishna, Daniel Taton, Suresh K. Jewrajka, Rebeca Marcilla, José A. Pomposo, Laboratoire de Chimie des polymères organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Institut de Chimie du CNRS (INC), Centre for Electrochemical Technologies, New Materials Dept (CIDETEC), CIDETEC, Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: Polymers and Plastics, micelles, Radical polymerization, 02 engineering and technology, Ionic liquid, 010402 general chemistry, Methacrylate, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Bromide, anion exchange, Polymer chemistry, Materials Chemistry, Copolymer, Organic Chemistry, Chain transfer, self-assembly, 021001 nanoscience & nanotechnology, Polyelectrolyte, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Methacrylic acid, double hydrophilic block copolymers, 0210 nano-technology, RAFT
Abstract: International audience; Three imidazolium-based ionic liquid (IL) monomers, namely, 3-(1-ethyl imidazolium-3-yl)propylmethacrylamido bromide (IL-1), 2-(1-methylimidazolium-3-yl)ethyl methacrylate bromide (IL-2), and 2-(1-ethylimidazolium-3-yl)ethyl methacrylate bromide (IL-3), and methacrylic acid (MAA) were polymerized by the reversible addition fragmentation chain transfer (RAFT) process in methanolic solutions at 70 °C, using either 2-cyanopropyl dithiobenzoate (CTA-1) or (4-cyanopentanoic acid)-4-dithiobenzoate (CTA-2) as chain transfer agents (CTAs). Under these conditions, polymers exhibited molar masses predetermined by the initial molar ratio of the monomers to the dithioester precursor, as evidenced by 1H NMR spectroscopy from chain ends analysis. These hydrophilic polymers were subsequently used as macro-CTAs in chain extension experiments in aqueous or in alcoholic solutions, affording IL-based double hydrophilic block copolymers (DHBCs) of the type PIL-1-b-PAm, PMAA-b-PIL-2 and PMAA-b-PIL-3, where PAm and PIL stand for polyacrylamide and polymeric ionic liquid. These DHBCs could be further manipulated and made to self-assemble in micelle-like structures in water by exchanging the bromide (Br−) counteranion of IL blocks for −N(SO2CF3)2. This anion exchange indeed turned the solution properties of the PIL blocks from hydrophilic to hydrophobic, as verified on the corresponding IL-based homopolymers which were immiscible with water after the anion switch. Investigations by 1H NMR evidenced that the diblock copolymers exhibited salt-responsive behavior in aqueous solutions: anion exchange induced the formation of water-soluble micellar aggregates consisting of hydrophobic − N(SO2CF3)2-based IL blocks at the core stabilized by water-soluble PAm or PMAA at the shell.
Published: 2008

50. Harnessing the Potential of N‐Heterocyclic Carbenes for the Rejuvenation of Group‐Transfer Polymerization of (Meth)Acrylics

Author: Jean Raynaud, Tsuyoshi Kato, Mathias Destarac, Yves Gnanou, Fabien Bonnette, Antoine Baceiredo, Daniel Taton, Andrés Eduardo Ciolino, Laboratoire de Chimie des polymères organiques (LCPO), Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Planta Piloto de Ingeniería Química [Bahía Blanca] (PLAPIQUI), Universidad Nacional del Sur [Argentina] (UNS)-Consejo Nacional de Investigaciones Científicas y Técnicas [Buenos Aires] (CONICET), Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
Subjects: 010402 general chemistry, 01 natural sciences, 7. Clean energy, Catalysis, Polymerization, chemistry.chemical_compound, Group (periodic table), Polymer chemistry, Organic chemistry, organocatalysis, ComputingMilieux_MISCELLANEOUS, Block Copolymers, Organocatalysis, 010405 organic chemistry, Otras Ciencias Químicas, Transition metal carbene complex, Ciencias Químicas, General Chemistry, Meth, General Medicine, 0104 chemical sciences, carbenes, block copolymers, Transfer (group theory), [CHIM.POLY]Chemical Sciences/Polymers, chemistry, polymerization, Carbenes, CIENCIAS NATURALES Y EXACTAS
Abstract: (Chemical Equation Presented) Neutral but versatile: N-heterocyclic carbenes are very efficient catalysts for the group-transfer polymerization of acrylates and methacrylates in both polar and apolar media. These organocatalysts were also used to design all-(meth)acrylic di-and triblock copolymers. Fil: Raynaud, Jean. Universite de Bordeaux; Francia. Centre National de la Recherche Scientifique; Francia Fil: Ciolino, Andrés Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina Fil: Baceiredo, Antoine. Université Paul Sabatier; Francia Fil: Destarac, Mathias. Université Paul Sabatier; Francia Fil: Bonnette, Fabien. Université Paul Sabatier; Francia Fil: Kato, Tsuyoshi. Université Paul Sabatier; Francia Fil: Gnanou, Yves. Universite de Bordeaux; Francia Fil: Taton, Daniel. Universite de Bordeaux; Francia
Published: 2008

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