Daniel Taton - Academia.edu (original) (raw)

Papers by Daniel Taton

This invention relates to a method for preparing copolymers of star-shaped having at least two ty... more This invention relates to a method for preparing copolymers of star-shaped having at least two types of polymeric arms of different chemical nature, said method comprising radical polymerization of step a composition comprising: - at least one monomer crosslinker, - a source of free radicals, and- at least two (co) first generation of polymers of different chemical nature and molecular weight possibly differente.Elle also relates to star copolymers may be prepared by this process and their uses .

Langmuir, Jun 29, 2005

Star diblock copolymers containing polystyrene (PS) and poly(ethylene oxide) (PEO) were investiga... more Star diblock copolymers containing polystyrene (PS) and poly(ethylene oxide) (PEO) were investigated as surface films at the air/water interface. Both classic and dendritic-like stars were prepared containing either a PS core and PEO corona or the reverse. The investigated polymers, consisting of systematic variations in architectures and compositions, were spread at the air/water interface, generating reproducible surface pressure-area isotherms. All of the films could be compressed to higher pressures than would be possible for pure PEO. For stars containing 20% or more PEO, three distinct regions appeared. At higher areas, the PEO absorbs in pancakelike structures at the interface with PS globules sitting atop. Upon compression, a pseudoplateau transition region appeared. Both regions strongly depended on PEO composition. The pancake area and the pseudoplateau width and pressure increased in a linear fashion with an increasing amount of PEO. In addition, minimum limits of PEO chain length and mass percentage were determined for observing a pseudoplateau. At small areas, the film proved less compressible, producing a rigid film in which PS dominated. Here, the film area increased with both molecular weight and the amount of PS. Comparison with pure linear PS showed the stars spread more, occupying greater areas. Among the stars, the PEO-core stars were more compact while the PS-core stars spread more. The influence of architecture in terms of the core/corona polymers and branching were also examined. The effects of architecture were subtle, proving less important than PEO chain length or mass percentage.

Polymer Chemistry, 2022

We report the synthesis of redox-and pH-sensitive block copolymer micelles that contain chiral co... more 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 stimuliresponsiveness 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.

Angewandte Chemie, Jul 17, 2023

Polymerization‐induced self‐assembly (PISA) enables the synthesis at large scale of a wide variet... more Polymerization‐induced self‐assembly (PISA) enables the synthesis at large scale of a wide variety of functional nanoparticles. However, a large number of works are related to controlled radical polymerization (CRP) methods and are generally undertaken at elevated temperatures (>50 °C). Here is the first report on methacrylate‐based nanoparticles fabricated by group transfer polymerization‐induced self‐assembly (GTPISA) in non‐polar media (n‐heptane). This GTPISA process is achieved at room temperature (RT) using 1‐methoxy‐1‐(trimethylsiloxy)‐2‐methylprop‐1‐ene (MTS) and tetrabutylammonium bis‐benzoate (TBABB) as initiator and organic catalyst, respectively. Under these conditions, well‐defined metal‐free and colorless diblock copolymers are produced with efficient crossover from the non‐polar stabilizing poly(lauryl methacrylate) (PLMA) block to the non‐soluble poly(benzyl methacrylate) (PBzMA) segment. The resulting PLMA‐b‐PBzMA block copolymers simultaneously self‐assemble into nanostructures of various sizes and morphologies. GTPISA in non‐polar solvent proceeds rapidly at RT and avoids the use of sulfur or halogenated compounds or metallic catalysts associated with the implementation of CRP methods, thus expanding the potential of PISA formulations for applications in non‐polar environments.

HAL (Le Centre pour la Communication Scientifique Directe), 2008

New micelle-like organic supports for single site catalysts based on the self-assembly of polysty... more New micelle-like organic supports for single site catalysts based on the self-assembly of polystyrene-b-poly(4-vinylbenzoic acid) block copolymers have been designed. These block copolymers were synthesized by sequential atom transfer radical polymerization (ATRP) of styrene and methyl 4-vinylbenzoate, followed by hydrolysis. As evidenced by dynamic light scattering, self-assembly in toluene that is a selective solvent of polystyrene, induced the formation of micelle-like nanoparticles composed of a poly(4-vinylbenzoic acid) core and a polystyrene corona. Further addition of trimethylaluminium (TMA) afforded in situ MAO-like species by diffusion of TMA into the core of the micelles and its subsequent reaction with the benzoic acid groups. Such reactive micelles then served as nanoreactors, MAO-like species being efficient activators of 2,6-bis[1-{(2,6-diisopropylphenyl)imino}ethyl]pyridinyl iron toward ethylene polymerization. These new micelle-like organic supports enabled the production of polyethylene beads with a spherical morphology and a high bulk density through homogeneous-like catalysis. V

HAL (Le Centre pour la Communication Scientifique Directe), Apr 8, 2008

Springer eBooks, 2015

Poly(ionic liquid)s (PILs) have been recently introduced into block copolymer (BCP) architectures... more Poly(ionic liquid)s (PILs) have been recently introduced into block copolymer (BCP) architectures to combine the specific properties of PILs, such as responsiveness to ion exchange, ionic conductivity, and/or gas transport, with the self-assembling properties of BCPs, enabling the access to a wide range of robust nanostructured morphologies, either in solution or at the solid state. This chapter describes synthetic strategies to such PIL BCPs utilizing “controlled/living” polymerization methods and/or post-chemical modification of preformed copolymers, as well as their self-assembling properties in a selective solvent and in bulk. Potential applications of this emerging class of materials, for instance, in energy conversion devices or in gas separation membranes, are also briefly presented.

Macromolecules, Aug 21, 1998

A C60 derivatized triarm poly(ethylene oxide) copolymer was synthesized and characterized. The so... more A C60 derivatized triarm poly(ethylene oxide) copolymer was synthesized and characterized. The soluble polymer produced spread at aqueous interfaces to form highly expanded fluid Langmuir monolayers. The onset area of 1300 A2/arm is likely due to the polymer disrupting cohesion between C60 units. Compression/expansion studies revealed a significant elastic region, beyond which the C60 units condensed, and a compact rigid and irreversible monolayer formed.

Macromolecules, Jan 30, 2003

Mixtures of poly(ethylene oxide) (PEO) end-capped on one or both ends with hexadecyl, but with th... more Mixtures of poly(ethylene oxide) (PEO) end-capped on one or both ends with hexadecyl, but with the same hydrophilic-lypophilic balance, were studied using static and dynamic light scattering and dynamic mechanical measurements. In aqueous solution the mixtures form polymeric micelles with aggregation numbers that are independent of the fraction of difunctionalized PEO. Difunctionalized PEO bridges between two micelles, which leads to reversible association of the micelles. The phase behavior and the association of the micelles can be described by modeling the micelles as adhesive spheres with an adhesion parameter that depends on the fraction of difunctionalized PEO and the temperature. Above a given concentration the micelles percolate, leading to a strong increase of the viscosity and the highfrequency shear modulus. The viscosity has an Arrhenius temperature dependence with an activation energy close to that of the relaxation time that characterizes the decay of the shear modulus. At even higher concentrations an abrupt transition is observed that is characterized by the appearance of a second relaxation process with a very long relaxation time. The transition can be induced by small increases of the temperature or the concentration. The slow relaxation is attributed to restructuring of a solution of close packed micelles (e.g., hopping of micelles) while the fast relaxation, which is still visible at high concentrations, is attributed to the breakup of elastic bridges by the escape of end groups from the micelles.

Macromolecules, Sep 26, 1998

2-bromopropionyloxy)calix[8]arene (1) which was readily synthesized in one step, was used to init... more 2-bromopropionyloxy)calix[8]arene (1) which was readily synthesized in one step, was used to initiate the bulk atom transfer radical polymerization (ATRP) of styrene, at 100°C , in the presence of CuBr/2,2′-bipyridyl. Polystyrene (PS) stars of narrow polydispersity with precisely eight arms could be synthesized by restricting the polymerization to low conversion, typically below 15-20%. At higher conversions, irreversible coupling occurred between stars as evidenced by a size exclusion chromatography line equipped with a multiangle laser light scattering detector (MALLS/SEC). Octafunctional stars of molar masses up to 340 000 g mol-1 could be prepared by using high ratios of the monomer to the initiator ([M]/[I]) 12 000). The precise octafunctional structure of the stars was confirmed, on one hand, by studying the kinetics of ATRP of styrene initiated by an equimolar mixture of 1 and its monofunctional equivalent, namely 4-tert-butylphenyl(2-bromopropionate) (2) and, on the other hand, by the characterization of the individual arms obtained upon hydrolysis of the ester link between the core and the branches of the stars.

HAL (Le Centre pour la Communication Scientifique Directe), 2008

Control of the free-radical polymerization of styrene was achieved using a series of eight xantha... more Control of the free-radical polymerization of styrene was achieved using a series of eight xanthates of the general structure R [BOND] S (C [DOUBLE BOND] S) OEt as reversible addition fragmentation chain-transfer agents. The influence of the nature of the R leaving ...

HAL (Le Centre pour la Communication Scientifique Directe), 2009

Nanoscale, 2022

Electronic Supplementary Information (ESI) available: Materials. General procedures. Ru content d... more Electronic Supplementary Information (ESI) available: Materials. General procedures. Ru content determination by TGA. TEM Analysis of Ru nanoparticles. X-ray diffraction (XRD) patterns of Ru NPs. ζ-potentials of Ru NPs. XPS analysis. Catalytic activity. Activity switching of Ru NPs. References. See

Polymer Chemistry, 2021

Herein, we present a straightforward and versatile methodology to achieve functional polymeric na... more Herein, we present a straightforward and versatile methodology to achieve functional polymeric nanoobjects 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. † Electronic supplementary information (ESI) available. See

Macromolecules, Feb 19, 2010

The present study describes innovations in the ring-opening polymerization (ROP) of ethylene oxid... more 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 α,ω-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 char...

Macromolecules, May 1, 2023

HAL (Le Centre pour la Communication Scientifique Directe), May 9, 2018

This invention relates to a method for preparing copolymers of star-shaped having at least two ty... more This invention relates to a method for preparing copolymers of star-shaped having at least two types of polymeric arms of different chemical nature, said method comprising radical polymerization of step a composition comprising: - at least one monomer crosslinker, - a source of free radicals, and- at least two (co) first generation of polymers of different chemical nature and molecular weight possibly differente.Elle also relates to star copolymers may be prepared by this process and their uses .

Langmuir, Jun 29, 2005

Star diblock copolymers containing polystyrene (PS) and poly(ethylene oxide) (PEO) were investiga... more Star diblock copolymers containing polystyrene (PS) and poly(ethylene oxide) (PEO) were investigated as surface films at the air/water interface. Both classic and dendritic-like stars were prepared containing either a PS core and PEO corona or the reverse. The investigated polymers, consisting of systematic variations in architectures and compositions, were spread at the air/water interface, generating reproducible surface pressure-area isotherms. All of the films could be compressed to higher pressures than would be possible for pure PEO. For stars containing 20% or more PEO, three distinct regions appeared. At higher areas, the PEO absorbs in pancakelike structures at the interface with PS globules sitting atop. Upon compression, a pseudoplateau transition region appeared. Both regions strongly depended on PEO composition. The pancake area and the pseudoplateau width and pressure increased in a linear fashion with an increasing amount of PEO. In addition, minimum limits of PEO chain length and mass percentage were determined for observing a pseudoplateau. At small areas, the film proved less compressible, producing a rigid film in which PS dominated. Here, the film area increased with both molecular weight and the amount of PS. Comparison with pure linear PS showed the stars spread more, occupying greater areas. Among the stars, the PEO-core stars were more compact while the PS-core stars spread more. The influence of architecture in terms of the core/corona polymers and branching were also examined. The effects of architecture were subtle, proving less important than PEO chain length or mass percentage.

Polymer Chemistry, 2022

We report the synthesis of redox-and pH-sensitive block copolymer micelles that contain chiral co... more 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 stimuliresponsiveness 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.

Angewandte Chemie, Jul 17, 2023

Polymerization‐induced self‐assembly (PISA) enables the synthesis at large scale of a wide variet... more Polymerization‐induced self‐assembly (PISA) enables the synthesis at large scale of a wide variety of functional nanoparticles. However, a large number of works are related to controlled radical polymerization (CRP) methods and are generally undertaken at elevated temperatures (>50 °C). Here is the first report on methacrylate‐based nanoparticles fabricated by group transfer polymerization‐induced self‐assembly (GTPISA) in non‐polar media (n‐heptane). This GTPISA process is achieved at room temperature (RT) using 1‐methoxy‐1‐(trimethylsiloxy)‐2‐methylprop‐1‐ene (MTS) and tetrabutylammonium bis‐benzoate (TBABB) as initiator and organic catalyst, respectively. Under these conditions, well‐defined metal‐free and colorless diblock copolymers are produced with efficient crossover from the non‐polar stabilizing poly(lauryl methacrylate) (PLMA) block to the non‐soluble poly(benzyl methacrylate) (PBzMA) segment. The resulting PLMA‐b‐PBzMA block copolymers simultaneously self‐assemble into nanostructures of various sizes and morphologies. GTPISA in non‐polar solvent proceeds rapidly at RT and avoids the use of sulfur or halogenated compounds or metallic catalysts associated with the implementation of CRP methods, thus expanding the potential of PISA formulations for applications in non‐polar environments.

HAL (Le Centre pour la Communication Scientifique Directe), 2008

New micelle-like organic supports for single site catalysts based on the self-assembly of polysty... more New micelle-like organic supports for single site catalysts based on the self-assembly of polystyrene-b-poly(4-vinylbenzoic acid) block copolymers have been designed. These block copolymers were synthesized by sequential atom transfer radical polymerization (ATRP) of styrene and methyl 4-vinylbenzoate, followed by hydrolysis. As evidenced by dynamic light scattering, self-assembly in toluene that is a selective solvent of polystyrene, induced the formation of micelle-like nanoparticles composed of a poly(4-vinylbenzoic acid) core and a polystyrene corona. Further addition of trimethylaluminium (TMA) afforded in situ MAO-like species by diffusion of TMA into the core of the micelles and its subsequent reaction with the benzoic acid groups. Such reactive micelles then served as nanoreactors, MAO-like species being efficient activators of 2,6-bis[1-{(2,6-diisopropylphenyl)imino}ethyl]pyridinyl iron toward ethylene polymerization. These new micelle-like organic supports enabled the production of polyethylene beads with a spherical morphology and a high bulk density through homogeneous-like catalysis. V

HAL (Le Centre pour la Communication Scientifique Directe), Apr 8, 2008

Springer eBooks, 2015

Poly(ionic liquid)s (PILs) have been recently introduced into block copolymer (BCP) architectures... more Poly(ionic liquid)s (PILs) have been recently introduced into block copolymer (BCP) architectures to combine the specific properties of PILs, such as responsiveness to ion exchange, ionic conductivity, and/or gas transport, with the self-assembling properties of BCPs, enabling the access to a wide range of robust nanostructured morphologies, either in solution or at the solid state. This chapter describes synthetic strategies to such PIL BCPs utilizing “controlled/living” polymerization methods and/or post-chemical modification of preformed copolymers, as well as their self-assembling properties in a selective solvent and in bulk. Potential applications of this emerging class of materials, for instance, in energy conversion devices or in gas separation membranes, are also briefly presented.

Macromolecules, Aug 21, 1998

A C60 derivatized triarm poly(ethylene oxide) copolymer was synthesized and characterized. The so... more A C60 derivatized triarm poly(ethylene oxide) copolymer was synthesized and characterized. The soluble polymer produced spread at aqueous interfaces to form highly expanded fluid Langmuir monolayers. The onset area of 1300 A2/arm is likely due to the polymer disrupting cohesion between C60 units. Compression/expansion studies revealed a significant elastic region, beyond which the C60 units condensed, and a compact rigid and irreversible monolayer formed.

Macromolecules, Jan 30, 2003

Mixtures of poly(ethylene oxide) (PEO) end-capped on one or both ends with hexadecyl, but with th... more Mixtures of poly(ethylene oxide) (PEO) end-capped on one or both ends with hexadecyl, but with the same hydrophilic-lypophilic balance, were studied using static and dynamic light scattering and dynamic mechanical measurements. In aqueous solution the mixtures form polymeric micelles with aggregation numbers that are independent of the fraction of difunctionalized PEO. Difunctionalized PEO bridges between two micelles, which leads to reversible association of the micelles. The phase behavior and the association of the micelles can be described by modeling the micelles as adhesive spheres with an adhesion parameter that depends on the fraction of difunctionalized PEO and the temperature. Above a given concentration the micelles percolate, leading to a strong increase of the viscosity and the highfrequency shear modulus. The viscosity has an Arrhenius temperature dependence with an activation energy close to that of the relaxation time that characterizes the decay of the shear modulus. At even higher concentrations an abrupt transition is observed that is characterized by the appearance of a second relaxation process with a very long relaxation time. The transition can be induced by small increases of the temperature or the concentration. The slow relaxation is attributed to restructuring of a solution of close packed micelles (e.g., hopping of micelles) while the fast relaxation, which is still visible at high concentrations, is attributed to the breakup of elastic bridges by the escape of end groups from the micelles.

Macromolecules, Sep 26, 1998

2-bromopropionyloxy)calix[8]arene (1) which was readily synthesized in one step, was used to init... more 2-bromopropionyloxy)calix[8]arene (1) which was readily synthesized in one step, was used to initiate the bulk atom transfer radical polymerization (ATRP) of styrene, at 100°C , in the presence of CuBr/2,2′-bipyridyl. Polystyrene (PS) stars of narrow polydispersity with precisely eight arms could be synthesized by restricting the polymerization to low conversion, typically below 15-20%. At higher conversions, irreversible coupling occurred between stars as evidenced by a size exclusion chromatography line equipped with a multiangle laser light scattering detector (MALLS/SEC). Octafunctional stars of molar masses up to 340 000 g mol-1 could be prepared by using high ratios of the monomer to the initiator ([M]/[I]) 12 000). The precise octafunctional structure of the stars was confirmed, on one hand, by studying the kinetics of ATRP of styrene initiated by an equimolar mixture of 1 and its monofunctional equivalent, namely 4-tert-butylphenyl(2-bromopropionate) (2) and, on the other hand, by the characterization of the individual arms obtained upon hydrolysis of the ester link between the core and the branches of the stars.

HAL (Le Centre pour la Communication Scientifique Directe), 2008

Control of the free-radical polymerization of styrene was achieved using a series of eight xantha... more Control of the free-radical polymerization of styrene was achieved using a series of eight xanthates of the general structure R [BOND] S (C [DOUBLE BOND] S) OEt as reversible addition fragmentation chain-transfer agents. The influence of the nature of the R leaving ...

HAL (Le Centre pour la Communication Scientifique Directe), 2009

Nanoscale, 2022

Electronic Supplementary Information (ESI) available: Materials. General procedures. Ru content d... more Electronic Supplementary Information (ESI) available: Materials. General procedures. Ru content determination by TGA. TEM Analysis of Ru nanoparticles. X-ray diffraction (XRD) patterns of Ru NPs. ζ-potentials of Ru NPs. XPS analysis. Catalytic activity. Activity switching of Ru NPs. References. See

Polymer Chemistry, 2021

Herein, we present a straightforward and versatile methodology to achieve functional polymeric na... more Herein, we present a straightforward and versatile methodology to achieve functional polymeric nanoobjects 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. † Electronic supplementary information (ESI) available. See

Macromolecules, Feb 19, 2010

The present study describes innovations in the ring-opening polymerization (ROP) of ethylene oxid... more 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 α,ω-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 char...

Macromolecules, May 1, 2023

HAL (Le Centre pour la Communication Scientifique Directe), May 9, 2018