Pierre-yves Dugas - Academia.edu (original) (raw)
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Papers by Pierre-yves Dugas
Polymer Chemistry
Block copolymers can be obtained by combining catalytic chain transfer polymerization (CCTP) and ... more Block copolymers can be obtained by combining catalytic chain transfer polymerization (CCTP) and conventional free radical emulsion polymerization of ethylene.
ACS catalysis, Feb 1, 2024
Macromolecules, May 26, 2022
Angewandte Chemie, Apr 14, 2020
Poly(ethylene oxide) (PEO) with dithiocarbamate chain ends (PEO-SC(=S)-N(CH3)Ph and PEO-SC(=S)-NP... more Poly(ethylene oxide) (PEO) with dithiocarbamate chain ends (PEO-SC(=S)-N(CH3)Ph and PEO-SC(=S)-NPh2, named PEO-1 and PEO-2, respectively) were used as macromolecular chain transfer agents (macro-CTA) to mediate the reversible additionfragmentation chain transfer (RAFT) polymerization of ethylene in dimethyl carbonate (DMC) under relatively mild conditions (80 °C, 80 bar). While only a slow consumption of PEO-1 was observed, the rapid consumption of PEO-2 led to a clean chain extension and the formation of a polyethylene (PE) segment. Upon polymerization, the resulting block copolymers PEO-b-PE self-assembled into nanometric objects according to a polymerization-induced self-assembly (PISA).
arXiv (Cornell University), Mar 29, 2023
Chemistry – A European Journal
Journal of Controlled Release
Polymer Chemistry, 2020
MgAl-layered double hydroxide (LDH)-armored latexes were produced by Pickering emulsion polymeriz... more MgAl-layered double hydroxide (LDH)-armored latexes were produced by Pickering emulsion polymerization of styrene using 2-hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) as auxiliary comonomers.
Langmuir, 2018
We report an efficient and easy to implement waterborne sol-gel process for the synthesis of nano... more We report an efficient and easy to implement waterborne sol-gel process for the synthesis of nanometric organosilica particles. In this process, tetraethyl orthosilicate (TEOS) and 3-(methacryloxy)propyl trimethoxy silane (-MPS), employed as silica sources, are heterogeneously delivered in an aqueous solution of L-arginine, a basic amino acid used as catalyst, from a top organic layer. Co-condensation of TEOS with γ-MPS led to organosilica particles with diameters comprised between 30 and 230 nm when increasing the -MPS content from 0 to 10.1 mol % in the silica source. Nitrogen sorption analyses confirmed the microporous nature of the obtained particles after calcination. The Brunauer-Emmett-Teller (BET) surface areas increased from 27 (before calcination) to 684 m 2 g-1 (after calcination) for the organosilica particles containing 10.1 mol% of -MPS. Fourier transform infrared (FTIR) spectroscopy and 29 Si nuclear magnetic resonance (NMR) were employed to analyze the chemical structure of the organosilica spheres and provide insight into the mechanism of particle formation. In a second part, hybrid organosilica particles with a core-shell morphology were synthesized through the combination of Pickering emulsion and the sol-gel process. -MPS emulsion droplets stabilized by tiny silica particles (formed in a separate step) 2 were firstly generated, and used as seeds to grow a silica shell on their surface through TEOS addition from the top organic layer. TEM and pore size analyses of the resulting particles after calcination revealed a unique dual-porosity structure with a mesoporous inner core and a micro/mesoporous silica shell with ink-bottle type pores.
Polymer, 2013
ABSTRACT The polymerization-induced self-assembly of amphiphilic block copolymers in water was pe... more ABSTRACT The polymerization-induced self-assembly of amphiphilic block copolymers in water was performed following a reversible addition-fragmentation chain transfer (RAFT) controlled radical polymerization mechanism in emulsion. Poly(methacrylic acid-co-poly(ethylene oxide) methyl ether methacrylate), P(MAA-co-PEOMA), with a trithiocarbonate reactive end-group was selected as the water-soluble living precursor and synthesized in situ via a RAFT aqueous solution polymerization process. The study focused on the polymerization of methyl methacrylate (MMA) at pH 3.5, 5 and 7 and its copolymerization with various proportions of styrene (S) at pH 3.5. In the homopolymerization of MMA, the reaction was well-controlled at pH 3.5, while a low blocking efficiency was observed at higher pH. The systems led to spherical micelles, fibers and then vesicles when the molar mass of the hydrophobic block was increased, irrespective of the pH of the aqueous phase. In the case of the copolymerization with styrene at pH 3.5 and in chain length conditions leading to fibers for the homopolymerization of MMA, the control was very good but the final morphology was that of spherical particles only, at all compositions studied, exactly like in the homopolymerization of styrene performed under similar experimental conditions [Zhang et al. Macromolecules 2011; 44:7584–93]. The results were interpreted on the basis of an influence of the polymerization kinetics, especially in the early stage of the reaction in the aqueous phase.
The emulsion photopolymerization under visible light of acrylate and methacrylate monomers is rep... more The emulsion photopolymerization under visible light of acrylate and methacrylate monomers is reported. We previously introduced an NHC-borane-based system that was efficient for the emulsion photo...
Macromolecules
Silica/polymer latexes with concentric core–shell–corona, half-capped, snowman-like vesicular, ta... more Silica/polymer latexes with concentric core–shell–corona, half-capped, snowman-like vesicular, tadpole- and centipede-like morphologies have been produced by nitroxide-mediated polymerization-induced self-assembly (PISA) performed in the presence of aqueous suspensions of colloidal silica. A hydrosoluble brush-like PEO-based macroalkoxyamine (P[(poly(ethylene oxide) methyl ether methacrylate)12-co-styrene]-SG1, Mn = 11 700 g mol–1 and Mw/Mn = 1.11) was first adsorbed onto the surface of submicronic silica particles. The obtained suspension was then used in the emulsion polymerization of n-butyl methacrylate with 8 mol % of styrene. This led to the formation of amphiphilic block copolymers (BCPs) that self-assembled in situ at the silica surface into well-defined hybrid nano-objects of various morphologies, in agreement with the principles of polymerization-induced micellization. The influence of the pH was more specifically investigated, using silica particles of different size ranging from 30 to 230 nm. ...
Macromolecules
Iron oxide (IO)-based composite latex particles with a patchy IO overlayer were successfully prep... more Iron oxide (IO)-based composite latex particles with a patchy IO overlayer were successfully prepared by Pickering emulsion polymerization of acrylic monomers and/or styrene using acrylic acid or methacrylic acid as auxiliary comonomers. The ultrasmall IO particles adsorbed at the latex surface and played the role of a solid stabilizer. The influence of the synthesis conditions on the composite particle size, polymerization kinetics, IO incorporation efficiency, and particle morphology was studied. Thermogravimetric analysis indicated that the efficiency of iron oxide incorporation was improved with increasing the suspension pH, the amount of auxiliary comonomer, or the IO content and reached ca. 90% under optimized conditions. Reducing the initial iron oxide concentration at constant monomer concentration led to an increased particle size and a reduced colloid stability, indicating that the magnetic nanoparticles stabilized the colloidal nanocomposites. Transmission electron microscopy studies confirmed ...
Polym. Chem.
Comb-like P(PEOMA300-co-MAA-co-S)-SG1 macroalkoxyamine terpolymer initiators with dual pH/tempera... more Comb-like P(PEOMA300-co-MAA-co-S)-SG1 macroalkoxyamine terpolymer initiators with dual pH/temperature responsive behavior were synthesized by nitroxide-mediated polymerization and used to control the emulsion polymerization of BMA with a small proportion of styrene.
Macromolecules, 2016
The reversible addition–fragmentation chain transfer (RAFT) polymerization technique was used to ... more The reversible addition–fragmentation chain transfer (RAFT) polymerization technique was used to synthesize random copolymers of poly(ethylene glycol) methyl ether acrylate) (PEGA) and n-butyl acrylate (BA) and terpolymers of acrylic acid (AA), PEGA and BA with a trithiocarbonate reactive end-group. These macromolecular RAFT agents (macro-RAFTs) were subsequently adsorbed at the surface of size-monodisperse colloidal silica particles with diameters varying between 40 and 450 nm. Adsorption isotherms for both macro-RAFTs could be well fitted to the Langmuir adsorption model, the AA-based macro-RAFT agent showing however a lower maximum adsorption. The adsorbed macro-RAFT agents were subsequently chain extended with a mixture of methyl methacrylate (MMA) and BA by starved feed emulsion polymerization. Cryo-TEM analysis of the resulting hybrid latexes synthesized in the presence of the P(AA-co-PEGA-co-BA) terpolymers resulted in multipod-like particles while the P(PEGA-co-BA) copolymers showed the formation ...
Macromolecules
We report the first nitroxide-mediated synthesis of multipod-like silica/polymer latexes by polym... more We report the first nitroxide-mediated synthesis of multipod-like silica/polymer latexes by polymerization-induced self-assembly (PISA) of amphiphilic block copolymers in aqueous emulsion. A water-soluble brush-type PEO-based macroalkoxyamine initiator composed of poly(ethylene oxide) methacrylate and a small amount of styrene (P[(PEOMA950)12-co-S1]-SG1, Mn = 11?700 g mol?1 and Mw/Mn = 1.11) was synthesized and physically adsorbed on the surface of silica particles through hydrogen-bonding interactions. The adsorbed macroalkoxyamine initiator was subsequently employed to initiate the emulsion polymerization of n-butyl methacrylate with a small amount of styrene under mild conditions (85 °C). Kinetic analysis indicates that the polymerizations exhibit the same behavior (i.e., the same reaction rates and the same level of control) as those reported in our previous work in the absence of silica under otherwise similar experimental conditions [Qiao Macromolecules 2013, 46, 4285?4295]. T...
Polymer Chemistry
A robust and straightforward synthesis of surfactant-free poly(vinylidene fluoride) (PVDF) latexe... more A robust and straightforward synthesis of surfactant-free poly(vinylidene fluoride) (PVDF) latexes is presented using RAFT/MADIX-mediated emulsion polymerization. VDF emulsion polymerizations were conducted in the presence of commercial poly(ethylene glycol) chains...
Advanced Materials Interfaces
Polymer Chemistry
Block copolymers can be obtained by combining catalytic chain transfer polymerization (CCTP) and ... more Block copolymers can be obtained by combining catalytic chain transfer polymerization (CCTP) and conventional free radical emulsion polymerization of ethylene.
ACS catalysis, Feb 1, 2024
Macromolecules, May 26, 2022
Angewandte Chemie, Apr 14, 2020
Poly(ethylene oxide) (PEO) with dithiocarbamate chain ends (PEO-SC(=S)-N(CH3)Ph and PEO-SC(=S)-NP... more Poly(ethylene oxide) (PEO) with dithiocarbamate chain ends (PEO-SC(=S)-N(CH3)Ph and PEO-SC(=S)-NPh2, named PEO-1 and PEO-2, respectively) were used as macromolecular chain transfer agents (macro-CTA) to mediate the reversible additionfragmentation chain transfer (RAFT) polymerization of ethylene in dimethyl carbonate (DMC) under relatively mild conditions (80 °C, 80 bar). While only a slow consumption of PEO-1 was observed, the rapid consumption of PEO-2 led to a clean chain extension and the formation of a polyethylene (PE) segment. Upon polymerization, the resulting block copolymers PEO-b-PE self-assembled into nanometric objects according to a polymerization-induced self-assembly (PISA).
arXiv (Cornell University), Mar 29, 2023
Chemistry – A European Journal
Journal of Controlled Release
Polymer Chemistry, 2020
MgAl-layered double hydroxide (LDH)-armored latexes were produced by Pickering emulsion polymeriz... more MgAl-layered double hydroxide (LDH)-armored latexes were produced by Pickering emulsion polymerization of styrene using 2-hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) as auxiliary comonomers.
Langmuir, 2018
We report an efficient and easy to implement waterborne sol-gel process for the synthesis of nano... more We report an efficient and easy to implement waterborne sol-gel process for the synthesis of nanometric organosilica particles. In this process, tetraethyl orthosilicate (TEOS) and 3-(methacryloxy)propyl trimethoxy silane (-MPS), employed as silica sources, are heterogeneously delivered in an aqueous solution of L-arginine, a basic amino acid used as catalyst, from a top organic layer. Co-condensation of TEOS with γ-MPS led to organosilica particles with diameters comprised between 30 and 230 nm when increasing the -MPS content from 0 to 10.1 mol % in the silica source. Nitrogen sorption analyses confirmed the microporous nature of the obtained particles after calcination. The Brunauer-Emmett-Teller (BET) surface areas increased from 27 (before calcination) to 684 m 2 g-1 (after calcination) for the organosilica particles containing 10.1 mol% of -MPS. Fourier transform infrared (FTIR) spectroscopy and 29 Si nuclear magnetic resonance (NMR) were employed to analyze the chemical structure of the organosilica spheres and provide insight into the mechanism of particle formation. In a second part, hybrid organosilica particles with a core-shell morphology were synthesized through the combination of Pickering emulsion and the sol-gel process. -MPS emulsion droplets stabilized by tiny silica particles (formed in a separate step) 2 were firstly generated, and used as seeds to grow a silica shell on their surface through TEOS addition from the top organic layer. TEM and pore size analyses of the resulting particles after calcination revealed a unique dual-porosity structure with a mesoporous inner core and a micro/mesoporous silica shell with ink-bottle type pores.
Polymer, 2013
ABSTRACT The polymerization-induced self-assembly of amphiphilic block copolymers in water was pe... more ABSTRACT The polymerization-induced self-assembly of amphiphilic block copolymers in water was performed following a reversible addition-fragmentation chain transfer (RAFT) controlled radical polymerization mechanism in emulsion. Poly(methacrylic acid-co-poly(ethylene oxide) methyl ether methacrylate), P(MAA-co-PEOMA), with a trithiocarbonate reactive end-group was selected as the water-soluble living precursor and synthesized in situ via a RAFT aqueous solution polymerization process. The study focused on the polymerization of methyl methacrylate (MMA) at pH 3.5, 5 and 7 and its copolymerization with various proportions of styrene (S) at pH 3.5. In the homopolymerization of MMA, the reaction was well-controlled at pH 3.5, while a low blocking efficiency was observed at higher pH. The systems led to spherical micelles, fibers and then vesicles when the molar mass of the hydrophobic block was increased, irrespective of the pH of the aqueous phase. In the case of the copolymerization with styrene at pH 3.5 and in chain length conditions leading to fibers for the homopolymerization of MMA, the control was very good but the final morphology was that of spherical particles only, at all compositions studied, exactly like in the homopolymerization of styrene performed under similar experimental conditions [Zhang et al. Macromolecules 2011; 44:7584–93]. The results were interpreted on the basis of an influence of the polymerization kinetics, especially in the early stage of the reaction in the aqueous phase.
The emulsion photopolymerization under visible light of acrylate and methacrylate monomers is rep... more The emulsion photopolymerization under visible light of acrylate and methacrylate monomers is reported. We previously introduced an NHC-borane-based system that was efficient for the emulsion photo...
Macromolecules
Silica/polymer latexes with concentric core–shell–corona, half-capped, snowman-like vesicular, ta... more Silica/polymer latexes with concentric core–shell–corona, half-capped, snowman-like vesicular, tadpole- and centipede-like morphologies have been produced by nitroxide-mediated polymerization-induced self-assembly (PISA) performed in the presence of aqueous suspensions of colloidal silica. A hydrosoluble brush-like PEO-based macroalkoxyamine (P[(poly(ethylene oxide) methyl ether methacrylate)12-co-styrene]-SG1, Mn = 11 700 g mol–1 and Mw/Mn = 1.11) was first adsorbed onto the surface of submicronic silica particles. The obtained suspension was then used in the emulsion polymerization of n-butyl methacrylate with 8 mol % of styrene. This led to the formation of amphiphilic block copolymers (BCPs) that self-assembled in situ at the silica surface into well-defined hybrid nano-objects of various morphologies, in agreement with the principles of polymerization-induced micellization. The influence of the pH was more specifically investigated, using silica particles of different size ranging from 30 to 230 nm. ...
Macromolecules
Iron oxide (IO)-based composite latex particles with a patchy IO overlayer were successfully prep... more Iron oxide (IO)-based composite latex particles with a patchy IO overlayer were successfully prepared by Pickering emulsion polymerization of acrylic monomers and/or styrene using acrylic acid or methacrylic acid as auxiliary comonomers. The ultrasmall IO particles adsorbed at the latex surface and played the role of a solid stabilizer. The influence of the synthesis conditions on the composite particle size, polymerization kinetics, IO incorporation efficiency, and particle morphology was studied. Thermogravimetric analysis indicated that the efficiency of iron oxide incorporation was improved with increasing the suspension pH, the amount of auxiliary comonomer, or the IO content and reached ca. 90% under optimized conditions. Reducing the initial iron oxide concentration at constant monomer concentration led to an increased particle size and a reduced colloid stability, indicating that the magnetic nanoparticles stabilized the colloidal nanocomposites. Transmission electron microscopy studies confirmed ...
Polym. Chem.
Comb-like P(PEOMA300-co-MAA-co-S)-SG1 macroalkoxyamine terpolymer initiators with dual pH/tempera... more Comb-like P(PEOMA300-co-MAA-co-S)-SG1 macroalkoxyamine terpolymer initiators with dual pH/temperature responsive behavior were synthesized by nitroxide-mediated polymerization and used to control the emulsion polymerization of BMA with a small proportion of styrene.
Macromolecules, 2016
The reversible addition–fragmentation chain transfer (RAFT) polymerization technique was used to ... more The reversible addition–fragmentation chain transfer (RAFT) polymerization technique was used to synthesize random copolymers of poly(ethylene glycol) methyl ether acrylate) (PEGA) and n-butyl acrylate (BA) and terpolymers of acrylic acid (AA), PEGA and BA with a trithiocarbonate reactive end-group. These macromolecular RAFT agents (macro-RAFTs) were subsequently adsorbed at the surface of size-monodisperse colloidal silica particles with diameters varying between 40 and 450 nm. Adsorption isotherms for both macro-RAFTs could be well fitted to the Langmuir adsorption model, the AA-based macro-RAFT agent showing however a lower maximum adsorption. The adsorbed macro-RAFT agents were subsequently chain extended with a mixture of methyl methacrylate (MMA) and BA by starved feed emulsion polymerization. Cryo-TEM analysis of the resulting hybrid latexes synthesized in the presence of the P(AA-co-PEGA-co-BA) terpolymers resulted in multipod-like particles while the P(PEGA-co-BA) copolymers showed the formation ...
Macromolecules
We report the first nitroxide-mediated synthesis of multipod-like silica/polymer latexes by polym... more We report the first nitroxide-mediated synthesis of multipod-like silica/polymer latexes by polymerization-induced self-assembly (PISA) of amphiphilic block copolymers in aqueous emulsion. A water-soluble brush-type PEO-based macroalkoxyamine initiator composed of poly(ethylene oxide) methacrylate and a small amount of styrene (P[(PEOMA950)12-co-S1]-SG1, Mn = 11?700 g mol?1 and Mw/Mn = 1.11) was synthesized and physically adsorbed on the surface of silica particles through hydrogen-bonding interactions. The adsorbed macroalkoxyamine initiator was subsequently employed to initiate the emulsion polymerization of n-butyl methacrylate with a small amount of styrene under mild conditions (85 °C). Kinetic analysis indicates that the polymerizations exhibit the same behavior (i.e., the same reaction rates and the same level of control) as those reported in our previous work in the absence of silica under otherwise similar experimental conditions [Qiao Macromolecules 2013, 46, 4285?4295]. T...
Polymer Chemistry
A robust and straightforward synthesis of surfactant-free poly(vinylidene fluoride) (PVDF) latexe... more A robust and straightforward synthesis of surfactant-free poly(vinylidene fluoride) (PVDF) latexes is presented using RAFT/MADIX-mediated emulsion polymerization. VDF emulsion polymerizations were conducted in the presence of commercial poly(ethylene glycol) chains...
Advanced Materials Interfaces