Catherine Lefay

First Nitroxide-Mediated Controlled Free-Radical Polymerization of Acrylic Acid

Controlled poly(acrylic acid) homopolymers were synthesized for the first time by direct nitroxide-mediated polymerization of acrylic acid. The polymerizations were performed in 1,4-dioxane solution at 120 °C, using an alkoxyamine initiator based on the N-tert-butyl-N-(1-diethyl phosphono-2,2-dimethyl propyl) nitroxide, SG1. The kinetics were controlled by the addition of free nitroxide at the beginning of the polymerization and the optimal amount was 9 mol % with respect to the initiator. In this case, whatever the initiator concentration, all polymerizations exhibited the same rate and conversion reached 85−90% within 5 h. Although the rate constant of propagation of acrylic acid is very large, its reactivity is moderated by a low activation−deactivation equilibrium constant between active macroradicals and SG1-capped dormant chains. Various alkoxyamine concentrations were investigated to target different molar masses. At high initiator concentrations, the number-average molar mass, Mn, increased linear...

Aqueous suspension of amphiphilic diblock copolymer nanoparticles prepared in situ from a water-soluble poly(sodium acrylate) alkoxyamine macroinitiator

The simple, one step synthesis of aqueous suspensions of amphiphilic nanoparticles is presented. Those particles are prepared in the batch heterophase polymerization of styrene or -butyl acrylate, using a water-soluble poly(sodium acrylate) alkoxyamine macroinitiator. The nitroxide-mediated controlled growth of the hydrophobic block leads to the formation of poly(sodium acrylate)--polystyrene or poly(sodium acrylate)--poly(-butyl acrylate) amphiphilic diblock copolymers, able to self-assemble in water simultaneously to the growth step. When the diblock copolymers become strongly asymmetrical, with a short poly(sodium acrylate) block and a long hydrophobic one, the formed hairy nanoparticles are analogous to amphiphilic diblock copolymer crew-cut micelles.

Surfactant-free synthesis of amphiphilic diblock copolymer nanoparticles via nitroxide-mediated emulsion polymerization

Amphiphilic hairy nanoparticles are prepared in a one step, batch, heterogeneous polymerization of styrene or n-butyl acrylate, using a water-soluble poly(sodium acrylate) alkoxyamine macroinitiator based on the SG1 nitroxide.

Radical Ring-Opening Polymerization: Scope, Limitations, and Application to (Bio)Degradable Materials

Cyclic monomers bearing either vinyl or exomethylene groups have the ability to be polymerized through a radical pathway via a ring-opening mechanism (addition-fragmentation process), leading to the introduction of functionalities in the polymer backbone. Radical ring-opening polymerization (rROP) combines the advantages of both ring-opening polymerization and radical polymerization, that is the preparation of polymers bearing heteroatoms in the backbone but with the ease and robustness of a radical process. This current review presents a comprehensive description of rROP by detailing: (i) the various monomers that polymerize through rROP; (ii) the main parameters that govern the rROP mechanism; (iii) the copolymerization by conventional or controlled/living radical polymerization between rROP monomers and traditional vinyl monomers to obtain copolymers with advanced properties; (iv) the different applications (low shrinkage materials and preparation of (bio)degradable materials) of rROP monomer-containing materials, and (v) the main alternatives to rROP to induce degradability to materials obtained by a radical polymerization.

Heterogeneous modification of chitosan via nitroxide-mediated polymerization

Chitosan (CS) was modified by SG1-based nitroxide-mediated polymerization under heterogeneous conditions. After introduction of acrylamide and/or acrylate functions onto the CS backbone followed by intermolecular 1,2 radical addition of the BlocBuilder alkoxyamine (CS–BB), methyl methacrylate (MMA) in the presence of a small amount of acrylonitrile (AN) or sodium 4-styrenesulfonate (SS) was polymerized by nitroxide-mediated polymerization (NMP). ESR and free-solution capillary electrophoresis confirmed the synthesis of CS–BB. The successful synthesis of CS-g-P(MMA-co-AN) and CS-g-PSS grafted copolymers was proved by TGA and solid-state NMR spectroscopy with ca. 20 to 30 wt% of grafted synthetic polymer in the final product.

Intermolecular radical 1,2-addition of the BlocBuilder MA alkoxyamine onto activated olefins: a versatile tool for the synthesis of complex macromolecular architecture

This review described the potential of the intermolecular radical 1,2-addition from the commercially available BlocBuilder MA alkoxyamine onto activated olefins to synthesize either new functionalized alkoxyamines or various macromolecular architectures. Following this approach, diblock, triblock copolymers, star polymers and hybrid materials are then easily prepared. The various applications of such architectures will be briefly reviewed. Interestingly this new synthetic tool widely expands the range of complex macromolecular architectures which could be obtained by the nitroxide-mediated polymerization (NMP) process.

Scope and limitations of the nitroxide-mediated radical ring-opening polymerization of cyclic ketene acetals

The ring-opening polymerization of cyclic ketene acetals (CKAs) by controlled radical mechanisms represents an alternative route for the synthesis of aliphatic polyesters. For the first time, 5,6-benzo-2-methylene-1,3-dioxepane (BMDO) and 2-methylene-4-phenyl-1,3-dioxolane (MPDL) were homopolymerized by nitroxide mediated polymerization (NMP), from the commercially available SG1-based BlocBuilder MA alkoxyamine. Various experimental conditions (i.e., reaction temperature, nature of solvent, and nature of the alkyl initiating radical) were varied to determine the optimized conditions in terms of polymerization kinetics and living character of the final polymer. Chain-end extensions from either PS-SG1 or PBMDO-SG1 were also performed in order to furnish PS-b-PBMDO and PBMDO-b-PS, respectively, thus demonstrating the synthesis of block copolymers comprising a CKA block. In order to have a better insight into the polymerization mechanism, the occurrence of side reactions was analyzed by 31P NMR spectroscopy and ESI-MS. It was supposed that the ketal-based macroradical could be irreversibly trapped by nitroxide and thus the corresponding macroalkoxyamine decomposed by CO–N bond dissociation. DFT calculations as well as PREDICI modeling were also undertaken in order to support this hypothesis.

Synthesis of polystyrene-grafted cellulose acetate copolymers via nitroxide-mediated polymerization

Cellulose acetate-g-polystyrene (CA-g-PS) grafted copolymers have been synthesized by nitroxide-mediated polymerization (NMP) under homogeneous conditions by using the 1,2-intermolecular radical addition (1,2-IRA) methodology to introduce the SG1-based alkoxyamine BlocBuilder MA (BB) on the polysaccharide backbone. A preliminary study conducted on model sugar-based alkoxyamines proved that whatever the position of the alkoxyamine on the sugar unit, the number of sugar units and the presence of OH groups, one could expect a controlled/living polymerization process. This was confirmed by the graft polymerization of styrene from the BB-modified cellulose acetate backbone with two different grafting ratios (3 and 20%) and different grafted chain lengths (40 000 and 80 000 g mol−1 targeted Mn). The grafted copolymers were carefully analyzed, in particular, by DOSY NMR to confirm their grafted structure.

Miniemulsion Polymerization Stabilized by a Well-Defined, Amphiphilic Gradient Poly(styrene-co-acrylic acid) Copolymer

The nitroxide-mediated controlled free-radical copolymerization of styrene (St) and acrylic acid (AA) was used to synthesize a well-defined poly(St30%-co-AA70%) amphiphilic gradient copolymer. The latter proved to be an efficient stabilizer in the 45 wt.-% solids content, batch miniemulsion polymerizations of St and of mixtures of methyl methacrylate/n-butyl acrylate (35/65 w/w). With 2,2´-azobisisobutyronitrile as an oil-soluble initiator, polystyrene latexes with a very narrow particle distribution were obtained, whereas the water-soluble initiator, potassium persulfate, led to broad, multimodal particle size distributions. Such results were explained by the contribution of two nucleation mechanisms: droplet nucleation and homogeneous nucleation. In contrast, the poly(methyl methacrylate-co-n-butyl acrylate) latexes exhibited larger particle size and narrower particle size distributions with persulfate initiator, than the polystyrene latexes.

Separation of poly(acrylic acid) salts according to topology using capillary electrophoresis in the critical conditions

AbstractBranching was detected in polyacrylates synthesised through radical polymerization via solution-state NMR, while inconsistencies have been reported for the determination of the molar mass of hydrophilic polyacrylates using aqueous-phase and organic-phase size-exclusion chromatography. In this work, poly(sodium acrylate)s, PNaAs, of various topologies were separated for the first time using free-solution capillary electrophoresis (CE). Free-solution CE does not separate the PNaAs by their molar mass, similarly to separations by liquid chromatography in the critical conditions, rather by different topologies (linear, star branched, and hyperbranched). The electrophoretic mobility of PNaAs increases as the degree of branching decreases. Separation is shown to be not only by the topology but also by the end groups as expected for a separation in the critical conditions: replacing a relatively bulky nitroxide end group with hydrogen atom yielded a higher electrophoretic mobility. This novel method, capillary electrophoresis in the critical conditions enabled, for the first time, the separation of hydrophilic polyacrylates according to their topology (branching) and their chain ends. This will allow meaningful and accurate characterization of their branched topologies as well as molar masses and progress in for advanced applications such as drug delivery or flocculation. FigureFree solution Capillary Electrophoresis (CE) of polyacrylates with various topologies