The Experts below are selected from a list of 582 Experts worldwide ranked by ideXlab platform
Virgil Percec - One of the best experts on this subject based on the ideXlab platform.
-
synthesis of high molar mass poly n butyl Acrylate and poly 2 ethylhexyl Acrylate by set lrp in mixtures of fluorinated alcohols with dmso
Polymer Chemistry, 2014Co-Authors: Shampa R Samanta, Virgil PercecAbstract:SET-LRP of n-butyl Acrylate (nBA) and 2-Ethylhexyl Acrylate (EHA) initiated with bis(2-bromopropionyl)ethane (BPE) to synthesize high molar mass poly(nBA) and poly(EHA) was carried out in binary mixtures of 2,2,2-trifluoroethanol (TFE) or 2,2,3,3-tetrafluoropropanol (TFP) with DMSO at 50 °C. Using a solvent mixture of TFP containing 30% DMSO led for the first time to the synthesis of poly(nBA) with Mn = 527700, Mw/Mn = 1.21 in 12 h, and poly(EHA) with Mn = 913100, Mw/Mn = 1.20 in 15 h via SET-LRP. Although these two fluorinated alcohols provide complete solubilization of the hydrophobic monomers, nBA and EHA, and of the resulting polymers in addition to an efficient disproportionation of Cu(I)Br and subsequent stabilization of the Cu(II)Br2/L complex, SET-LRP targeting high molar mass poly(nBA) and poly(EHA) in these solvents alone resulted in a relatively slow polymerization with limited conversion. By contrast, DMSO, in spite of being the preferred solvent for SET-LRP with ability to disproportionate Cu(I)Br, stabilizes the “nascent” Cu(0) nanoparticle and provides an efficient SET process, generating a non-living polymerization for these hydrophobic monomers due to the insolubility of the resulting polymers. Remarkably, by a cooperative and synergistic effect, the binary mixtures of TFE or TFP with DMSO provide excellent reaction media for the synthesis of high molar mass poly(nBA) and poly(EHA) by SET-LRP.
-
set lrp of hydrophobic and hydrophilic Acrylates in trifluoroethanol
Polymer Chemistry, 2013Co-Authors: Shampa R Samanta, Martin E Levere, Virgil PercecAbstract:Efficient disproportionation of CuBr–Me6-TREN in 2,2,2-trifluoroethanol (TFE) to produce “nascent” Cu(0) and CuBr2–Me6-TREN indicates that this semifluorinated alcohol has the potential to be an excellent solvent for Cu(0) mediated single electron transfer-living radical polymerization (SET-LRP). Herein, we report the SET-LRP of a range of hydrophobic and hydrophilic Acrylates, including methyl Acrylate (MA), n-butyl Acrylate (nBA), tert-butyl Acrylate (tBA), 2-Ethylhexyl Acrylate (EHA) and 2-hydroxyethyl Acrylate (HEA) using 2-bromopropionate (MBP) and 2-ethylbromoisopropionate (EBiB) as initiators, and Me6-TREN as ligand in TFE. Analysis of the kinetics of polymerization and of the polymer chain ends by a combination of 1H NMR, GPC, MALDI-TOF and chain-end functionalization by “thio-bromo” click reaction demonstrated the synthesis of perfect or near-perfect chain-end functional polyAcrylates by SET-LRP in TFE.
-
synthesis of poly vinyl chloride b poly 2 ethylhexyl Acrylate b poly vinyl chloride by the competitive single electron transfer degenerative chain transfer mediated living radical polymerization of vinyl chloride initiated from α ω di iodo poly 2 ethylhexyl Acrylate and catalyzed with sodium dithionite in water
Journal of Polymer Science Part A, 2005Co-Authors: Virgil Percec, Anatoliy V Popov, Ernesto Ramirezcastillo, Luis A HinojosafalconAbstract:α,ω-Di(iodo)poly(2-Ethylhexyl Acrylate)s [α,ω-di(iodo)P2EHAs] with number-average molecular weights of 13,700 and 20,400 were synthesized by the single-electron-transfer/degenerative-chain-transfer mediated living radical polymerization (SET–DTLRP) of 2-Ethylhexyl Acrylate initiated with iodoform and catalyzed by sodium dithionite in water at 23 and 30 °C. These α,ω-di(iodo)P2EHAs were used as macroinitiators for the SET–DTLRP of vinyl chloride, which was carried out under similar reaction conditions to synthesize ABA block copolymers containing poly(vinyl chloride) in the A blocks and poly(2-Ethylhexyl Acrylate) in the B block. Poly(vinyl chloride)-b-poly(2-Ethylhexyl Acrylate)-b-poly(vinyl chloride) was synthesized with 100% initiator efficiency. This synthetic method provides for the first time access to a diversity of block copolymers and other complex architectures based on combinations of thermoplastic poly(vinyl chloride)and elastomeric polyAcrylates. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2276–2280, 2005
Lisa Houillot - One of the best experts on this subject based on the ideXlab platform.
-
two dimensional chromatographic characterization of block copolymers of 2 ethylhexyl Acrylate and methyl Acrylate p2eha b pma produced via raft mediated polymerization in organic dispersion
Macromolecules, 2010Co-Authors: Jacquesantoine Raust, Bernadette Charleux, Lisa Houillot, Claudine Moire, Celine Farcet, Maud Save, Harald PaschAbstract:For the precise characterization of block copolymers of 2-Ethylhexyl Acrylate (2EHA) and methyl Acrylate (MA) produced via RAFT (reversible addition−fragmentation chain transfer)-mediated dispersio...
-
dispersion polymerization of methyl Acrylate in nonpolar solvent stabilized by block copolymers formed in situ via the raft process
ACS Applied Materials & Interfaces, 2010Co-Authors: Lisa Houillot, Jacquesantoine Raust, Claudine Moire, Celine Farcet, Maud Save, Harald Pasch, Bernadette CharleuxAbstract:The free-radical dispersion polymerization of methyl Acrylate (MA) in isododecane was carried out in the presence of a poly(2-Ethylhexyl Acrylate) macromolecular RAFT (reversible addition−fragmentation chain transfer) agent bearing a trithiocarbonate reactive group in the middle of the chain (P2EHA-TTC). The presence of the trithiocarbonate function was crucial for the synthesis of monodisperse colloidal poly(methyl Acrylate) (PMA) particles stabilized by the P2EHA segments. The hydrodynamic diameters ranged from 100 to 300 nm, using particularly low amounts of the macro(RAFT agent) (1−6 wt % vs. MA) in dispersion polymerizations carried out at 20 wt % solids content. As shown by 2D liquid chromatography, P2EHA-b-PMA or P2EHA-b-PMA-b-P2EHA block copolymers formed in situ at the early stage of the dispersion polymerization due to the reversible transfer process and played the role of particle stabilizer. The glass-transition temperature of the derived polymer films was not affected by the low amount of the...
-
Two dimensional chromatographic characterization of block copolymers of 2-Ethylhexyl Acrylate and methyl Acrylate, P2EHA-b-PMA, produced via RAFT-mediated polymerization in organic dispersion
Macromolecules, 2010Co-Authors: Jacquesantoine Raust, Bernadette Charleux, Lisa Houillot, Claudine Moire, Celine Farcet, M. Save, H. PaschAbstract:For the precise characterization of block copolymers of 2-Ethylhexyl Acrylate (2EHA) and methyl Acrylate (MA) produced via RAFT (reversible addition-fragmentation chain transfer)-mediated dispersion polymerization, novel liquid chromatographic separations have been developed. SEC showed multimodal molar mass distributions (MMD) and HPLC showed multimodal chemical composition distributions (CCD). The analyses of MMD and CCD of the reaction products indicated the formation of the expected block copolymer along with remaining P2EHA and PMA homopolymer fractions. Online coupling of SEC and gradient HPLC in a two-dimensional liquid chromatography (2D-LC) setup proved to be an efficient method to fractionate all polymer species present in the samples. Different kinds of copolymer molecules were identified in addition to the two homopolymers. The quantification of P2EHA using liquid chromatography at critical conditions (LC-CC) showed that the unreacted macro(RAFT agent) amount remained unchanged during at least the first 4 h of polymerization. LC-CC experiments also allowed the relative molar mass of the PMA blocks contained in the copolymers to be determined. The implementation of 2D-LC combining SEC and LC-CC allowed a more precise characterization of the different copolymer structures in particular in terms of block size. Finally, the results obtained by SEC/HPLC were confirmed by LC-1H NMR (proton nuclear magnetic resonance) experiments. It was concluded that the dispersed state of the polymerization system was the important factor for the formation of broadly distributed, complex copolymers when using a dithiobenzoate-based reactive macromolecular stabilizer. The detailed characterization of the system highlighted the enhancement of irreversible termination at the interface of the dispersed particles. © 2010 American Chemical Society.
-
Synthesis of well-defined polyAcrylate particle dispersions in organic medium using simultaneous RAFT polymerization and self-assembly of block copolymers. A strong influence of the selected thiocarbonylthio chain transfer agent
Macromolecules, 2007Co-Authors: Lisa Houillot, Chuong Bui, Bernadette Charleux, Jacquesantoine Raust, Claudine Moire, Celine Farcet, Maud Save, Ivan RodriguezAbstract:The RAFT-mediated nonaqueous dispersion polymerization of methyl Acrylate in isododecane, a nonsolvent for poly(methyl Acrylate), was carried out using two soluble poly(2-Ethylhexyl Acrylate) macromolecular RAFT agents, containing either a dithiobenzoate reactive function or a trithiocarbonate one. The method produced stable colloidal particles, with hydrodynamic diameters below 100 nm. Using poly(2-Ethylhexyl Acrylate) with a dithiobenzoate end group, strong rate retardation and poor control over the polymer chains were observed. In contrast, when the trithiocarbonate-functionalized poly(2-Ethylhexyl Acrylate) was used, the formation of monodisperse micellar aggregates of well-defined self-assembled block copolymers was obtained with fast polymerization rates, irrespective of the RAFT agent concentration. Such differences were explained by the dispersed state of the system rather than by the intrinsic reactivity of the soluble macromolecular RAFT agent.
Bernadette Charleux - One of the best experts on this subject based on the ideXlab platform.
-
two dimensional chromatographic characterization of block copolymers of 2 ethylhexyl Acrylate and methyl Acrylate p2eha b pma produced via raft mediated polymerization in organic dispersion
Macromolecules, 2010Co-Authors: Jacquesantoine Raust, Bernadette Charleux, Lisa Houillot, Claudine Moire, Celine Farcet, Maud Save, Harald PaschAbstract:For the precise characterization of block copolymers of 2-Ethylhexyl Acrylate (2EHA) and methyl Acrylate (MA) produced via RAFT (reversible addition−fragmentation chain transfer)-mediated dispersio...
-
dispersion polymerization of methyl Acrylate in nonpolar solvent stabilized by block copolymers formed in situ via the raft process
ACS Applied Materials & Interfaces, 2010Co-Authors: Lisa Houillot, Jacquesantoine Raust, Claudine Moire, Celine Farcet, Maud Save, Harald Pasch, Bernadette CharleuxAbstract:The free-radical dispersion polymerization of methyl Acrylate (MA) in isododecane was carried out in the presence of a poly(2-Ethylhexyl Acrylate) macromolecular RAFT (reversible addition−fragmentation chain transfer) agent bearing a trithiocarbonate reactive group in the middle of the chain (P2EHA-TTC). The presence of the trithiocarbonate function was crucial for the synthesis of monodisperse colloidal poly(methyl Acrylate) (PMA) particles stabilized by the P2EHA segments. The hydrodynamic diameters ranged from 100 to 300 nm, using particularly low amounts of the macro(RAFT agent) (1−6 wt % vs. MA) in dispersion polymerizations carried out at 20 wt % solids content. As shown by 2D liquid chromatography, P2EHA-b-PMA or P2EHA-b-PMA-b-P2EHA block copolymers formed in situ at the early stage of the dispersion polymerization due to the reversible transfer process and played the role of particle stabilizer. The glass-transition temperature of the derived polymer films was not affected by the low amount of the...
-
Two dimensional chromatographic characterization of block copolymers of 2-Ethylhexyl Acrylate and methyl Acrylate, P2EHA-b-PMA, produced via RAFT-mediated polymerization in organic dispersion
Macromolecules, 2010Co-Authors: Jacquesantoine Raust, Bernadette Charleux, Lisa Houillot, Claudine Moire, Celine Farcet, M. Save, H. PaschAbstract:For the precise characterization of block copolymers of 2-Ethylhexyl Acrylate (2EHA) and methyl Acrylate (MA) produced via RAFT (reversible addition-fragmentation chain transfer)-mediated dispersion polymerization, novel liquid chromatographic separations have been developed. SEC showed multimodal molar mass distributions (MMD) and HPLC showed multimodal chemical composition distributions (CCD). The analyses of MMD and CCD of the reaction products indicated the formation of the expected block copolymer along with remaining P2EHA and PMA homopolymer fractions. Online coupling of SEC and gradient HPLC in a two-dimensional liquid chromatography (2D-LC) setup proved to be an efficient method to fractionate all polymer species present in the samples. Different kinds of copolymer molecules were identified in addition to the two homopolymers. The quantification of P2EHA using liquid chromatography at critical conditions (LC-CC) showed that the unreacted macro(RAFT agent) amount remained unchanged during at least the first 4 h of polymerization. LC-CC experiments also allowed the relative molar mass of the PMA blocks contained in the copolymers to be determined. The implementation of 2D-LC combining SEC and LC-CC allowed a more precise characterization of the different copolymer structures in particular in terms of block size. Finally, the results obtained by SEC/HPLC were confirmed by LC-1H NMR (proton nuclear magnetic resonance) experiments. It was concluded that the dispersed state of the polymerization system was the important factor for the formation of broadly distributed, complex copolymers when using a dithiobenzoate-based reactive macromolecular stabilizer. The detailed characterization of the system highlighted the enhancement of irreversible termination at the interface of the dispersed particles. © 2010 American Chemical Society.
-
Synthesis of well-defined polyAcrylate particle dispersions in organic medium using simultaneous RAFT polymerization and self-assembly of block copolymers. A strong influence of the selected thiocarbonylthio chain transfer agent
Macromolecules, 2007Co-Authors: Lisa Houillot, Chuong Bui, Bernadette Charleux, Jacquesantoine Raust, Claudine Moire, Celine Farcet, Maud Save, Ivan RodriguezAbstract:The RAFT-mediated nonaqueous dispersion polymerization of methyl Acrylate in isododecane, a nonsolvent for poly(methyl Acrylate), was carried out using two soluble poly(2-Ethylhexyl Acrylate) macromolecular RAFT agents, containing either a dithiobenzoate reactive function or a trithiocarbonate one. The method produced stable colloidal particles, with hydrodynamic diameters below 100 nm. Using poly(2-Ethylhexyl Acrylate) with a dithiobenzoate end group, strong rate retardation and poor control over the polymer chains were observed. In contrast, when the trithiocarbonate-functionalized poly(2-Ethylhexyl Acrylate) was used, the formation of monodisperse micellar aggregates of well-defined self-assembled block copolymers was obtained with fast polymerization rates, irrespective of the RAFT agent concentration. Such differences were explained by the dispersed state of the system rather than by the intrinsic reactivity of the soluble macromolecular RAFT agent.
Jacquesantoine Raust - One of the best experts on this subject based on the ideXlab platform.
-
two dimensional chromatographic characterization of block copolymers of 2 ethylhexyl Acrylate and methyl Acrylate p2eha b pma produced via raft mediated polymerization in organic dispersion
Macromolecules, 2010Co-Authors: Jacquesantoine Raust, Bernadette Charleux, Lisa Houillot, Claudine Moire, Celine Farcet, Maud Save, Harald PaschAbstract:For the precise characterization of block copolymers of 2-Ethylhexyl Acrylate (2EHA) and methyl Acrylate (MA) produced via RAFT (reversible addition−fragmentation chain transfer)-mediated dispersio...
-
dispersion polymerization of methyl Acrylate in nonpolar solvent stabilized by block copolymers formed in situ via the raft process
ACS Applied Materials & Interfaces, 2010Co-Authors: Lisa Houillot, Jacquesantoine Raust, Claudine Moire, Celine Farcet, Maud Save, Harald Pasch, Bernadette CharleuxAbstract:The free-radical dispersion polymerization of methyl Acrylate (MA) in isododecane was carried out in the presence of a poly(2-Ethylhexyl Acrylate) macromolecular RAFT (reversible addition−fragmentation chain transfer) agent bearing a trithiocarbonate reactive group in the middle of the chain (P2EHA-TTC). The presence of the trithiocarbonate function was crucial for the synthesis of monodisperse colloidal poly(methyl Acrylate) (PMA) particles stabilized by the P2EHA segments. The hydrodynamic diameters ranged from 100 to 300 nm, using particularly low amounts of the macro(RAFT agent) (1−6 wt % vs. MA) in dispersion polymerizations carried out at 20 wt % solids content. As shown by 2D liquid chromatography, P2EHA-b-PMA or P2EHA-b-PMA-b-P2EHA block copolymers formed in situ at the early stage of the dispersion polymerization due to the reversible transfer process and played the role of particle stabilizer. The glass-transition temperature of the derived polymer films was not affected by the low amount of the...
-
Two dimensional chromatographic characterization of block copolymers of 2-Ethylhexyl Acrylate and methyl Acrylate, P2EHA-b-PMA, produced via RAFT-mediated polymerization in organic dispersion
Macromolecules, 2010Co-Authors: Jacquesantoine Raust, Bernadette Charleux, Lisa Houillot, Claudine Moire, Celine Farcet, M. Save, H. PaschAbstract:For the precise characterization of block copolymers of 2-Ethylhexyl Acrylate (2EHA) and methyl Acrylate (MA) produced via RAFT (reversible addition-fragmentation chain transfer)-mediated dispersion polymerization, novel liquid chromatographic separations have been developed. SEC showed multimodal molar mass distributions (MMD) and HPLC showed multimodal chemical composition distributions (CCD). The analyses of MMD and CCD of the reaction products indicated the formation of the expected block copolymer along with remaining P2EHA and PMA homopolymer fractions. Online coupling of SEC and gradient HPLC in a two-dimensional liquid chromatography (2D-LC) setup proved to be an efficient method to fractionate all polymer species present in the samples. Different kinds of copolymer molecules were identified in addition to the two homopolymers. The quantification of P2EHA using liquid chromatography at critical conditions (LC-CC) showed that the unreacted macro(RAFT agent) amount remained unchanged during at least the first 4 h of polymerization. LC-CC experiments also allowed the relative molar mass of the PMA blocks contained in the copolymers to be determined. The implementation of 2D-LC combining SEC and LC-CC allowed a more precise characterization of the different copolymer structures in particular in terms of block size. Finally, the results obtained by SEC/HPLC were confirmed by LC-1H NMR (proton nuclear magnetic resonance) experiments. It was concluded that the dispersed state of the polymerization system was the important factor for the formation of broadly distributed, complex copolymers when using a dithiobenzoate-based reactive macromolecular stabilizer. The detailed characterization of the system highlighted the enhancement of irreversible termination at the interface of the dispersed particles. © 2010 American Chemical Society.
-
Synthesis of well-defined polyAcrylate particle dispersions in organic medium using simultaneous RAFT polymerization and self-assembly of block copolymers. A strong influence of the selected thiocarbonylthio chain transfer agent
Macromolecules, 2007Co-Authors: Lisa Houillot, Chuong Bui, Bernadette Charleux, Jacquesantoine Raust, Claudine Moire, Celine Farcet, Maud Save, Ivan RodriguezAbstract:The RAFT-mediated nonaqueous dispersion polymerization of methyl Acrylate in isododecane, a nonsolvent for poly(methyl Acrylate), was carried out using two soluble poly(2-Ethylhexyl Acrylate) macromolecular RAFT agents, containing either a dithiobenzoate reactive function or a trithiocarbonate one. The method produced stable colloidal particles, with hydrodynamic diameters below 100 nm. Using poly(2-Ethylhexyl Acrylate) with a dithiobenzoate end group, strong rate retardation and poor control over the polymer chains were observed. In contrast, when the trithiocarbonate-functionalized poly(2-Ethylhexyl Acrylate) was used, the formation of monodisperse micellar aggregates of well-defined self-assembled block copolymers was obtained with fast polymerization rates, irrespective of the RAFT agent concentration. Such differences were explained by the dispersed state of the system rather than by the intrinsic reactivity of the soluble macromolecular RAFT agent.
Claudine Moire - One of the best experts on this subject based on the ideXlab platform.
-
two dimensional chromatographic characterization of block copolymers of 2 ethylhexyl Acrylate and methyl Acrylate p2eha b pma produced via raft mediated polymerization in organic dispersion
Macromolecules, 2010Co-Authors: Jacquesantoine Raust, Bernadette Charleux, Lisa Houillot, Claudine Moire, Celine Farcet, Maud Save, Harald PaschAbstract:For the precise characterization of block copolymers of 2-Ethylhexyl Acrylate (2EHA) and methyl Acrylate (MA) produced via RAFT (reversible addition−fragmentation chain transfer)-mediated dispersio...
-
dispersion polymerization of methyl Acrylate in nonpolar solvent stabilized by block copolymers formed in situ via the raft process
ACS Applied Materials & Interfaces, 2010Co-Authors: Lisa Houillot, Jacquesantoine Raust, Claudine Moire, Celine Farcet, Maud Save, Harald Pasch, Bernadette CharleuxAbstract:The free-radical dispersion polymerization of methyl Acrylate (MA) in isododecane was carried out in the presence of a poly(2-Ethylhexyl Acrylate) macromolecular RAFT (reversible addition−fragmentation chain transfer) agent bearing a trithiocarbonate reactive group in the middle of the chain (P2EHA-TTC). The presence of the trithiocarbonate function was crucial for the synthesis of monodisperse colloidal poly(methyl Acrylate) (PMA) particles stabilized by the P2EHA segments. The hydrodynamic diameters ranged from 100 to 300 nm, using particularly low amounts of the macro(RAFT agent) (1−6 wt % vs. MA) in dispersion polymerizations carried out at 20 wt % solids content. As shown by 2D liquid chromatography, P2EHA-b-PMA or P2EHA-b-PMA-b-P2EHA block copolymers formed in situ at the early stage of the dispersion polymerization due to the reversible transfer process and played the role of particle stabilizer. The glass-transition temperature of the derived polymer films was not affected by the low amount of the...
-
Two dimensional chromatographic characterization of block copolymers of 2-Ethylhexyl Acrylate and methyl Acrylate, P2EHA-b-PMA, produced via RAFT-mediated polymerization in organic dispersion
Macromolecules, 2010Co-Authors: Jacquesantoine Raust, Bernadette Charleux, Lisa Houillot, Claudine Moire, Celine Farcet, M. Save, H. PaschAbstract:For the precise characterization of block copolymers of 2-Ethylhexyl Acrylate (2EHA) and methyl Acrylate (MA) produced via RAFT (reversible addition-fragmentation chain transfer)-mediated dispersion polymerization, novel liquid chromatographic separations have been developed. SEC showed multimodal molar mass distributions (MMD) and HPLC showed multimodal chemical composition distributions (CCD). The analyses of MMD and CCD of the reaction products indicated the formation of the expected block copolymer along with remaining P2EHA and PMA homopolymer fractions. Online coupling of SEC and gradient HPLC in a two-dimensional liquid chromatography (2D-LC) setup proved to be an efficient method to fractionate all polymer species present in the samples. Different kinds of copolymer molecules were identified in addition to the two homopolymers. The quantification of P2EHA using liquid chromatography at critical conditions (LC-CC) showed that the unreacted macro(RAFT agent) amount remained unchanged during at least the first 4 h of polymerization. LC-CC experiments also allowed the relative molar mass of the PMA blocks contained in the copolymers to be determined. The implementation of 2D-LC combining SEC and LC-CC allowed a more precise characterization of the different copolymer structures in particular in terms of block size. Finally, the results obtained by SEC/HPLC were confirmed by LC-1H NMR (proton nuclear magnetic resonance) experiments. It was concluded that the dispersed state of the polymerization system was the important factor for the formation of broadly distributed, complex copolymers when using a dithiobenzoate-based reactive macromolecular stabilizer. The detailed characterization of the system highlighted the enhancement of irreversible termination at the interface of the dispersed particles. © 2010 American Chemical Society.
-
Synthesis of well-defined polyAcrylate particle dispersions in organic medium using simultaneous RAFT polymerization and self-assembly of block copolymers. A strong influence of the selected thiocarbonylthio chain transfer agent
Macromolecules, 2007Co-Authors: Lisa Houillot, Chuong Bui, Bernadette Charleux, Jacquesantoine Raust, Claudine Moire, Celine Farcet, Maud Save, Ivan RodriguezAbstract:The RAFT-mediated nonaqueous dispersion polymerization of methyl Acrylate in isododecane, a nonsolvent for poly(methyl Acrylate), was carried out using two soluble poly(2-Ethylhexyl Acrylate) macromolecular RAFT agents, containing either a dithiobenzoate reactive function or a trithiocarbonate one. The method produced stable colloidal particles, with hydrodynamic diameters below 100 nm. Using poly(2-Ethylhexyl Acrylate) with a dithiobenzoate end group, strong rate retardation and poor control over the polymer chains were observed. In contrast, when the trithiocarbonate-functionalized poly(2-Ethylhexyl Acrylate) was used, the formation of monodisperse micellar aggregates of well-defined self-assembled block copolymers was obtained with fast polymerization rates, irrespective of the RAFT agent concentration. Such differences were explained by the dispersed state of the system rather than by the intrinsic reactivity of the soluble macromolecular RAFT agent.
