The Experts below are selected from a list of 3039 Experts worldwide ranked by ideXlab platform
Bruno Ameduri - One of the best experts on this subject based on the ideXlab platform.
-
influence of trans 1 3 3 3 tetrafluoropropene on the structure properties relationship of vdf and trfe based Terpolymers
Macromolecules, 2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Pedro Marcelino Dos Santos Filho, Gilles Silly, Fabrice Domingues Dos Santos, Cedric Totee, Bruno AmeduriAbstract:trans-1,3,3,3-Tetrafluoropropene (1234ze) was copolymerized under free radical conditions with vinylidene fluoride (VDF) and trifluoroethylene (TrFE), for the first time, leading to statistical poly(VDF-ter-TrFE-ter-1234ze) electroactive Terpolymers. The reactivity ratios of the three comonomer couples were determined (rVDF = 0.77; rTrFE = 0.32), (rVDF = 1.67; r1234ze = 0.00), and (rTrFE = 7.56; r1234ze = 0.00), at 48 °C, using the nonlinear fitting Mayo–Lewis method. 1234ze was shown to be regularly incorporated in the terpolymer chains over the entire course of the reaction providing terpolymer chains with statistical monomer distribution and almost constant composition. These new VDF/TrFE-based Terpolymers were characterized by 1H and 19F liquid state NMR spectroscopy. The characteristic NMR signals of the VDF–1234ze dyads were identified by comparing the NMR spectral signatures of a poly(VDF82-co-1234ze18) copolymer and of a terpolymer. The thermal and electroactive properties of poly(VDF-ter-TrFE-ter...
-
Influence of trans-1,3,3,3-Tetrafluoropropene on the Structure–Properties Relationship of VDF- and TrFE-Based Terpolymers
2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Pedro Marcelino Dos Santos Filho, Cedric Totée, Gilles Silly, Fabrice Domingues Dos Santos, Bruno AmeduriAbstract:trans-1,3,3,3-Tetrafluoropropene (1234ze) was copolymerized under free radical conditions with vinylidene fluoride (VDF) and trifluoroethylene (TrFE), for the first time, leading to statistical poly(VDF-ter-TrFE-ter-1234ze) electroactive Terpolymers. The reactivity ratios of the three comonomer couples were determined (rVDF = 0.77; rTrFE = 0.32), (rVDF = 1.67; r1234ze = 0.00), and (rTrFE = 7.56; r1234ze = 0.00), at 48 °C, using the nonlinear fitting Mayo–Lewis method. 1234ze was shown to be regularly incorporated in the terpolymer chains over the entire course of the reaction providing terpolymer chains with statistical monomer distribution and almost constant composition. These new VDF/TrFE-based Terpolymers were characterized by 1H and 19F liquid state NMR spectroscopy. The characteristic NMR signals of the VDF–1234ze dyads were identified by comparing the NMR spectral signatures of a poly(VDF82-co-1234ze18) copolymer and of a terpolymer. The thermal and electroactive properties of poly(VDF-ter-TrFE-ter-1234ze) Terpolymers, with 1234ze content ranging from 0 to 6 mol % and molar masses above 55 kg/mol, were assessed. The randomly distributed 1234ze termonomer units induced the decreases of both the Curie and the melting temperatures of the terpolymer even at low termonomer content (TCurie = 70 °C and Tm = 126 °C and TCurie = 72 °C and Tm = 150 °C; for a poly(VDF69-ter-TrFE28-ter-1234ze3) terpolymer and a poly(VDF65-co-TrFE35) copolymer, respectively). Films of the Terpolymers were cast, and their electroactive properties were examined by D–E loops measurements. They showed that the presence of 1234ze decreased the remnant polarization (Pr = 45 mC/m2 for a poly(VDF65-co-TrFE35) copolymer to 28 mC/m2 for a poly(VDF69-ter-TrFE25-ter-1234ze6) terpolymer) probably because it also decreased the crystallinity of the terpolymer. The combination of the studies of the reactivity of the monomers, of the terpolymer microstructures, and of the assessment of their physical properties provides insights into their structure–property relationship
-
Differences in electroactive Terpolymers based on VDF, TrFE and 2,3,3,3-tetrafluoropropene prepared by batch solution and semi-continuous aqueous suspension polymerizations.
Polymer Chemistry, 2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Fabrice Santos-dominguez, Bruno AmeduriAbstract:In the search for new fluorinated electroactive copolymers, 0–8 mol% of 2,3,3,3-tetrafluoropropene (1234yf) was terpolymerized with vinylidene fluoride (VDF) and trifluoroethylene (TrFE). The reactivity in batch solution polymerization of 1234yf was evaluated. First, reactivity ratio measurements showed that homopropagation of 1234yf is favored compared to cross propagation with VDF or TrFE (rVDF-1234yf = 0.079, r1234yf-VDF = 2.6; and rTrFE-1234yf = 0.089, r1234yf-TrFE = 4.9, at 48 °C). Then, the study of a typical batch solution polymerization revealed that the polymerization time was not affected by the initial amount of 1234yf and that polymer chains with strong compositional heterogeneity were obtained. Based on these results, a semi-continuous aqueous suspension polymerization process was used for the synthesis of Terpolymers with a more homogeneous composition. Calculation of addition probabilities exemplified the changes in the drift of composition. The monomer sequences in the poly(VDF-ter-TrFE-ter-1234yf) Terpolymers, carefully studied by 19F NMR spectroscopy, were not affected by the polymerization process and were dominated by VDF-TrFE and VDF-1234yf dyads. Finally, the thermal and ferroelectric (FE) properties of the homogeneous and heterogeneous Terpolymers were characterized and compared. In the case of heterogeneous Terpolymers, increasing the 1234yf content from 0 to 6 mol% slightly decreased the crystal size and the overall crystallinity (Tm = 60 °C and ΔHm = 144 J g−1 for a poly(VDF66-ter-TrFE26-ter-1234yf8) terpolymer). On the contrary, for homogeneous Terpolymers, 5 mol% of 1234yf strongly affected both the Curie and melting transitions at TCurie = 37 °C and Tm = 107 °C. The reduced coercive field (Ec = 40 MV m−1) and remnant polarization (Pr = 22 mC m−2) for the homogeneous terpolymer compared to a reference poly(VDF65-co-TrFE35) (Ec = 62 MVm−1 and Pr = 45 mCm−2) transcribed modifications of the FE domains.
-
on the reactivity of α trifluoromethylstyrene in radical copolymerizations with various fluoroalkenes
European Polymer Journal, 2016Co-Authors: Justyna Walkowiakkulikowska, Frederic Boschet, Georgi Kostov, Veronique Gouverneur, Bruno AmeduriAbstract:Abstract The synthesis and radical co- and terpolymerizations of α -trifluoromethylstyrene (TFMST) with various fluorinated and hydrogenated comonomers are presented. The selected fluorinated comonomers were: vinylidene fluoride (VDF), chlorotrifluoroethylene (CTFE), 3,3,3-trifluoropropene (TFP), 1 H ,1 H ,2 H ,2 H -perfluoro-1-decyl vinyl ether (FAVE-8), while the hydrogenated one was ethyl vinyl ether (EVE). Though the homopolymerization and most copolymerizations of TFMST failed, the radical terpolymerization of TFMST with VDF and CTFE led to successful reaction in ca. 40–80% yield, when the TFMST feed was lower than 9 mol%. The resulting Terpolymers were characterized by 1 H and 19 F NMR spectroscopy that enabled to assess the molar percentages of the three comonomer units and revealed VDF-TFMST and CTFE-TFMST dyads besides expected VDF-VDF, VDF-CTFE, CTFE-CTFE dyads, and various triads composed of these monomers. Molecular weights were in the range of 2000–5000 g mol −1 indicating that oligomers were obtained. TGA under air indicated that poly (CTFE- ter -VDF- ter -TFMST) Terpolymers do not degrade below 150 °C, while DSC experiments confirmed the terpolymer structure as only a single glass transition temperature at about −35 °C.
-
new semi ipn pemfc membranes composed of crosslinked fluorinated copolymer bearing triazole groups and speek for operation at low relative humidity
International Journal of Hydrogen Energy, 2015Co-Authors: Bruno Ameduri, Benjamin Campagne, Ghislain David, Deborah J Jones, Jacques Roziere, Ivan RocheAbstract:Abstract The synthesis, processing, crosslinking, and characterization of original proton conducting membranes are presented. First, fluorinated Terpolymers were obtained from the radical terpolymerization of chlorotrifluoroethylene (CTFE), 2-chloroethyl vinyl ether (CEVE) and glycerine carbonate vinyl ether (GCVE) followed by two chemical modifications into poly(IEVE- alt -CTFE) x - g -1H-1,2,4-triazole-3-thiol- co -(GCVE- alt -CTFE) y terpolymer that bear dangling cyclocarbonate and triazole functions (where IEVE stands for 2-iodoethyl vinyl ether). The successful grafting (overall yields >80%) of these Terpolymers was monitored by 1 H and 19 F NMR spectroscopy and by thermal analyses (DSC and TGA) and did not shown any opening of the cyclocarbonate ring. Such fluorofunctional Terpolymers were involved in the preparation of blend membranes with sulfonated PEEK (sPEEK), followed by the crosslinking in the presence of two telechelic diamines of different chain lengths via cyclocarbonate/amine reaction. The characterizations of these resulting membranes (thickness = 35–50 μm) in term of thermal stability (>200 °C under air), water uptake (as low as −1 for a blend membrane containing 60%-wt of s-PEEK and 40%-wt of poly(CTFE- alt -IEVE) 82% - g -1H-1,2,4-triazole-3-thiol 86% - co -(CTFE- alt -GCVE) 18% terpolymer. They displayed glass transition temperatures, Young modulus and tensile strengths up to 223 °C, 4 MPa and 6%, respectively.
Timothy P Lodge - One of the best experts on this subject based on the ideXlab platform.
-
precisely tunable sol gel transition temperature by blending thermoresponsive abc triblock Terpolymers
ACS Macro Letters, 2018Co-Authors: Michika Onoda, Takeshi Ueki, Timothy P Lodge, Ryota Tamate, Aya Mizutani Akimoto, Cecilia Hall, Ryo YoshidaAbstract:Here, we report a facile methodology to control the sol–gel transition temperature (Tgel) of a physically cross-linked hydrogel by blending two kinds of ABC triblock Terpolymers. Well-defined triblock Terpolymers including thermosensitive N-isopropylacrylamide (NIPAAm), ABC1, and ABC2, were prepared by sequential reversible addition–fragmentation chain transfer polymerization. The chemical structure as well as the molecular weight of the A and B blocks for both polymers are identical, whereas the C blocks are different. The C block of ABC1 (C1) is a statistical copolymer of NIPAAm with hydrophobic n-butyl acrylate (BA), while that of ABC2 (C2) is a PNIPAAm homopolymer. Independently prepared ABC triblock terpolymer solutions exhibit well-defined sol–gel transitions. The Tgel of ABC1 is lower than that of ABC2 since hydrophobic BA is copolymerized into block C1. Remarkably, the Tgel varies linearly within this temperature range by simply blending the two polymers, while the resultant gel strength (∼G′) rem...
-
Precisely Tunable Sol–Gel Transition Temperature by Blending Thermoresponsive ABC Triblock Terpolymers
2018Co-Authors: Michika Onoda, Takeshi Ueki, Timothy P Lodge, Ryota Tamate, Aya Mizutani Akimoto, Cecilia C. Hall, Ryo YoshidaAbstract:Here, we report a facile methodology to control the sol–gel transition temperature (Tgel) of a physically cross-linked hydrogel by blending two kinds of ABC triblock Terpolymers. Well-defined triblock Terpolymers including thermosensitive N-isopropylacrylamide (NIPAAm), ABC1, and ABC2, were prepared by sequential reversible addition–fragmentation chain transfer polymerization. The chemical structure as well as the molecular weight of the A and B blocks for both polymers are identical, whereas the C blocks are different. The C block of ABC1 (C1) is a statistical copolymer of NIPAAm with hydrophobic n-butyl acrylate (BA), while that of ABC2 (C2) is a PNIPAAm homopolymer. Independently prepared ABC triblock terpolymer solutions exhibit well-defined sol–gel transitions. The Tgel of ABC1 is lower than that of ABC2 since hydrophobic BA is copolymerized into block C1. Remarkably, the Tgel varies linearly within this temperature range by simply blending the two polymers, while the resultant gel strength (∼G′) remains almost unchanged. Therefore, the Tgel can be precisely adjusted by the mixing ratio of the two polymers. This method for straightforward manipulation of Tgel has great potential for various soft material applications such as biomaterials for tissue engineering, drug delivery systems, and injectable gels
-
efficient formation of multicompartment hydrogels by stepwise self assembly of thermoresponsive abc triblock Terpolymers
Journal of the American Chemical Society, 2012Co-Authors: Can Zhou, Marc A Hillmyer, Timothy P LodgeAbstract:The gelation behavior of a poly(ethylene-alt-propylene)-b-poly(ethylene oxide)-b-poly(N-isopropylacrylamide) (PON) triblock terpolymer and a poly(N-isopropylacrylamide)-b-poly(ethylene oxide)-b-poly(N-isopropylacrylamide) (NON) triblock copolymer was studied by rheology over the concentration range 1–5 wt %. In comparison to the NON copolymer, gelation of the PON terpolymer was achieved at a much lower concentration, with a much sharper sol–gel transition. This is due to a stepwise gelation of PON Terpolymers involving micellization at room temperature and gelation at elevated temperatures. The separation of micellization and gelation leads to the formation of a two-compartment network as observed by cryoTEM. The results highlight the intricate and tunable nanostructures and new properties accessible from ABC terpolymer hydrogels.
-
morphologies of multicompartment micelles formed by abc miktoarm star Terpolymers
Langmuir, 2006Co-Authors: Marc A Hillmyer, Timothy P LodgeAbstract:Several new multicompartment micellar structures have been identified by cryogenic transmission electron microscopy (cryoTEM) from the aqueous self-assembly of mu-[poly(ethylethylene)][poly(ethylene oxide)][poly(perfluoropropylene oxide)] (mu-EOF) miktoarm star Terpolymers. This work extends our previous studies, in which it was found that, upon decreasing the length of the hydrophilic block (O), the resulting micelles evolved from "hamburger" micelles to segmented worms and ultimately to nanostructured bilayers and vesicles. In the Terpolymers examined here segmented ribbons and bilayers were found at an intermediate composition between segmented worms and nanostructured bilayers, provided that the fluoropolymer (F) was the minority component in the micelle core. On the other hand, when the F block exceeded the chain length of the hydrocarbon block (E), the superhydrophobic F block imposed a "double frustration" on the self-assembly of the mu-EOF(2-9-5) terpolymer; while F prefers to minimize its interfacial contact with the O corona, it must occupy the majority of the micellar core. Therefore, a richer variety of multicompartment micelles, including well-defined segmented worms, raspberry-like micelles, and multicompartmentalized worms, were formed from one terpolymer, as revealed by cryoTEM. Despite the complexity and variety of the observed aggregate morphologies, a small number of common structural elements can be invoked to interpret the observed micelles and to relate a given structure to the terpolymer composition.
Thibaut Soulestin - One of the best experts on this subject based on the ideXlab platform.
-
influence of trans 1 3 3 3 tetrafluoropropene on the structure properties relationship of vdf and trfe based Terpolymers
Macromolecules, 2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Pedro Marcelino Dos Santos Filho, Gilles Silly, Fabrice Domingues Dos Santos, Cedric Totee, Bruno AmeduriAbstract:trans-1,3,3,3-Tetrafluoropropene (1234ze) was copolymerized under free radical conditions with vinylidene fluoride (VDF) and trifluoroethylene (TrFE), for the first time, leading to statistical poly(VDF-ter-TrFE-ter-1234ze) electroactive Terpolymers. The reactivity ratios of the three comonomer couples were determined (rVDF = 0.77; rTrFE = 0.32), (rVDF = 1.67; r1234ze = 0.00), and (rTrFE = 7.56; r1234ze = 0.00), at 48 °C, using the nonlinear fitting Mayo–Lewis method. 1234ze was shown to be regularly incorporated in the terpolymer chains over the entire course of the reaction providing terpolymer chains with statistical monomer distribution and almost constant composition. These new VDF/TrFE-based Terpolymers were characterized by 1H and 19F liquid state NMR spectroscopy. The characteristic NMR signals of the VDF–1234ze dyads were identified by comparing the NMR spectral signatures of a poly(VDF82-co-1234ze18) copolymer and of a terpolymer. The thermal and electroactive properties of poly(VDF-ter-TrFE-ter...
-
Influence of trans-1,3,3,3-Tetrafluoropropene on the Structure–Properties Relationship of VDF- and TrFE-Based Terpolymers
2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Pedro Marcelino Dos Santos Filho, Cedric Totée, Gilles Silly, Fabrice Domingues Dos Santos, Bruno AmeduriAbstract:trans-1,3,3,3-Tetrafluoropropene (1234ze) was copolymerized under free radical conditions with vinylidene fluoride (VDF) and trifluoroethylene (TrFE), for the first time, leading to statistical poly(VDF-ter-TrFE-ter-1234ze) electroactive Terpolymers. The reactivity ratios of the three comonomer couples were determined (rVDF = 0.77; rTrFE = 0.32), (rVDF = 1.67; r1234ze = 0.00), and (rTrFE = 7.56; r1234ze = 0.00), at 48 °C, using the nonlinear fitting Mayo–Lewis method. 1234ze was shown to be regularly incorporated in the terpolymer chains over the entire course of the reaction providing terpolymer chains with statistical monomer distribution and almost constant composition. These new VDF/TrFE-based Terpolymers were characterized by 1H and 19F liquid state NMR spectroscopy. The characteristic NMR signals of the VDF–1234ze dyads were identified by comparing the NMR spectral signatures of a poly(VDF82-co-1234ze18) copolymer and of a terpolymer. The thermal and electroactive properties of poly(VDF-ter-TrFE-ter-1234ze) Terpolymers, with 1234ze content ranging from 0 to 6 mol % and molar masses above 55 kg/mol, were assessed. The randomly distributed 1234ze termonomer units induced the decreases of both the Curie and the melting temperatures of the terpolymer even at low termonomer content (TCurie = 70 °C and Tm = 126 °C and TCurie = 72 °C and Tm = 150 °C; for a poly(VDF69-ter-TrFE28-ter-1234ze3) terpolymer and a poly(VDF65-co-TrFE35) copolymer, respectively). Films of the Terpolymers were cast, and their electroactive properties were examined by D–E loops measurements. They showed that the presence of 1234ze decreased the remnant polarization (Pr = 45 mC/m2 for a poly(VDF65-co-TrFE35) copolymer to 28 mC/m2 for a poly(VDF69-ter-TrFE25-ter-1234ze6) terpolymer) probably because it also decreased the crystallinity of the terpolymer. The combination of the studies of the reactivity of the monomers, of the terpolymer microstructures, and of the assessment of their physical properties provides insights into their structure–property relationship
-
Differences in electroactive Terpolymers based on VDF, TrFE and 2,3,3,3-tetrafluoropropene prepared by batch solution and semi-continuous aqueous suspension polymerizations.
Polymer Chemistry, 2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Fabrice Santos-dominguez, Bruno AmeduriAbstract:In the search for new fluorinated electroactive copolymers, 0–8 mol% of 2,3,3,3-tetrafluoropropene (1234yf) was terpolymerized with vinylidene fluoride (VDF) and trifluoroethylene (TrFE). The reactivity in batch solution polymerization of 1234yf was evaluated. First, reactivity ratio measurements showed that homopropagation of 1234yf is favored compared to cross propagation with VDF or TrFE (rVDF-1234yf = 0.079, r1234yf-VDF = 2.6; and rTrFE-1234yf = 0.089, r1234yf-TrFE = 4.9, at 48 °C). Then, the study of a typical batch solution polymerization revealed that the polymerization time was not affected by the initial amount of 1234yf and that polymer chains with strong compositional heterogeneity were obtained. Based on these results, a semi-continuous aqueous suspension polymerization process was used for the synthesis of Terpolymers with a more homogeneous composition. Calculation of addition probabilities exemplified the changes in the drift of composition. The monomer sequences in the poly(VDF-ter-TrFE-ter-1234yf) Terpolymers, carefully studied by 19F NMR spectroscopy, were not affected by the polymerization process and were dominated by VDF-TrFE and VDF-1234yf dyads. Finally, the thermal and ferroelectric (FE) properties of the homogeneous and heterogeneous Terpolymers were characterized and compared. In the case of heterogeneous Terpolymers, increasing the 1234yf content from 0 to 6 mol% slightly decreased the crystal size and the overall crystallinity (Tm = 60 °C and ΔHm = 144 J g−1 for a poly(VDF66-ter-TrFE26-ter-1234yf8) terpolymer). On the contrary, for homogeneous Terpolymers, 5 mol% of 1234yf strongly affected both the Curie and melting transitions at TCurie = 37 °C and Tm = 107 °C. The reduced coercive field (Ec = 40 MV m−1) and remnant polarization (Pr = 22 mC m−2) for the homogeneous terpolymer compared to a reference poly(VDF65-co-TrFE35) (Ec = 62 MVm−1 and Pr = 45 mCm−2) transcribed modifications of the FE domains.
-
Importance of Microstructure Control for Designing New Electroactive Terpolymers Based on Vinylidene Fluoride and Trifluoroethylene
2015Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Fabrice Domingues Dos Santos, Bruno AmeduriAbstract:A new family of electroactive fluorinated Terpolymers of vinylidene fluoride (VDF), trifluoroethylene (TrFE) and 3,3,3-trifluoropropene (TFP) is presented. Statistical poly(VDF-ter-TrFE-ter-TFP) Terpolymers with a VDF/TrFE molar ratio of ca. 65/35 and a TFP composition ranging from 0 to 10 mol % were prepared in high yields by free radical terpolymerization in dimethyl carbonate (DMC), initiated by a symmetrical peroxydicarbonate initiator. The choice of TFP as a termonomer was driven by the potential property of the CF3 side groups to limit crystal growth and potentially favor the formation of nanodomains known to enhance electrostrictive properties. For the first time, the reactivity ratios of the TrFE/TFP (rTrFE = 0.13 and rTFP = 3.72 at 48 °C) couple were determined using the Kelen–Tudos linear method, and used in combination with VDF/TrFE and VDF/TFP reactivity ratios to better understand the structures of the Terpolymers. Detailed 1H and 19F solution NMR spectroscopic studies were performed and afforded the in-depth characterization of the Terpolymers microstructures. The examination of the terpolymer’s composition as a function of the three monomers conversions revealed a strong structural heterogeneity where a 62/33/5 VDF/TrFE/TFP initial monomer composition resulted in a 47/11/42 poly(VDF-ter-TrFE-ter-TFP) terpolymer at low conversion. It was indeed found that TFP preferentially homopolymerizes despite its low initial concentration. The influence of the TFP units on the thermal transitions (TCurie = 65 °C and Tm = 148 °C for a 67/28/5 poly(VDF-ter-TrFE-ter-TFP) terpolymer), thermal stability and electroactivity (Ec = 63 MV/m at 150 MV/m) was also examined. The combination of the determination of the monomers’ reactivity ratios of the terpolymer microstructures and of the assessment of the physical properties of the Terpolymers provided insights on the structure–property relationship of the poly(VDF-ter-TrFE-ter-TFP) Terpolymers
Vincent Ladmiral - One of the best experts on this subject based on the ideXlab platform.
-
influence of trans 1 3 3 3 tetrafluoropropene on the structure properties relationship of vdf and trfe based Terpolymers
Macromolecules, 2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Pedro Marcelino Dos Santos Filho, Gilles Silly, Fabrice Domingues Dos Santos, Cedric Totee, Bruno AmeduriAbstract:trans-1,3,3,3-Tetrafluoropropene (1234ze) was copolymerized under free radical conditions with vinylidene fluoride (VDF) and trifluoroethylene (TrFE), for the first time, leading to statistical poly(VDF-ter-TrFE-ter-1234ze) electroactive Terpolymers. The reactivity ratios of the three comonomer couples were determined (rVDF = 0.77; rTrFE = 0.32), (rVDF = 1.67; r1234ze = 0.00), and (rTrFE = 7.56; r1234ze = 0.00), at 48 °C, using the nonlinear fitting Mayo–Lewis method. 1234ze was shown to be regularly incorporated in the terpolymer chains over the entire course of the reaction providing terpolymer chains with statistical monomer distribution and almost constant composition. These new VDF/TrFE-based Terpolymers were characterized by 1H and 19F liquid state NMR spectroscopy. The characteristic NMR signals of the VDF–1234ze dyads were identified by comparing the NMR spectral signatures of a poly(VDF82-co-1234ze18) copolymer and of a terpolymer. The thermal and electroactive properties of poly(VDF-ter-TrFE-ter...
-
Influence of trans-1,3,3,3-Tetrafluoropropene on the Structure–Properties Relationship of VDF- and TrFE-Based Terpolymers
2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Pedro Marcelino Dos Santos Filho, Cedric Totée, Gilles Silly, Fabrice Domingues Dos Santos, Bruno AmeduriAbstract:trans-1,3,3,3-Tetrafluoropropene (1234ze) was copolymerized under free radical conditions with vinylidene fluoride (VDF) and trifluoroethylene (TrFE), for the first time, leading to statistical poly(VDF-ter-TrFE-ter-1234ze) electroactive Terpolymers. The reactivity ratios of the three comonomer couples were determined (rVDF = 0.77; rTrFE = 0.32), (rVDF = 1.67; r1234ze = 0.00), and (rTrFE = 7.56; r1234ze = 0.00), at 48 °C, using the nonlinear fitting Mayo–Lewis method. 1234ze was shown to be regularly incorporated in the terpolymer chains over the entire course of the reaction providing terpolymer chains with statistical monomer distribution and almost constant composition. These new VDF/TrFE-based Terpolymers were characterized by 1H and 19F liquid state NMR spectroscopy. The characteristic NMR signals of the VDF–1234ze dyads were identified by comparing the NMR spectral signatures of a poly(VDF82-co-1234ze18) copolymer and of a terpolymer. The thermal and electroactive properties of poly(VDF-ter-TrFE-ter-1234ze) Terpolymers, with 1234ze content ranging from 0 to 6 mol % and molar masses above 55 kg/mol, were assessed. The randomly distributed 1234ze termonomer units induced the decreases of both the Curie and the melting temperatures of the terpolymer even at low termonomer content (TCurie = 70 °C and Tm = 126 °C and TCurie = 72 °C and Tm = 150 °C; for a poly(VDF69-ter-TrFE28-ter-1234ze3) terpolymer and a poly(VDF65-co-TrFE35) copolymer, respectively). Films of the Terpolymers were cast, and their electroactive properties were examined by D–E loops measurements. They showed that the presence of 1234ze decreased the remnant polarization (Pr = 45 mC/m2 for a poly(VDF65-co-TrFE35) copolymer to 28 mC/m2 for a poly(VDF69-ter-TrFE25-ter-1234ze6) terpolymer) probably because it also decreased the crystallinity of the terpolymer. The combination of the studies of the reactivity of the monomers, of the terpolymer microstructures, and of the assessment of their physical properties provides insights into their structure–property relationship
-
Differences in electroactive Terpolymers based on VDF, TrFE and 2,3,3,3-tetrafluoropropene prepared by batch solution and semi-continuous aqueous suspension polymerizations.
Polymer Chemistry, 2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Fabrice Santos-dominguez, Bruno AmeduriAbstract:In the search for new fluorinated electroactive copolymers, 0–8 mol% of 2,3,3,3-tetrafluoropropene (1234yf) was terpolymerized with vinylidene fluoride (VDF) and trifluoroethylene (TrFE). The reactivity in batch solution polymerization of 1234yf was evaluated. First, reactivity ratio measurements showed that homopropagation of 1234yf is favored compared to cross propagation with VDF or TrFE (rVDF-1234yf = 0.079, r1234yf-VDF = 2.6; and rTrFE-1234yf = 0.089, r1234yf-TrFE = 4.9, at 48 °C). Then, the study of a typical batch solution polymerization revealed that the polymerization time was not affected by the initial amount of 1234yf and that polymer chains with strong compositional heterogeneity were obtained. Based on these results, a semi-continuous aqueous suspension polymerization process was used for the synthesis of Terpolymers with a more homogeneous composition. Calculation of addition probabilities exemplified the changes in the drift of composition. The monomer sequences in the poly(VDF-ter-TrFE-ter-1234yf) Terpolymers, carefully studied by 19F NMR spectroscopy, were not affected by the polymerization process and were dominated by VDF-TrFE and VDF-1234yf dyads. Finally, the thermal and ferroelectric (FE) properties of the homogeneous and heterogeneous Terpolymers were characterized and compared. In the case of heterogeneous Terpolymers, increasing the 1234yf content from 0 to 6 mol% slightly decreased the crystal size and the overall crystallinity (Tm = 60 °C and ΔHm = 144 J g−1 for a poly(VDF66-ter-TrFE26-ter-1234yf8) terpolymer). On the contrary, for homogeneous Terpolymers, 5 mol% of 1234yf strongly affected both the Curie and melting transitions at TCurie = 37 °C and Tm = 107 °C. The reduced coercive field (Ec = 40 MV m−1) and remnant polarization (Pr = 22 mC m−2) for the homogeneous terpolymer compared to a reference poly(VDF65-co-TrFE35) (Ec = 62 MVm−1 and Pr = 45 mCm−2) transcribed modifications of the FE domains.
-
Importance of Microstructure Control for Designing New Electroactive Terpolymers Based on Vinylidene Fluoride and Trifluoroethylene
2015Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Fabrice Domingues Dos Santos, Bruno AmeduriAbstract:A new family of electroactive fluorinated Terpolymers of vinylidene fluoride (VDF), trifluoroethylene (TrFE) and 3,3,3-trifluoropropene (TFP) is presented. Statistical poly(VDF-ter-TrFE-ter-TFP) Terpolymers with a VDF/TrFE molar ratio of ca. 65/35 and a TFP composition ranging from 0 to 10 mol % were prepared in high yields by free radical terpolymerization in dimethyl carbonate (DMC), initiated by a symmetrical peroxydicarbonate initiator. The choice of TFP as a termonomer was driven by the potential property of the CF3 side groups to limit crystal growth and potentially favor the formation of nanodomains known to enhance electrostrictive properties. For the first time, the reactivity ratios of the TrFE/TFP (rTrFE = 0.13 and rTFP = 3.72 at 48 °C) couple were determined using the Kelen–Tudos linear method, and used in combination with VDF/TrFE and VDF/TFP reactivity ratios to better understand the structures of the Terpolymers. Detailed 1H and 19F solution NMR spectroscopic studies were performed and afforded the in-depth characterization of the Terpolymers microstructures. The examination of the terpolymer’s composition as a function of the three monomers conversions revealed a strong structural heterogeneity where a 62/33/5 VDF/TrFE/TFP initial monomer composition resulted in a 47/11/42 poly(VDF-ter-TrFE-ter-TFP) terpolymer at low conversion. It was indeed found that TFP preferentially homopolymerizes despite its low initial concentration. The influence of the TFP units on the thermal transitions (TCurie = 65 °C and Tm = 148 °C for a 67/28/5 poly(VDF-ter-TrFE-ter-TFP) terpolymer), thermal stability and electroactivity (Ec = 63 MV/m at 150 MV/m) was also examined. The combination of the determination of the monomers’ reactivity ratios of the terpolymer microstructures and of the assessment of the physical properties of the Terpolymers provided insights on the structure–property relationship of the poly(VDF-ter-TrFE-ter-TFP) Terpolymers
Thierry Lannuzel - One of the best experts on this subject based on the ideXlab platform.
-
influence of trans 1 3 3 3 tetrafluoropropene on the structure properties relationship of vdf and trfe based Terpolymers
Macromolecules, 2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Pedro Marcelino Dos Santos Filho, Gilles Silly, Fabrice Domingues Dos Santos, Cedric Totee, Bruno AmeduriAbstract:trans-1,3,3,3-Tetrafluoropropene (1234ze) was copolymerized under free radical conditions with vinylidene fluoride (VDF) and trifluoroethylene (TrFE), for the first time, leading to statistical poly(VDF-ter-TrFE-ter-1234ze) electroactive Terpolymers. The reactivity ratios of the three comonomer couples were determined (rVDF = 0.77; rTrFE = 0.32), (rVDF = 1.67; r1234ze = 0.00), and (rTrFE = 7.56; r1234ze = 0.00), at 48 °C, using the nonlinear fitting Mayo–Lewis method. 1234ze was shown to be regularly incorporated in the terpolymer chains over the entire course of the reaction providing terpolymer chains with statistical monomer distribution and almost constant composition. These new VDF/TrFE-based Terpolymers were characterized by 1H and 19F liquid state NMR spectroscopy. The characteristic NMR signals of the VDF–1234ze dyads were identified by comparing the NMR spectral signatures of a poly(VDF82-co-1234ze18) copolymer and of a terpolymer. The thermal and electroactive properties of poly(VDF-ter-TrFE-ter...
-
Influence of trans-1,3,3,3-Tetrafluoropropene on the Structure–Properties Relationship of VDF- and TrFE-Based Terpolymers
2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Pedro Marcelino Dos Santos Filho, Cedric Totée, Gilles Silly, Fabrice Domingues Dos Santos, Bruno AmeduriAbstract:trans-1,3,3,3-Tetrafluoropropene (1234ze) was copolymerized under free radical conditions with vinylidene fluoride (VDF) and trifluoroethylene (TrFE), for the first time, leading to statistical poly(VDF-ter-TrFE-ter-1234ze) electroactive Terpolymers. The reactivity ratios of the three comonomer couples were determined (rVDF = 0.77; rTrFE = 0.32), (rVDF = 1.67; r1234ze = 0.00), and (rTrFE = 7.56; r1234ze = 0.00), at 48 °C, using the nonlinear fitting Mayo–Lewis method. 1234ze was shown to be regularly incorporated in the terpolymer chains over the entire course of the reaction providing terpolymer chains with statistical monomer distribution and almost constant composition. These new VDF/TrFE-based Terpolymers were characterized by 1H and 19F liquid state NMR spectroscopy. The characteristic NMR signals of the VDF–1234ze dyads were identified by comparing the NMR spectral signatures of a poly(VDF82-co-1234ze18) copolymer and of a terpolymer. The thermal and electroactive properties of poly(VDF-ter-TrFE-ter-1234ze) Terpolymers, with 1234ze content ranging from 0 to 6 mol % and molar masses above 55 kg/mol, were assessed. The randomly distributed 1234ze termonomer units induced the decreases of both the Curie and the melting temperatures of the terpolymer even at low termonomer content (TCurie = 70 °C and Tm = 126 °C and TCurie = 72 °C and Tm = 150 °C; for a poly(VDF69-ter-TrFE28-ter-1234ze3) terpolymer and a poly(VDF65-co-TrFE35) copolymer, respectively). Films of the Terpolymers were cast, and their electroactive properties were examined by D–E loops measurements. They showed that the presence of 1234ze decreased the remnant polarization (Pr = 45 mC/m2 for a poly(VDF65-co-TrFE35) copolymer to 28 mC/m2 for a poly(VDF69-ter-TrFE25-ter-1234ze6) terpolymer) probably because it also decreased the crystallinity of the terpolymer. The combination of the studies of the reactivity of the monomers, of the terpolymer microstructures, and of the assessment of their physical properties provides insights into their structure–property relationship
-
Differences in electroactive Terpolymers based on VDF, TrFE and 2,3,3,3-tetrafluoropropene prepared by batch solution and semi-continuous aqueous suspension polymerizations.
Polymer Chemistry, 2017Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Fabrice Santos-dominguez, Bruno AmeduriAbstract:In the search for new fluorinated electroactive copolymers, 0–8 mol% of 2,3,3,3-tetrafluoropropene (1234yf) was terpolymerized with vinylidene fluoride (VDF) and trifluoroethylene (TrFE). The reactivity in batch solution polymerization of 1234yf was evaluated. First, reactivity ratio measurements showed that homopropagation of 1234yf is favored compared to cross propagation with VDF or TrFE (rVDF-1234yf = 0.079, r1234yf-VDF = 2.6; and rTrFE-1234yf = 0.089, r1234yf-TrFE = 4.9, at 48 °C). Then, the study of a typical batch solution polymerization revealed that the polymerization time was not affected by the initial amount of 1234yf and that polymer chains with strong compositional heterogeneity were obtained. Based on these results, a semi-continuous aqueous suspension polymerization process was used for the synthesis of Terpolymers with a more homogeneous composition. Calculation of addition probabilities exemplified the changes in the drift of composition. The monomer sequences in the poly(VDF-ter-TrFE-ter-1234yf) Terpolymers, carefully studied by 19F NMR spectroscopy, were not affected by the polymerization process and were dominated by VDF-TrFE and VDF-1234yf dyads. Finally, the thermal and ferroelectric (FE) properties of the homogeneous and heterogeneous Terpolymers were characterized and compared. In the case of heterogeneous Terpolymers, increasing the 1234yf content from 0 to 6 mol% slightly decreased the crystal size and the overall crystallinity (Tm = 60 °C and ΔHm = 144 J g−1 for a poly(VDF66-ter-TrFE26-ter-1234yf8) terpolymer). On the contrary, for homogeneous Terpolymers, 5 mol% of 1234yf strongly affected both the Curie and melting transitions at TCurie = 37 °C and Tm = 107 °C. The reduced coercive field (Ec = 40 MV m−1) and remnant polarization (Pr = 22 mC m−2) for the homogeneous terpolymer compared to a reference poly(VDF65-co-TrFE35) (Ec = 62 MVm−1 and Pr = 45 mCm−2) transcribed modifications of the FE domains.
-
Importance of Microstructure Control for Designing New Electroactive Terpolymers Based on Vinylidene Fluoride and Trifluoroethylene
2015Co-Authors: Thibaut Soulestin, Vincent Ladmiral, Thierry Lannuzel, Fabrice Domingues Dos Santos, Bruno AmeduriAbstract:A new family of electroactive fluorinated Terpolymers of vinylidene fluoride (VDF), trifluoroethylene (TrFE) and 3,3,3-trifluoropropene (TFP) is presented. Statistical poly(VDF-ter-TrFE-ter-TFP) Terpolymers with a VDF/TrFE molar ratio of ca. 65/35 and a TFP composition ranging from 0 to 10 mol % were prepared in high yields by free radical terpolymerization in dimethyl carbonate (DMC), initiated by a symmetrical peroxydicarbonate initiator. The choice of TFP as a termonomer was driven by the potential property of the CF3 side groups to limit crystal growth and potentially favor the formation of nanodomains known to enhance electrostrictive properties. For the first time, the reactivity ratios of the TrFE/TFP (rTrFE = 0.13 and rTFP = 3.72 at 48 °C) couple were determined using the Kelen–Tudos linear method, and used in combination with VDF/TrFE and VDF/TFP reactivity ratios to better understand the structures of the Terpolymers. Detailed 1H and 19F solution NMR spectroscopic studies were performed and afforded the in-depth characterization of the Terpolymers microstructures. The examination of the terpolymer’s composition as a function of the three monomers conversions revealed a strong structural heterogeneity where a 62/33/5 VDF/TrFE/TFP initial monomer composition resulted in a 47/11/42 poly(VDF-ter-TrFE-ter-TFP) terpolymer at low conversion. It was indeed found that TFP preferentially homopolymerizes despite its low initial concentration. The influence of the TFP units on the thermal transitions (TCurie = 65 °C and Tm = 148 °C for a 67/28/5 poly(VDF-ter-TrFE-ter-TFP) terpolymer), thermal stability and electroactivity (Ec = 63 MV/m at 150 MV/m) was also examined. The combination of the determination of the monomers’ reactivity ratios of the terpolymer microstructures and of the assessment of the physical properties of the Terpolymers provided insights on the structure–property relationship of the poly(VDF-ter-TrFE-ter-TFP) Terpolymers
