Jean-françois Pilard - Academia.edu (original) (raw)
Papers by Jean-françois Pilard
ChemPhysChem, 2013
A simple route to form a mixed 16 organic layer on a metallic surface is described: 17 it consist... more A simple route to form a mixed 16 organic layer on a metallic surface is described: 17 it consists in the electrografting from two 18 different diazoniums salts generated in situ in an 19 electrochemical cell. A mixture of sulphanilic acid 20 and aniline treated in situ by NaNO 2 in acidic 21 medium (HCl 1M), at room temperature, led to 22
Journal of Applied Polymer Science, 2016
Journal of Polymer Science Part B Polymer Physics
New segmented polyurethanes (thermoplastic-elastomers) based on previously described hydroxytelec... more New segmented polyurethanes (thermoplastic-elastomers) based on previously described hydroxytelechelic cis-1,4-polyisoprene (HTPI), miscellaneous isocyanates and chain extenders at various equivalent ratios were prepared by the classical one-shot method. The influence of the nature of isocyanate and chain extender, as well as their equivalent ratios, on the mechanical and thermal materials behavior was investigated. Thus, a comparative assessment of material properties was performed. Microphase separation of hard and soft segments was observed by DMTA, DSC and AFM. Moreover, according to Thermogravimetric Analysis (TGA), linear relationships depending on the isocyanate and chain extender nature were found between the weight loss (%) and the percentages of hard segments. A classification of thermal stability in terms of weight loss was established. With the aim of a thermo-mechanical comparative study, polyurethane elastomers based on HTPI and isocyanates without chain extender, were...
Polymer, 2005
Carbonyl telechelic cis-1,4-oligoisoprene (CTPI) obtained from high molecular weight polyisoprene... more Carbonyl telechelic cis-1,4-oligoisoprene (CTPI) obtained from high molecular weight polyisoprene through an oxidative chain cleavage reaction have been chemically modified. Thus, new well defined amino telechelic cis-1,4-oligoisoprenes have been obtained in a mass range of 1600-2300 g/mol according to two different pathways. The first approach involved a standard mesylate displacement by sodium azide followed by smooth reduction using triphenylphosphine. The second pathway implied a reductive amination sequence. Primary or secondary amine functions have thus been selectively obtained at both oligomer chain-ends depending on reaction conditions. Peculiar NMR experiments conducted on these functional oligomers confirmed a precise control of functionality during the chemical modification. Moreover, their abilities to react with toluene diisocyanate or bis(succinimidyl)carbonate have been investigated. q
Tetrahedron Letters, 2000
The synthesis of a polyamine precursor was performed at a modified electrode interface. The chemi... more The synthesis of a polyamine precursor was performed at a modified electrode interface. The chemical behaviour of the polythiophene matrix appeared identical to that of polystyrene beads. The target molecule, obtained with good yield, was released from the solid support by cathodic S-N bond scission, using the conducting properties of the polymer.
ChemBioChem, 2014
Transposases are specific DNA-binding proteins that promote the mobility of discrete DNA segments... more Transposases are specific DNA-binding proteins that promote the mobility of discrete DNA segments. We used a combination of physicochemical approaches to describe the association of MOS1 (an eukaryotic transposase) with its specific target DNA, an event corresponding to the first steps of the transposition cycle. Because the kinetic constants of the reaction are still unknown, we aimed to determine them by using quartz crystal microbalance on two sources of recombinant MOS1: one produced in insect cells and the other produced in bacteria. The prokaryotic-expressed MOS1 showed no cooperativity and displayed a Kd of about 300 nM. In contrast, the eukaryotic-expressed MOS1 generated a cooperative system, with a lower Kd (∼ 2 nm). The origins of these differences were investigated by IR spectroscopy and AFM imaging. Both support the conclusion that prokaryotic- and eukaryotic-expressed MOS1 are not similarly folded, thereby resulting in differences in the early steps of transposition.
Advanced Materials Research, 2011
Waterborne Polyurethane: Effect of Functional Groups in Aromatic Isocyanate and the Chain Length ... more Waterborne Polyurethane: Effect of Functional Groups in Aromatic Isocyanate and the Chain Length of Hydroxyl Terminated Natural Rubber Lalita Kaenhin 1,a , Pairote Klinpituksa 2,b , Adisai Rungvichaniwat 1,c ... Vol. 117 (2010), p. 1279 [3] X. Wei, Y. Ying and X. Yu: J. Appl. ...
Spectroscopy Letters, 2014
ABSTRACT Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy is classi... more ABSTRACT Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy is classically used to monitor homopolymerizations. In this article, this analytical technique was extended to monitor the synthesis of VIVIPRINT 300, which is a copolymer of 2-hydroxyethyl methacrylate (HEMA) and N-[3-dimethylaminopropyl]methacrylamide (DMAPMA). The calibration curves devised for this study were based on the two homopolymers P(HEMA) and P(DMAPMA). A good correlation was realized between the FTIR absorbance intensities observed respectively at 1300 cm−1 (polymerized C-O ester bond) and 1230 cm−1 (polymerized C-N amide bond) and the level of residual HEMA and DMAPMA monomers determined by GC. Application of these calibration curves to the copolymerization also exhibited a good correlation of data relating to residual monomer determination by FTIR and GC, validating the success of this spectroscopic in situ technique.
A simple and fast electrochemical process for gold surface functionalization aimed to immobilize ... more A simple and fast electrochemical process for gold surface functionalization aimed to immobilize biomolecules is presented here. Raman spectroscopy was used to characterize the complete system starting from surface functionalization to final structure with immobilized proteins.
Materials Science Forum, 2011
... Wannarat Panwiriyarat 1,a , Varaporn Tanrattanakul 1,b* , Pilard Jean-François 2,c and Chuanp... more ... Wannarat Panwiriyarat 1,a , Varaporn Tanrattanakul 1,b* , Pilard Jean-François 2,c and Chuanpit Khaokong 1,d ... [7] Heijkants, RGJC Calck, RV Tienen, TG Groot, JH Buma, P. Pennings, AJ Veth, RPH Schouten, AJ Biomaterials, 26 (2005) 4219. Fig. ...
Journal of Applied Polymer Science, 2014
ABSTRACT The accumulation of waste tires is a big environmental issue and different approaches ha... more ABSTRACT The accumulation of waste tires is a big environmental issue and different approaches have been proposed to eliminate or recycle this material in the end of its life. However, each approach presents drawbacks and the need for a real valorization of the tire components is still of interest. In a previous work by our group, it was demonstrated that an oxidative cleavage of the polyisoprene and polybutadiene chains contained in the tires led to the synthesis of telechelic oligomers with a ketone and an aldehyde at the chains ends. In this work, the process to obtain these carbonyl oligomers has been improved, with a particular concern for the elimination of the maximum amount of carbon black. The carbonyl oligomers can be easily reduced to hydroxyl oligomers and, in order to show the benefit of the recycling process, an application of these hydroxyl oligomers is reported: they have been used as building blocks (polyol precursors) in the preparation of polyurethane (PU) foams. The morphology of the resulting foams was observed by scanning electron microscopy technique: the images showed an almost open-cell structure and a homogeneous distribution of cell size. Mechanical (tensile and compressive strength) and thermal properties of PU foams synthesized from “recycled” oligomers from waste tires were compared to those of PU foams synthesized from analogue oligomers derived from natural rubber. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41326.
Tetrahedron Letters, 2001
The synthesis of new chiral auxiliaries was performed onto conducting polythiophene. The electroc... more The synthesis of new chiral auxiliaries was performed onto conducting polythiophene. The electrochemical behaviour of such a matrix was investigated and one of them present a noticeable stability when an adequate spacer is introduced between the redox centre and the chiral unit.
Tetrahedron Letters, 2007
The first selective reductive amination of carbonyl telechelic oligoisoprene (CTPI) using NaBH(OA... more The first selective reductive amination of carbonyl telechelic oligoisoprene (CTPI) using NaBH(OAc) 3 as the reducing agent is described. An access to tri-and tetrafunctionalized oligoisoprenes is realized in two or three steps from CTPI in high yield.
Polymer, 2009
The first [4+2] inverse electrodemand heterocycloaddition between hydroxytelechelic oligoisoprene... more The first [4+2] inverse electrodemand heterocycloaddition between hydroxytelechelic oligoisoprenes and the benzylidene pyruvic methyl ester promoted by tin tetrachloride is described. A partial hydrogenation of hydroxytelechelic oligoisoprenes was necessary to selectively promote the cycloaddition.
New Journal of Chemistry, 2007
Electrochemical behaviour of a functionalized fluorenylidene 1 is studied in comparison with a cy... more Electrochemical behaviour of a functionalized fluorenylidene 1 is studied in comparison with a cyclopentadithiophene analogue 2. The influence of the main aromatic group on the electropolymerization ability is reported. We demonstrated that the lack of sulfur atoms in the monomer structure leads to an absence of polymerization due to the spin density located on the methylidene bridge in the radical cation. From modelling considerations, we have evaluated the participation of the methylidene bridge in the p-doping process. The good correlation between the p-doping level and the partial atomic charge carried by the methylidene bridge for poly(2) and poly indicates that an extension of the conjugated area improves the p-doping level when the side chain is electronically connected to the main chain of polymer. w The HTML version of this article has been enhanced with additional colour images. z Electronic supplementary information (ESI) available: Optimized Cartesian coordinates and corresponding energies for 1 0 , 2 0 and 3 (both neutral and radical cation species). Complete listing of Mulliken and NPA spin densities and of CHelpG, NPA and MKS charges. See
Macromolecules, 2011
ABSTRACT
Macromolecular Symposia, 2010
ABSTRACT Composite polyurethane/polyaniline (PU/PANI) films have been chemically prepared by oxid... more ABSTRACT Composite polyurethane/polyaniline (PU/PANI) films have been chemically prepared by oxidative in-situ polymerization of aniline inside the previously swelled PU film. Swelling kinetic studies have shown that for PU films the swelling degree of aniline is 25 wt.%. The dielectric and electrical properties of the composite films were measured using dielectric relaxation spectroscopy and four-probe method. Dielectric measurements as a function of temperature and frequency revealed the presence of a relaxation process for the composite PU/PANI-HCl film. This relaxation was explained in terms of interfacial polarization due to the double-layered structure of the composite film. The activation energy values found by dielectric and electrical measurements are close and this result confirms the conducting character of the PANI containing layer.
Journal of Polymers and the Environment, 2013
Natural rubber grafted with poly(vinyl acetate) copolymer (NR-g-PVAc) was synthesized by emulsion... more Natural rubber grafted with poly(vinyl acetate) copolymer (NR-g-PVAc) was synthesized by emulsion polymerization. Three graft copolymers were prepared with different PVAc contents: 1 % (G1), 5 % (G5) and 12 % (G12). Poly(lactic acid) (PLA) was melt blended with natural rubber (NR) and/or NR-g-PVAc in a twin screw extruder. The blends contained 10-20 wt% rubber. The notched Izod impact strength and tensile properties were determined from the compression molded specimens. The effect of NR mastication on the mechanical properties of the PLA/NR/NR-g-PVAc blend was evaluated. Characterization by DMTA and DSC showed an enhancement in miscibility of the PLA/NR-g-PVAc blend. The temperature of the maximum tan d of the PLA decreased with increasing PVAc content in the graft copolymer, i.e., from 71°C (pure PLA) to 63°C (the blend containing 10 % G12). The increase in miscibility brought about a reduction in the rubber particle diameter. These changes were attributed to the enhancement of toughness and ductility of PLA after blending with NR-g-PVAc. Therefore, NR-g-PVAc could be used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. NR mastication was an efficient method for increasing the toughness and ductility of the blends which depended on the blend composition and the number of mastications.
Journal of Polymers and the Environment, 2013
Novel polyurethanes were successfully synthesized by a one-shot polymerization. They contained po... more Novel polyurethanes were successfully synthesized by a one-shot polymerization. They contained poly(e-caprolactone) diol (PCL diol) and hydroxyl telechelic natural rubber (HTNR) as the soft segment. The effect of the NCO:OH molar ratio (0.75:1.00-2.25:1.00), chain extender and PCL:HTNR molar ratio (1:1, 0.7:0.3 and 0.3:0.7) on the thermal and mechanical properties of the resulting polyurethane were investigated. FTIR analysis showed the presence of urethane linkages and crosslinking or chain branching. The derived polyurethanes demonstrated excellent mechanical properties, which depended on their chemical composition. Their tensile behavior seemed to have typical elastomeric characteristics. Polyurethanes became amorphous and showed a phase separation between the PCL diol and HTNR segments. The phase separation between the soft and the hard segments was observed by the DMTA technique whereas DSC results showed only the glass transition temperatures of the soft segment. The longer and more flexible chain and non-polarity of HTNR was responsible of a decrease in the mechanical properties and transition temperatures.
ChemPhysChem, 2013
A simple route to form a mixed 16 organic layer on a metallic surface is described: 17 it consist... more A simple route to form a mixed 16 organic layer on a metallic surface is described: 17 it consists in the electrografting from two 18 different diazoniums salts generated in situ in an 19 electrochemical cell. A mixture of sulphanilic acid 20 and aniline treated in situ by NaNO 2 in acidic 21 medium (HCl 1M), at room temperature, led to 22
Journal of Applied Polymer Science, 2016
Journal of Polymer Science Part B Polymer Physics
New segmented polyurethanes (thermoplastic-elastomers) based on previously described hydroxytelec... more New segmented polyurethanes (thermoplastic-elastomers) based on previously described hydroxytelechelic cis-1,4-polyisoprene (HTPI), miscellaneous isocyanates and chain extenders at various equivalent ratios were prepared by the classical one-shot method. The influence of the nature of isocyanate and chain extender, as well as their equivalent ratios, on the mechanical and thermal materials behavior was investigated. Thus, a comparative assessment of material properties was performed. Microphase separation of hard and soft segments was observed by DMTA, DSC and AFM. Moreover, according to Thermogravimetric Analysis (TGA), linear relationships depending on the isocyanate and chain extender nature were found between the weight loss (%) and the percentages of hard segments. A classification of thermal stability in terms of weight loss was established. With the aim of a thermo-mechanical comparative study, polyurethane elastomers based on HTPI and isocyanates without chain extender, were...
Polymer, 2005
Carbonyl telechelic cis-1,4-oligoisoprene (CTPI) obtained from high molecular weight polyisoprene... more Carbonyl telechelic cis-1,4-oligoisoprene (CTPI) obtained from high molecular weight polyisoprene through an oxidative chain cleavage reaction have been chemically modified. Thus, new well defined amino telechelic cis-1,4-oligoisoprenes have been obtained in a mass range of 1600-2300 g/mol according to two different pathways. The first approach involved a standard mesylate displacement by sodium azide followed by smooth reduction using triphenylphosphine. The second pathway implied a reductive amination sequence. Primary or secondary amine functions have thus been selectively obtained at both oligomer chain-ends depending on reaction conditions. Peculiar NMR experiments conducted on these functional oligomers confirmed a precise control of functionality during the chemical modification. Moreover, their abilities to react with toluene diisocyanate or bis(succinimidyl)carbonate have been investigated. q
Tetrahedron Letters, 2000
The synthesis of a polyamine precursor was performed at a modified electrode interface. The chemi... more The synthesis of a polyamine precursor was performed at a modified electrode interface. The chemical behaviour of the polythiophene matrix appeared identical to that of polystyrene beads. The target molecule, obtained with good yield, was released from the solid support by cathodic S-N bond scission, using the conducting properties of the polymer.
ChemBioChem, 2014
Transposases are specific DNA-binding proteins that promote the mobility of discrete DNA segments... more Transposases are specific DNA-binding proteins that promote the mobility of discrete DNA segments. We used a combination of physicochemical approaches to describe the association of MOS1 (an eukaryotic transposase) with its specific target DNA, an event corresponding to the first steps of the transposition cycle. Because the kinetic constants of the reaction are still unknown, we aimed to determine them by using quartz crystal microbalance on two sources of recombinant MOS1: one produced in insect cells and the other produced in bacteria. The prokaryotic-expressed MOS1 showed no cooperativity and displayed a Kd of about 300 nM. In contrast, the eukaryotic-expressed MOS1 generated a cooperative system, with a lower Kd (∼ 2 nm). The origins of these differences were investigated by IR spectroscopy and AFM imaging. Both support the conclusion that prokaryotic- and eukaryotic-expressed MOS1 are not similarly folded, thereby resulting in differences in the early steps of transposition.
Advanced Materials Research, 2011
Waterborne Polyurethane: Effect of Functional Groups in Aromatic Isocyanate and the Chain Length ... more Waterborne Polyurethane: Effect of Functional Groups in Aromatic Isocyanate and the Chain Length of Hydroxyl Terminated Natural Rubber Lalita Kaenhin 1,a , Pairote Klinpituksa 2,b , Adisai Rungvichaniwat 1,c ... Vol. 117 (2010), p. 1279 [3] X. Wei, Y. Ying and X. Yu: J. Appl. ...
Spectroscopy Letters, 2014
ABSTRACT Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy is classi... more ABSTRACT Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy is classically used to monitor homopolymerizations. In this article, this analytical technique was extended to monitor the synthesis of VIVIPRINT 300, which is a copolymer of 2-hydroxyethyl methacrylate (HEMA) and N-[3-dimethylaminopropyl]methacrylamide (DMAPMA). The calibration curves devised for this study were based on the two homopolymers P(HEMA) and P(DMAPMA). A good correlation was realized between the FTIR absorbance intensities observed respectively at 1300 cm−1 (polymerized C-O ester bond) and 1230 cm−1 (polymerized C-N amide bond) and the level of residual HEMA and DMAPMA monomers determined by GC. Application of these calibration curves to the copolymerization also exhibited a good correlation of data relating to residual monomer determination by FTIR and GC, validating the success of this spectroscopic in situ technique.
A simple and fast electrochemical process for gold surface functionalization aimed to immobilize ... more A simple and fast electrochemical process for gold surface functionalization aimed to immobilize biomolecules is presented here. Raman spectroscopy was used to characterize the complete system starting from surface functionalization to final structure with immobilized proteins.
Materials Science Forum, 2011
... Wannarat Panwiriyarat 1,a , Varaporn Tanrattanakul 1,b* , Pilard Jean-François 2,c and Chuanp... more ... Wannarat Panwiriyarat 1,a , Varaporn Tanrattanakul 1,b* , Pilard Jean-François 2,c and Chuanpit Khaokong 1,d ... [7] Heijkants, RGJC Calck, RV Tienen, TG Groot, JH Buma, P. Pennings, AJ Veth, RPH Schouten, AJ Biomaterials, 26 (2005) 4219. Fig. ...
Journal of Applied Polymer Science, 2014
ABSTRACT The accumulation of waste tires is a big environmental issue and different approaches ha... more ABSTRACT The accumulation of waste tires is a big environmental issue and different approaches have been proposed to eliminate or recycle this material in the end of its life. However, each approach presents drawbacks and the need for a real valorization of the tire components is still of interest. In a previous work by our group, it was demonstrated that an oxidative cleavage of the polyisoprene and polybutadiene chains contained in the tires led to the synthesis of telechelic oligomers with a ketone and an aldehyde at the chains ends. In this work, the process to obtain these carbonyl oligomers has been improved, with a particular concern for the elimination of the maximum amount of carbon black. The carbonyl oligomers can be easily reduced to hydroxyl oligomers and, in order to show the benefit of the recycling process, an application of these hydroxyl oligomers is reported: they have been used as building blocks (polyol precursors) in the preparation of polyurethane (PU) foams. The morphology of the resulting foams was observed by scanning electron microscopy technique: the images showed an almost open-cell structure and a homogeneous distribution of cell size. Mechanical (tensile and compressive strength) and thermal properties of PU foams synthesized from “recycled” oligomers from waste tires were compared to those of PU foams synthesized from analogue oligomers derived from natural rubber. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41326.
Tetrahedron Letters, 2001
The synthesis of new chiral auxiliaries was performed onto conducting polythiophene. The electroc... more The synthesis of new chiral auxiliaries was performed onto conducting polythiophene. The electrochemical behaviour of such a matrix was investigated and one of them present a noticeable stability when an adequate spacer is introduced between the redox centre and the chiral unit.
Tetrahedron Letters, 2007
The first selective reductive amination of carbonyl telechelic oligoisoprene (CTPI) using NaBH(OA... more The first selective reductive amination of carbonyl telechelic oligoisoprene (CTPI) using NaBH(OAc) 3 as the reducing agent is described. An access to tri-and tetrafunctionalized oligoisoprenes is realized in two or three steps from CTPI in high yield.
Polymer, 2009
The first [4+2] inverse electrodemand heterocycloaddition between hydroxytelechelic oligoisoprene... more The first [4+2] inverse electrodemand heterocycloaddition between hydroxytelechelic oligoisoprenes and the benzylidene pyruvic methyl ester promoted by tin tetrachloride is described. A partial hydrogenation of hydroxytelechelic oligoisoprenes was necessary to selectively promote the cycloaddition.
New Journal of Chemistry, 2007
Electrochemical behaviour of a functionalized fluorenylidene 1 is studied in comparison with a cy... more Electrochemical behaviour of a functionalized fluorenylidene 1 is studied in comparison with a cyclopentadithiophene analogue 2. The influence of the main aromatic group on the electropolymerization ability is reported. We demonstrated that the lack of sulfur atoms in the monomer structure leads to an absence of polymerization due to the spin density located on the methylidene bridge in the radical cation. From modelling considerations, we have evaluated the participation of the methylidene bridge in the p-doping process. The good correlation between the p-doping level and the partial atomic charge carried by the methylidene bridge for poly(2) and poly indicates that an extension of the conjugated area improves the p-doping level when the side chain is electronically connected to the main chain of polymer. w The HTML version of this article has been enhanced with additional colour images. z Electronic supplementary information (ESI) available: Optimized Cartesian coordinates and corresponding energies for 1 0 , 2 0 and 3 (both neutral and radical cation species). Complete listing of Mulliken and NPA spin densities and of CHelpG, NPA and MKS charges. See
Macromolecules, 2011
ABSTRACT
Macromolecular Symposia, 2010
ABSTRACT Composite polyurethane/polyaniline (PU/PANI) films have been chemically prepared by oxid... more ABSTRACT Composite polyurethane/polyaniline (PU/PANI) films have been chemically prepared by oxidative in-situ polymerization of aniline inside the previously swelled PU film. Swelling kinetic studies have shown that for PU films the swelling degree of aniline is 25 wt.%. The dielectric and electrical properties of the composite films were measured using dielectric relaxation spectroscopy and four-probe method. Dielectric measurements as a function of temperature and frequency revealed the presence of a relaxation process for the composite PU/PANI-HCl film. This relaxation was explained in terms of interfacial polarization due to the double-layered structure of the composite film. The activation energy values found by dielectric and electrical measurements are close and this result confirms the conducting character of the PANI containing layer.
Journal of Polymers and the Environment, 2013
Natural rubber grafted with poly(vinyl acetate) copolymer (NR-g-PVAc) was synthesized by emulsion... more Natural rubber grafted with poly(vinyl acetate) copolymer (NR-g-PVAc) was synthesized by emulsion polymerization. Three graft copolymers were prepared with different PVAc contents: 1 % (G1), 5 % (G5) and 12 % (G12). Poly(lactic acid) (PLA) was melt blended with natural rubber (NR) and/or NR-g-PVAc in a twin screw extruder. The blends contained 10-20 wt% rubber. The notched Izod impact strength and tensile properties were determined from the compression molded specimens. The effect of NR mastication on the mechanical properties of the PLA/NR/NR-g-PVAc blend was evaluated. Characterization by DMTA and DSC showed an enhancement in miscibility of the PLA/NR-g-PVAc blend. The temperature of the maximum tan d of the PLA decreased with increasing PVAc content in the graft copolymer, i.e., from 71°C (pure PLA) to 63°C (the blend containing 10 % G12). The increase in miscibility brought about a reduction in the rubber particle diameter. These changes were attributed to the enhancement of toughness and ductility of PLA after blending with NR-g-PVAc. Therefore, NR-g-PVAc could be used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. NR mastication was an efficient method for increasing the toughness and ductility of the blends which depended on the blend composition and the number of mastications.
Journal of Polymers and the Environment, 2013
Novel polyurethanes were successfully synthesized by a one-shot polymerization. They contained po... more Novel polyurethanes were successfully synthesized by a one-shot polymerization. They contained poly(e-caprolactone) diol (PCL diol) and hydroxyl telechelic natural rubber (HTNR) as the soft segment. The effect of the NCO:OH molar ratio (0.75:1.00-2.25:1.00), chain extender and PCL:HTNR molar ratio (1:1, 0.7:0.3 and 0.3:0.7) on the thermal and mechanical properties of the resulting polyurethane were investigated. FTIR analysis showed the presence of urethane linkages and crosslinking or chain branching. The derived polyurethanes demonstrated excellent mechanical properties, which depended on their chemical composition. Their tensile behavior seemed to have typical elastomeric characteristics. Polyurethanes became amorphous and showed a phase separation between the PCL diol and HTNR segments. The phase separation between the soft and the hard segments was observed by the DMTA technique whereas DSC results showed only the glass transition temperatures of the soft segment. The longer and more flexible chain and non-polarity of HTNR was responsible of a decrease in the mechanical properties and transition temperatures.