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This report is the first one on a cationic waterborne polyurethane (cWPU) latex based on epoxidized hydroxyl telechelic natural rubber (eHTNR) polyol, providing potential for use as a coating made of renewable resources. A cWPU latex was synthesized by step growth emulsion polymerization from hydroxyl telechelic natural rubber (HTNR with M n = 3000 g.mol―1) with fixed N-methyl diethanol amine content of 5.6 wt% and 2,4-toluene diisocyanate (NCO index = 100). The effects of proportion of epoxide units on HTNR polyol from 0 to 30 % on preparing cWPU latex were investigated. Chemical structures of HTNR and eHTNR polyol were confirmed by 1H-NMR spectroscopy. The resulting HTNR and eHTNR polyols present a unimodal size exclusion chromatography trace. The viscosity increased with epoxide fraction. The synthesized cWPU latex based on eHTNR was a stable milky-blue emulsion with well-defined size dispersion. All cWPU-eHTNR films showed good wettability, good chemical resistance, and high thermal stability, improving with the proportion of epoxide units. The mechanical properties of cWPU-eHTNR films were studied from their stress-strain curves. Moreover, the electrical properties were investigated. The cWPU-eHTNR films showed relatively low conductivity. Wettability, chemical resistance, adhesion, thermal stability, and electrical properties of cWPU-HTNR films improved with the proportion of epoxide units on the HTNR polyol. These results demonstrate a new synthesis route to develop cWPU latex based on a biosource, for coating applications.

International audience; Renewable resource based cationic waterborne polyurethanes (cWPUs) have been prepared from hydroxyl telechelic natural rubber (HTNR) with a range of number average molecular weights (Mn) (2820, 1800, and 950 g mol−1), toluene-2,4-diisocyanate (TDI), N-methyl diethanolamine (NMDEA), and ethylene glycol (EG). The chemical structure of the cWPUs was confirmed by FT-IR and 1H NMR. Particle size and zeta potential of prepared cWPUs were also characterized by ZS nanosizer. By varying the levels of Mn of HTNR, the obtained cWPUs were stable with a milky blue appearance, forming yellowish films. The smallest particle sizes of 76.4 nm were achieved using Mn of HTNR of 2820 g mol−1 while zeta potential value ranges from 67 to 71 mV were observed with increasing Mn of HTNR. Lap shear testing of these WPUs indicates their potential in real cow leather adhesive applications, with the best adhesive result coming from cWPU based on an HTNR molecular weight of 1800 g mol−1. The results show the potential of natural rubber as a green adhesive material in suitable aqueous environments.

International audience; This paper reports on the synthesis and physical properties of conducting composites based on polyaniline and polystyrene. Polyaniline composite powders are synthesized by oxidative polymerization in an acidic medium. Thermal properties are characterized by thermo gravimetric analysis and differential scanning calorimetry. UV-Visible absorption spectroscopy is also used to study the optical properties of the deposited films. The optical gap decreases from 4.6 eV to 2.7 eV with increasing polyaniline content from 0.5 to 5 wt. % confirming the improvement of the semi-conductive properties. Due to the absorption properties in near infrared of the thin composite layers they can be promising materials for optoelectronic and photovoltaic applications.

Commercial surfactants, which are inexpensive and abundant, were covalently grafted to flat and transparent electrodes, and it appears to be a simple functionalization route to design biomembrane sensors at large-scale production. Sparsely tethered bilayer lipid membranes (stBLM) were stabilized using such molecular coatings composed of diluted anchor-harpoon surfactants that grab the membrane with an alkyl chain out of a PEGylated-hydrogel layer, which acts as a soft hydration cushion. The goal of avoiding the synthesis of complex organic molecules to scale up sensors was achieved here by grafting nonionic diblock oligomers (Brij58 = C xH2 x+1(OCH2CH2) nOH with x = 16 and n = 23) and PEO short chains ((OCH2CH2) nOH with n = 9 and n = 23) from their hydroxyl (-OH) end-moiety to a monolayer of -Ar-SO2Cl groups, which are easy to form on electrodes (metals, semiconducting materials, ...) from aryl-diazonium salt reduction. A hybrid molecular coating on gold, with scarce Ar-SO2-Brij58 and PEO oligomers, was used to monitor immobilization and fusion kinetics of DOPC small unilamellar vesicles (SUV) by both quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) techniques. Using flat and transparent thin chromium film electrodes, we designed biosensors to couple surface sensitive techniques for membranes, including X-ray reflectivity (XRR), atomic force microscopy (AFM) with subnanometer resolution, and optical microscopy, such as fluorescence recovery after photobleaching measurements (FRAP), in addition to electrochemistry techniques (cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS)). The advantages of this biomembrane-sensing platform are discussed for research and applications.

Grafting commercial surfactants appears to be a simple way to modify electrodes and conducting interfaces, avoiding the synthesis of complex organic molecules. A new surface functionalization route is presented to build surfactant coatings with monolayer thickness grafting molecules considered as nonreactive. A monolayer of -SO2Cl functions (from a p-benzenesulfonyl chloride) was first electrografted. It showed a high reactivity toward weak nucleophiles commonly found on surfactant end-moieties such as hydroxyl groups (-OH), and it was used to covalently graft the following: (1) nonionic diblock oligomers (Brij or CiEj, CxH2x + (OCH2CH2)nOH with x = 16 and n = 23 for Brij58, x = 16 and n = 10 for Brij C10, and x = 16 and n = 2 for Brij52); (2) poly(ethylene glycol) (PEG) short chains (PEO9 for (OCH2CH2)nOH with n = 9) and mixed formula. The surface modification due to these molecular coatings was investigated in terms of wetting properties and interfacial electrochemistry characteristics (charge transfer ...

Linear and crosslinked polyhydroxyurethanes (PHUs) based on natural rubber (NR) were synthesized by a polyaddition reaction without a solvent or catalyst to exploit the reactivity of diamines or triamines with dicyclic carbonate groups. Oligo-isoprenes were obtained from the controlled oxidative degradation of NR and successive modifications of the chain ends. The syntheses of linear PHU were carried out with two approaches. The first one consisted of a reaction between amino telechelic oligo-isoprenes and aromatic or aliphatic dicyclic carbonates. The second approach proceeded through a reaction between oligo-isoprenes bearing cyclic carbonate chain ends and difunctional or trifunctional amines. The evolution of these reactions was studied by Fourier transform infrared spectrometry. The influence of the carbonate-to-amine molar ratio, the chain length of the oligo-isoprenes, and the reaction temperatures were investigated. The thermal properties of the PHUs were studied by differential scanning calorimetry and thermogravimetric analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45427.

International audience; A controlled degradation process enabling Natural Rubber (NR) depolymerization and using the olefin metathesis reaction in ionic liquid medium is reported. Using trihexyl-(tetradecyl)phosphonium chloride (Cyphos101) and N,N-dioctylimidazolium bromide (C8C8ImBr), low-dispersity telechelic polymers are produced. With N,N-dioctylimidazolium bromide (C8C8ImBr), the degradation process could be performed for five consecutive cycles with excellent control. This degradation process was successfully applied to waste tires.

Bio-based polyurethane foam (PUF) was synthesized by a one-shot polymerization using hydroxyl telechelic natural rubber (HTNR) and polycaprolactone (PCL) diols as a soft segment. The effect of HTNR/PCL diol molar ratio (1/0, 1/0.5, 1/1 and 0.5/1) on the foam formation rate and physical and mechanical properties of the resulting PUF was investigated. The formation of urethane linkage and cross-linked structure were confirmed by FTIR analysis. The foams observed by scanning electron microscope revealed to have almost closed cells. The molar ratio of HTNR/PCL diol affected the foam formation rate, the average diameter of cell, the regularity of cell shape, the elongation at break and the compressive strength. The foam density slightly changed with this molar ratio whereas the specific tensile strength of all samples was in the same range. All PUFs showed relatively high compression set. The biodegradability was assessed according to a modified Sturm test. Low density polyethylene and sodium benzoate were used as a negative and positive control sample, respectively. PUF samples showed an induction time of 33 days in which the percentage of biodegradation was ~7–11 %. At the end of testing (60 days), the highest degradation (45.6 %) was found in the sample containing 1/0.5 of HTNR/PCL diol molar ratio.

International audience; Rubber is a widely available potential carbon neutral resource, both as native natural rubber state and as vulcanized state in waste tires. Herein, we describe a model synthesis of acrylate telechelic natural rubber (AcTNR) oligomers and the use of such oligomers to prepare novel acrylate resins. AcTNR oligomers are synthesized according to a two steps procedure implying a controlled C = C bond's scission of high-molecular-weight natural rubber and a further chain ends functionalization. The molar mass of the resulting AcTNR is found to be 2300 g/mol as determined by 1H NMR. AcTNR-based resins are then prepared by mixing AcTNR oligomers with various reactive diluents (RD) such as styrene, 1,4-butanediol ether, tri(propylene glycol) diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate (AcTNR:RD weight ratio 7:3). These bio-based resins are afterward cured in the presence of methyl ethyl ketone peroxide as initiator and cobalt octoate as accelerator at 80 °C and postcured at 120 °C. The cured resins offer a wide range of mechanical, thermal, and dynamic-mechanical performances. This approach could be extended to rubber tire wastes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43548.

Natural Rubber (NR) based Polyurethanes (PU) with phosphorylated polymers as chain extenders were studied. Two types of polymers were investigated: poly-phosphonate and poly-phosphate synthesized using a RAFT methodology. Two molecular weights (5000 and 3000 g mol −1 ) were targeted with dispersity close to 1.1. The PU films were prepared from a liquid Hydroxyl Telechelic Natural Rubber (HTNR) which was obtained through a controlled degradation. The mass percentage of the chain extenders added in the PU film was varied from 1 to 8%. The films were analysed using FTIR and Raman spectroscopy. A Raman mapping in particular was used to observe the phosphorus distribution in the PU film. In the case of the poly-phosphonate chain extender, the results highlighted that only with shorter chain lengths ( n = 13), a homogeneous distribution was observed.

Fast monitoring and control quality of food products become increasingly important for public health. Among foodborne pathogenic microorganisms, bacteria are the most common foodborne pathogens in which the currently used methods are time consuming, labour-intensive and costly. This work aims to develop a new biochip potentially used for an assessment of bacterial contamination on food product. An assessment for bacterial detection employs simple FTIR spectroscopic analysis with a complimentary surface characterization by SEM technique. The biochip based on carboxylic acid functionalized polyurethane (PU) film was synthesized for bacterial detection in particular Salmonella Typhimurium. The PU in this study was synthesized from the reaction of the alcohol groups of hydroxyl telechelic natural rubber based oligomer with the isocyanate groups of 2,4-toluene diisocyanate. The carboxylic acid functional group was incorporated into the PU chain by addition of dimethylol propionic acid as a chain extender during PU preparation. The PU film having different degree of carboxylic acid was explored for the detection of S. Typhimurium. The structural and morphological changes of the PU film after loading of the bacteria were successfully detected using ATR-FTIR and SEM, respectively. The PU film developed is considered a rapid tool for S. Typhimurium detection and has a potential application for rapid food control quality.

International audience; 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.

Three thiophene rings bearing n-ethoxy arylsulfonamide pendant groups were synthesized and their electropolymerization was performed at a platinum electrode. The electrochemical behaviour of the polythiophene matrix was studied both in organic and in aqueous solvent. If all polymers present a reversible n- and p-doping process in organic solvents, only one of them particularly possess a reversible p-doping in aqueous media. This phenomenon was shown to be directly related to the nature of the spacer between the thiophene ring and the aryl sulfonamide unit. Keywords: Solid phase synthesis, Aryl sulfonamide pendant unit, Modified cathode, Anodic polymerization

A novel fluorenylidene containing a ferrocene unit has been electropolymerized. In this polymer, the ferrocene unit is grafted to the main polyfluorenylidene chain as a pendant group. The polymer is electroactive in non-aqueous and aqueous media. Keywords: Anodic polymerization, Fluorenylidene, Polyfluorene, p-doping process, Post-functionalization, Ferrocenyl pendant unit

In the medical field, attached bacteria can cause infections associated with catheters, incisions, burns, and medical implants especially in immunocompromised patients. The problem is exacerbated by the fact that attached bacteria are ∼1000 times more resistant to antibiotics than planktonic cells. The rapid spread of antibiotic resistance in these and other organisms has led to a significant need to find new methods for preventing bacterial attachment. The goal of this research was to evaluate the effectiveness of novel polymer coatings to prevent the attachment of three medically relevant bacteria. Tests were conducted with Pseudomonas aeruginosa, Staphylococcus epidermidis, and Staphylococcus aureus for oligomers derived from modifications of natural rubber (cis 1,4-polyisoprene). The different oligomers were: PP04, with no quaternary ammonium (QA); MV067, one QA; PP06, three QA groups. In almost all experiments, cell attachment was inhibited to various extents as long as the oligomers were used. PP06 was the most effective as it decreased the planktonic cell numbers by at least 50% for all bacteria. Differences between species sensitivity were also observed. P. aeruginosa was the most resistant bacteria tested, S. aureus, the most sensitive. Further experiments are required to understand the full extent and mode of the antimicrobial properties of these surfaces.

International audience; So simple: The in situ synthesis of an aryldiazonium salt and an azo-aryldiazonium salt by azo coupling from sulfanilic acid and aniline is reported. Formation of a mixed organic layer is monitored by cyclic voltammetry and atomic force microscopy. A compact mixed layer is obtained with a global roughness of 0.4 nm and 10-15 % vertical extension in the range 1.5-6 nm.

International audience; Previous studies have demonstrated that ionic and non-ionic natural rubber-based coatings inhibit adhesion and growth of marine bacteria, fungi, microalgae, and spores of macroalgae. Nevertheless, the mechanism of action of these coatings on the different micro-organisms is not known. In the current study, antifouling activity of a series of these rubber-based coatings (one ionic and two non-ionic) was studied with respect to impacts on marine microalgal photosynthesis using pulse-amplitude-modulation (PAM) fluorescence. When grown in contact with the three different coatings, an inhibition of photosynthetic rate (relative electron transport rate, rETR) was observed in all of the four species of pennate diatoms involved in microfouling, Cocconeis scutellum, Amphora coffeaeformis, Cylindrotheca closterium, and Navicula jeffreyi. The percentage of inhibition ranged from 44% to 100% of the controls, depending on the species and the coating. The ionic coating was the most efficient antifouling (AF) treatment, and C. scutellum and A. coffeaeformis are the most sensitive and tolerant diatoms tested, respectively. Photosynthetic inhibition was reversible, as almost complete recovery of rETR was observed 48 h post exposure, after detachment of cells from the coatings. Thus, the antifouling activity seemed mostly due to an effect of contact with materials. It is hypothesized that photosynthetic activity was suppressed by coatings due to interference in calcium availability to the microalgal cells; Ca(2+) has been shown to be an essential micro/macro nutrient for photosynthesis, as well as being involved in cell adhesion and motility in pennate diatoms

International audience; Un polymère de type polythiophène comportant des groupements chlorure de parabenzenesulfonile a été synthétisé par voie électrochimique afin d'obtenir une surface destinée à ` l'immobilisation rapide et efficiente de biomolécules. Graceà une liaison sulfonamide, une protéine A a ainsi été fixée pour permettre l'accroche et l'orientation d'un anticorps spécifique. Le dispositif a pu être testé pour piéger une bactérie pathogène ''Salmonella enterica paratyphi''. La présence de la bactérie sur la surface a e ´té vérifiée conjointement par microbalance a ` quartz et par spectroscopie Raman. Les résultats obtenus ont e ´té comparés a ` ceux obtenus sur une surface d'or fonctionnalisée selon le même procédé et ils témoignent de la très grande réactivité de la surface polymère. Ce procédé de fonctionnalisation de surface, facile a ` mettre en oeuvre, spécifique et peu coûteux, constitue, par couplage avec la technique de diffusion Raman, une méthode alternative potentielle de détection et identification rapide de micro-organismes pathogènes.; A simple electrochemical procedure was used for the synthesis of a polythiophene containing para-ben-zenesulfonyl chloride groups. The obtained polymer was shown to be very reactive and directly able to covalently bind nucleophile biomolecules. Protein A and a specific antibody were then successively immobilized on the conductive polymer through a covalent bonding of Protein A with the as-prepared linker for bacteria trapping purpose. All reactions were controlled in situ by cyclic voltammetry, quartz crystal microbalance and Raman spectroscopy. The results were compared to those previously obtained on gold surface modified with the same chemical linker. The conductive polymer led to a very high rate of antibody recognition compared to the gold surface and to literature, probably due to a large available surface obtained after polymerization. One example of pathogenic bacteria ''Salmonella enterica paratyphi'' detection was successfully tested on the substrates. The presented results are promising for the future design of simple and inexpensive immunocapture-based sensors

Salmonella is a major cause of foodborne illness worldwide and is not allowed to be present in any food in all countries. The purpose of this study is to develop a simple alternative method for the detection of Salmonella based on functionalized polyethylene (PE) surfaces. Salmonella Typhimurium was used as a model bacterium. PE film was treated using dielectric plasma in order to alter the wettability of the PE surface and consequently introduce functionality on the surface. The PE film characterized by ATR-FTIR spectroscopy revealed the presence of C O stretching of ketones, aldehydes and carboxylic acids. The antibodies against O or H antigens of Salmonella and S. Typhimurium were then respectively immobilized on the PE surface after activation of the carboxylic group using NHS/EDC followed by protein A. The evidences from ATR-FTIR, scanning electron microscopy and optical microscopy showed the presence of S. Typhimurium attached to the plasma treated PE surfaces via the two types of anti-Salmonella antibody. The plasma treated PE film developed is simple and allows efficient association of bacterial cells on the treated surfaces without the necessity of time-consuming centrifugation and washing steps for isolation of the cells. This material is considered to be a smart material applicable for S. Typhimurium detection.

Interaction and surface binding characteristics of staphylococcal protein A (SpA) and an anti-Escherichia coli immunoglobulin G (IgG) were studied using the Raman spectroscopy. The tyrosine amino acid residues present in the α-helix structure of SpA were found to be involved in interaction with IgG. In bulk interaction condition the native structure of proteins was almost preserved where interaction-related changes were observed in the overall secondary structure (α-helix) of SpA. In the adsorbed state, the protein structure was largely modified, which allowed the identification of tyrosine amino acids involved in SpA and IgG interaction. This study constitutes a direct Raman spectroscopic investigation of SpA and IgG (receptor-antibody) interaction mechanism in the goal of a future biosensor application for detection of pathogenic microorganisms.

Owing to its origin, Natural Rubber exhibits more variation than synthetic polymers. If, over the years, NR specifications have evolved from mere visual inspections towards the more complex Technically Specified Rubber (TSR) schema, industrial practice shows that, even for typical TSR grades, significant variations still exist within each shipment, especially in regard to processability. It follows that mastication is quite systematically needed in industrial operations, without or with processing aids or so-called peptizers. Typical NR compounding operations consume therefore time and mixer capacity, a situation, which obviously calls both better characterization methods of (gum) natural rubber and eventually improved grades. There are nowadays promising new techniques to analyze and characterize polymer materials, some of which are a priori attractive for a better specification of NR grades. One such technique is the so-called Fourier Transform rheometry, a dynamic testing method to investigate both the linear and the non-linear viscoelastic domains of polymer materials. Other are spectroscopic methods like solid Nuclear Magnetic Resonance (NMR), either liquid or solid, whose results might be complemented by Size Exclusion Chromatography with special detection techniques, e.g. SEC-MALS, and Differential Scanning Calorimetry (DSC). The purpose of the work reported here was to investigate a series of gum NR grades using such techniques, with the objectives not only to demonstrate their interest but also to cross-validate their results. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Telechelic oligoisoprenes were successfully prepared by the selective controlled degradation of natural rubber, a renewable source, via epoxidation and cleavage reactions. The molar mass of the oligoisoprene product obtained depends on the degree of epoxidation of the starting materials. The chemically modified structures obtained via epoxidation, hydrogenation, and ring opening of epoxide groups were also studied, and the chemical structures and thermal properties of the oligoisoprene products were determined. Moreover, the preliminary study of preparation of hydroxytelechelic natural rubber (HTNR)-based polyurethane foam was performed. A novel HTNR-based polyurethane foam was successfully prepared and its thermal properties were investigated and the results indicated that the HTNR-based polyurethane foam has a good low temperature flexibility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

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.

A biosensor for direct label-free DNA detection based on a polythiophene matrix is investigated by electrochemical impedance spectroscopy (EIS). Impedimetric experiments are performed with and without redox probe in solution. The non-Faradaic impedance measurements reveal two relaxation processes located at 50 Hz and 5 kHz, respectively. The first relaxation process, located at low frequencies, allows to detect biorecognition events by measuring the phase angle decrease, in accordance with a hindrance of the polaronic conduction. The second relaxation process, located at 5 kHz and originating from DNA modification, seems to increase with the length of the target sequence. These results suggest that this loaded support provides a platform for impedimetric detection of hybridization at high frequencies, leading to less time-consuming detection procedure. For a better understanding, results obtained in non-Faradaic mode are compared with Faradaic approach.

A conducting polymer is tested for DNA delivery trials. The conducting matrix used is successful for electrochemical delivery of DNA accumulated by covalent immobilization. The electrochemical process consists of the reduction of arylsulfonamide moieties, which occur as linker groups. The specific design of the polymer allows the electronic properties to be promoted, making available the cleavage potential in physiological media. The amount of DNA released from a modified platinum electrode is investigated by quartz crystal microbalance. The released species used to prove the system performance are long sequences of DNA strands, which are amplified by PCR after liberation and identified by electrophoresis migration.

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(3) 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.

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.

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 also synthesized.

The reduction of weak acids in organic media was investigated. For diarylacetic acids cyclically conjugated, the reduction was found to consume less than one electron per molecule and gives side-products with almost no hydrogen evolution. In particular, the unexpected cathodic decarboxylation of fluorene-9-carboxylic and 4-(4H-cyclopenta[2,1-b;3,4-b′])dithiophene carboxylic acids was related. A mechanism is proposed to explain this original decarboxylation route. Keywords: Weak acid, Decarboxylation, Reduction, Conjugated carboxylic acid, Cyclopentadithiophene

Cathodic sensitive group (CSG) connected to a conducting polybithiophene by a π-conjugated spacer has been designed to study the conduction through the unsaturated spacer. By comparison with the electrochemical behaviour of the saturated spacer analogue, the cyclic voltammetry shows that, when the electronic communication is ensured, the CSG becomes reducible at the same potential than that of conducting matrix. This suggests that the electrons injected in the conducting polymer, CP, during the n-doping process can promote the CSG reduction. A n-doping catalytic process is evoked to explain this electron transfer mediated reduction. Furthermore, an electrocleavable group used as CSG, allows the access to a wide range of organic materials suitable for electrochemically controlled delivery systems. Keywords: Cyclopentadithiophene, π-Conjugated spacer, n-Doping catalytic process, Electrical stimulus, Controlled delivery

A conducting polythiophene sensor for direct label-free DNA detection is investigated by electrochemical impedance spectroscopy (EIS) and by quartz crystal microbalance. The end-modified DNA probe is covalently immobilized by using a new anchorage function. The hybridization detection is studied by EIS experiments. An equivalent circuit is suggested and the variations of individual values of parameters deduced from impedance fits are connected to the change of conformation during the hybridization process.

New telechelic cis -1,4-polyisoprene oligomers bearing an hydroxyl group at the end of the polyisoprene backbone and possessing controlled molecular weights were used as soft segments in the elaboration of polyurethane elastomers. Besides, the well defined hydroxytelechelic cis -1,4-polyisoprene (HTPI) structure obtained through a controlled methodology, was chemically modified leading to hydrogenated and epoxidized oligomers based polyurethanes. The influence of the structural changes of these precursors on the polyurethanes properties have been studied. Thus, mechanical parameters as well as glass transition and mechanical transition temperature measurements indicated an increase in PUs hardness when the length of soft segment decreases and when the degree of epoxidized and hydrogenated isoprenic moieties increases. Moreover, based on thermogravimetric analysis (TGA), a linear relationship was established between the weight loss in the urethane stage degradation and the amount of hard segments in the PUs. Otherwise, the hydrogenated soft segments were found more thermally stable than the epoxidized and the non modified ones. By comparison with similar investigations developed from commercial oligodienes (PBHT R20 LM ® and EPOL ® ), this study mainly showed that the PUs based on hydrogenated hydroxytelechelic cis -1,4-polyisoprenes were more thermally stable and softer than the EPOL ® based analogues.

Novel cationic waterborne polyurethane (cWPU) based on natural rubber (NR) have been prepared by the polymerization reaction of hydroxyl telechelic natural rubber (HTNR), toluene-2,4-diisocyanate (TDI), N-methyl diethanol amine (NMDEA, as emulsifier), and ethylene glycol (EG, chain extender). The polyol structures have been developed as alternative to produce cWPUs derived from a renewable resource. The effects of five parameters were studied – amount of NMDEA (0 – 2.25 mole), amount of EG (0 – 3 mole), molecular weight of HTNR (~1000 – 3000 g/mole), NCO index (100 – 150), and epoxide content on eHTNR soft segment (0 – 30%). The appearance of cWPU dispersion was milky-blue with long shelf life time, more than 10 months. Particle of prepared cWPU were spherical shape in the nano range size. The adhesive properties of cWPUs on the real leather surface, taking into account of the different molecular weights of HTNR and different degree of epoxide content on HTNR, were tested by lap shear test and 180 degree peel test and compared with commercial adhesives. Overall, to balance the stability and adhesive strength, the best conditions for preparing cWPU adhesive for leather application in this study was from the composition of HTNR3000 with epoxide content of 10%, NMDEA 5.67%wt, NCO index of 100 and 1 mole of EG. in condition of curing at 70 °C. In comparison to non-solvent based and solvent based commercial adhesives, the adhesive strengths of these synthesized cWPU adhesive were superior., Synthèse de nouveaux WPU (waterborne polyurethane) cationiques à partir du caoutchouc naturel (NR), et évaluation de leurs propriétés adhésives pour des surfaces de type cuir. Ces WPU ont été obtenus par réaction du caoutchouc liquide hydroxy téléchélique (HTNR), de toluene-2,4-diisocyanate (TDI), N-methyl diethanol amine (NMDEA, en tant qu’émulsifiant) et d’éthylène glycol (EG, extenseur de chaîne). Ces structures biosourcés sont développés comme alternatives aux WPU issus des ressources fossiles à fort impact environnemental. Les effets de cinq paramètres ont été étudiés, à savoir la quantité d'émulsifiant (de 0 à 2,25 mole), celle d’éthylène glycol (de 0 à 3 moles), le Mn du HTNR (de 100 à 3000 g/mole), l'indice NCO (de 100 à 150) et le taux d’époxydation des HTNR précurseurs (de 0 à 30%). Il a été en outre démontré que la stabilité des dispersions aqueuses pour les formulations optimales dépassait les 10 mois. La géométrie des particules dispersées a été étudiée, démontrant un aspect sphérique et une taille à l'échelle nanométrique. Ainsi, plusieurs facteurs ont été étudiés pour évaluer les propriétés adhésives optimales sur bandes de cuir (Mn, pourcentage d’'époxyde). Des tests standard (Peel test et Lap Shear test) ont été utilisés et les valeurs obtenues comparées avec celles issus de formulations adhésives commerciales avec ou sans solvants. Au bilan, une formulation optimale a été déterminée (Mn = 3000 g/mole, LR epoxydation = 10%, NMDEA 5.67%wt, NCO index de 100 et 1 mole d’EG) avec cuisson préalable des systèmes à 70°C. Ce WPU a montré une force d’'adhésion supérieure à toutes les formulations commerciales testées.

The aim of this research was to prepare a bio-based polyurethane foam (PUF) containing hydroxyl telechelic oligomers from natural rubber (HTNR) and waste tire crumbs (HTWT) and polycaprolactone diol (PCL) as soft segments. The studied parameters included type of polyols and molar ratio between HTNR/PCL and HTWT/PCL. The molecular weight of HTNR and HTWT derived from 1H-NMR spectra were 1,800 and 1,400 g/mol, respectively. The molecular weight of PCL diol was 2000 g/mol. The effect of HTNR/PCL and HTWT/PCL molar ratio (1/0, 1/0.5, 1/1 and 0.5/1) on the foam formation rate and physical and chemical properties of the resulting PUF was investigated. The chemical structure of HTNR, HTWT and PUF were confirmed by FTIR and 1H-NMR. PCL diol provided faster reaction, thus higher PCL diol content showed higher foam formation rate. The foam density slightly changed with the molar ratio whereas the specific tensile strength of all samples was in the same range. The average diameter of cell increased with increasing contents of PCL diol. The addition of PCL diol resulted in reduced elongation at break and compressive strength. The cellular structure observed by SEM micrographs of HTNR based foams showed an almost closed cell. The biodegradability was assessed according to a modified Sturm test. Low density polyethylene and sodium benzoate were used as a negative and positive control sample, respectively. PUF samples showed an induction time of 33 days in which the percentage of biodegradation was  7-11%. The biodegradation of PUF containing only HTNR was 8.4% and 31.89% at 28 days and 60 days of testing respectively whereas the PUF containing 1/0.5 HTNR/PCL (by mole) showed a higher biodegradation: 11.31% and 45.6% at 28 days and 60 days of testing respectively. The molar ratio of HTWT/PCL strongly affected the kinetic rate of foam formation and foam morphology. According to SEM micrographs, polyhedral closed cells were observed. The addition of the PCL diol increased the thermal degradation temperature of the PUF based on TGA results. A low kinetic rate provided PUF with a high density, small cell size and a broad cell size distribution. The biodegradation of PUF containing only HTWT was 31.2% and 51.3% at 28 days and 60 days of testing respectively whereas the PUF containing 1/0.5 HTWT/PCL diols (by mole) showed a higher biodegradation: 39.1% and 64.3% at 28 days and 60 days of testing respectively. The foam formation rate of HTWT based PUF was higher than the one of HTNR based PUF. All HTWT based PUF have a higher density than HTNR based PUF. The HTWT based PUF had an inferior cell size in comparison to HTNR based PUF. The cellular structure of HTNR based and HTWT based PUF were different, but all PUFs showed almost closed cells. The HTWT based PUF had a higher thermal degradation temperature and biodegradation properties than foams from HTNR., L’objectif de ces travaux de recherche était de synthétiser de mousses polyuréthane (PUF) bio-basées à partir d’oligomères hydroxytéléchéliques issus du caoutchouc naturel (HTNR) ou à partir de poudrettes de pneus usagés (HTWT) et du diol de la polycaprolactone (PCL) comme segments soft. Les paramètres étudiés ont été le type de polyol et le rapport molaire entre HTNR/PCL et HTWT/PCL. La masse molaire de HTNR, HTWT et PCL étaient respectivement 1,800, 1400 et 2000 g/mol. L’effet du rapport molaire HTNR/PCL et HTWT/PCL (1/0, 1/0/5/, 1/1, et 0.5/1) sur la vitesse de formation des mousses et sur les propriétés chimiques et physiques a été étudié. Les structures chimiques de HTNR, HTWT et PUF ont été confirmées par FTIR et 1H-RMN. Le diol de la PCL était le plus réactif donc augmentant le contenu de PCL-diol la vitesse de formation des mousses a augmenté. La densité des mousses a changé légèrement avec le rapport molaire cependant la résistance à la traction reste dans la même gamme. Le diamètre moyen des cellules a augmenté en fonction du contenu de PCL-diol et la tendance inverse a été observée pour l’allongement à la rupture et la résistance à la compression. L’observation au microscope électronique à balayage (MEB) a montré que les mousses basées sur les HTNR étaient alvéolées et fermées. La biodégradabilité a été évaluée selon le test de Sturm. Polyéthylène à baisse densité et benzoate de sodium ont été utilisés respectivement comme témoins négatif et positif. Les mousses ont montré une période d’induction de 33 jours dans lequel le pourcentage de dégradation était ~ 7-10%. La biodégradation de PUF contenant seulement HTNR a été 8.4% après 28 jours et 31.89% après 60 jours ; les PUF contenants 1/0.5 HTNR/PCL ont montré un pourcentage supérieure : 11.31% après 28 jours et 45.6% après 60 jours. Le rapport molaire HTWT/PCL a influencé beaucoup la vitesse de formation des mousses et leur morphologie. Cellules fermées de forme polyédrique ont été observé par microscopie électronique à balayage. Les résultats de l’analyse thermogravimétrique ont montré que l’addition du diol de la PCL a augmenté la température de dégradation. Il a été observé qu’une basse vitesse de réaction génère des mousses à haute densité, petit diamètre de cellule et haute distribution des diamètres. La biodégradation des PUF contenant seulement HTWT a été 31.2% après 28 jours et 51.3% après 60 jours, tandis que les PUF contenant 1/0.5 HTWT/PCL ont montré une dégradation plus élevée : 39.1% après 28 jours et 64.3% après 60 jours. La vitesse de formation des mousses basées sur les HTWT était supérieure à celle des mousses basées sur les HTNR. Toutes les mousses basées sur les HTWT ont une densité supérieure et une taille de cellule inférieure à celles basées sur HTNR. La structure des cellules des mousses basées sur les HTNR ou HTWT était différente cependant toutes les mousses ont montré des cellules quasi complètement fermées. Les mousses basées sur les HTWT ont montré des propriétés thermiques et de biodégradation meilleures par rapport aux mousses basées sur les HTNR., วัตถุประสงค์ของงานวิจัยนี้ เพื่อทำการเตรียมโฟมพอลิยูรีเทนชีวภาพ (PUF) จากยางธรรมชาติดัดแปรที่มีหมู่ปลายไฮดรอกซิล (HTNR) ยางคลัมบ์ดัดแปรที่มีหมู่ปลาย ไฮดรอกซิล (HTWT) และพอลิคาโปรแลคโทน (PCL) ศึกษาผลของชนิดพอลิออล และสัดส่วนโดยโมลระหว่าง HTNR/PCL และ HTWT/PCL ที่สัดส่วน 1/0, 1/0.5, 1/1 และ 0.5/1 โดยโมล นํ้าหนักโมเลกุลของ HTNR, HTWT และ PCL ที่ใช้สำหรับงานวิจัยนี้ คำนวณจาก 1H-NMR คือ 1,800, 1,400 และ 2,000 g/mol ตามลำดับ ลักษณะโครงสร้างทางเคมีของ HTNR, HTWT และPUF สามารถวิเคราะห์และยืนยันด้วยเทคนิค FTIR และ 1H-NMR รวมถึงทำการวัดอัตราการก่อโฟม (Foam formation rate) ทดสอบสมบัติทางกายภาพ ทางเคมี และสมบัติการย่อยสลายทางชีวภาพ พบว่าในกรณีของโฟมพอลิยูรีเทนจาก HTNR/PCL เมื่อใช้ PCL ในปริมาณที่มากขึ้นจะส่งผลให้อัตราการก่อโฟมเร็วขึ้น และขนาดของเซลโฟมมีขนาดใหญ่ขึ้นด้วย ในขณะที่ค่าความหนาแน่น และความต้านทานต่อแรงดึงจำเพาะมีการเปลี่ยนแปลงเล็กน้อย การเติม PCL ในส่วนผสมของโฟมยังส่งผลให้ความสามารถในการยืด ณ จุดขาด และความทนทานต่อการกดมีค่าลดลง การคืนตัวหลังการกดของโฟม PUF2 (สัดส่วนระหว่าง HTNR/PCL = 1/0.5) จะให้ค่าตํ่าที่สุดคือ 40% ลักษณะของโฟมที่ได้จากการทดลองนี้โดยส่วนใหญ่จะเป็นแบบเซลปิด ความสามารถในการย่อยสลายทางชีวภาพของโฟม ทดสอบโดยใช้วิธี Sturm Test มี LDPE เป็นตัวเปรียบเทียบเชิงลบ และใช้ Sodium benzoate เป็นตัวเปรียบเทียบเชิงบวก พบว่าโฟมเริ่มมีการย่อยสายเกิดขึ้นอย่างเห็นได้ชัดที่เวลา 33 วัน มีเปอร์เซ็นต์การย่อยสลายในช่วง 7-11 เปอร์เซ็นต์ เปอร์เซ็นต์การย่อยสลายของโฟมจาก HTNR (PUF1) อยู่ที่ระดับ 8.4 และ 31.89 เปอร์เซ็นต์ และเปอร์เซ็นต์การย่อยสลายของโฟมจาก HTNR/PCL (1/0.5) อยู่ที่ระดับ 11.31 และ 45.6 เปอร์เซ็นต์ ที่เวลาในการทดสอบ 28 และ 60 วัน ตามลำดับ กรณีของโฟมพอลิยูรีเทนจาก HTWT/PCL เมื่อใช้ PCL ในปริมาณที่มากขึ้นจะส่งผลให้ค่าความหนาแน่นสูงขึ้น ขนาดของเซลโฟมลดลงมีการกระจายของเซลในวงกว้างไม่สมํ่าเสมอ เปอร์เซ็นต์การย่อยสลายทางชีวภาพของโฟมจาก HTWT (PUF5) อยู่ที่ระดับ 31.2 และ 51.3 เปอร์เซ็นต์ และเปอร์เซ็นต์การย่อยสลายของโฟมจาก HTWT/PCL (1/0.5) อยู่ที่ระดับ 39.1 และ 64.3 เปอร์เซ็นต์ ที่เวลาในการทดสอบ 28 และ 60 วัน ตามลำดับ เมื่อทำการเปรียบเทียบโฟมที่ได้จากการเตรียมโดยใช้พอลิออลหลักเป็น HTNR และ HTWT พบว่าโฟมจากพอลิออลหลัก HTWT ให้อัตราการก่อตัวของโฟมเร็วกว่า ขนาดของเซลโฟมเล็กกว่า ความหนาแน่น ความต้านทานต่อความร้อน และเปอร์เซ็นต์การย่อยสลายทางชีวภาพสูงกว่า เมื่อเทียบกับโฟมจากพอลิออลหลัก HTNR

The aim of this research work was to improve the compatibility of polymer blends made from poly(lactic acid) and natural rubber (PLA/NR blends) by using modified natural rubber as a compatibilizer. Natural rubber was chemically modified into two categories: natural rubber grafted poly(vinyl acetate) copolymer (NR-g-PVAc) and block copolymers (PLA-NR diblock copolymer and PLA-NR-PLA triblock copolymer). PLA/NR blends were prepared by melting blending in a twin screw extruder and compression molded to obtain a 2-mm thick sheet. The blends contained 10-20 wt% of NR and modified NR, and the impact strength and tensile properties were investigated. The compatibilization effect was determined by DMTA, DSC and SEM. NR-g-PVAc was synthesized by emulsion polymerization to obtain different PVAc graft contents (1%, 5% and 12%). Characterization by DMTA showed an enhancement in miscibility of the PLA/NR-g-PVAc blends. NR-g-PVAc could be used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. The block copolymers were synthesized following two routes: (1) hydroxyl telechelic natural rubber (HTNR) and lactide and (2) HTNR and PLA prepolymer. In the former route, lactide was in situ polymerized via a ring opening polymerization to be a PLA block segment during block copolymerization. In the latter route PLA prepolymer was synthesized by a condensation polymerization of L-lactic acid prior to block copolymerization. Both block copolymers acted as good compatibilizers for the PLA/NR blend by increasing the impact strength and decreasing the NR particle size. Triblock copolymers provided higher impact strength than diblock copolymers, and they were a less effective compatibilizer than NR-g-PVAc. In contrast to NR and NR-g-PVAc, the block copolymer was not a good toughening agent for PLA., L’objectif de ce travail de thèse était l’amélioration de la compatibilité de mélanges d’acide polylactique et de caoutchouc naturel (mélanges PLA/NR) par l’ajout de dérivés du caoutchouc naturel comme agents compatibilisants. Le caoutchouc naturel a été modifié selon deux approches : synthèse d’un copolymère greffé caoutchouc- poly(vinyl acétate) (NR-g-PVAc) et synthèse de polymères à blocks PLA-NR et PLA-NR-PLA. Les mélanges PLA/NR ont été préparés par extrusion dans une extrudeuse à double vis et moulées par compression pour obtenir des feuilles de 2 mm d’épaisseur. Les mélanges contenaient 10-20% en poids de NR et NR modifiée. La résistance au choc et les propriétés en traction ont été étudiées. L’effet de compatibilisation a été déterminé par DMTA, DSC et MEB. NR-g-PVAc a été synthétisé par polymérisation en émulsion pour obtenir de copolymères avec différents contenus en PVAc greffé (1%, 5% and 12%). La caractérisation des matériaux par DMTA a montré une augmentation de la miscibilité des mélanges PLA/NR-g-PVAc.NR-g-PVAc a résulté être un agent durcissant pour le PLA et un agent compatibilisant pour les mélanges PLA/NR. Les polymères à bloc ont été synthétisés selon deux routes : (1) NR hydroxy téléquelique (HTNR) et lactide et (2) NR hydroxy téléquelique et pré-polymère PLA. Dans la première approche, le lactide a été polymérisé in situ à travers la polymérisation par ouverture de cycle pour donner un bloc. Dans la deuxième approche, le pré-polymère PLA a été synthétisé par polymérisation directe de l’acide L-lactique avant copolymérisation à blocs. Les deux types de copolymères se sont révélés de bons agents compatibilisants pour les mélanges PLA/NR, car ils ont augmenté la résistance au choc et ils ont diminué la taille des particules de caoutchouc.

The aim of this research work was to prepare a novel bio-based polyurethane (PU) composed by chemically modified natural rubber (NR) and poly(ε-caprolactone) diol (PCL), with and without isocyanate. Hydroxyl telechelic natural rubber (HTNR) was synthesized via epoxidized and carbonyl telechelic natural rubber. The parameters studied included type and relative amount of diisocyanate, molar ratio between diisocyante and diol (NCO:OH), molecular weight of HTNR and PCL diol, 1,4-butane diol (BDO, chain extender) content and molar ratio between HTNR:PCL diols. Three types of diisocyanate were employed: isophorone diisocyanate (IPDI), toluene-2,4-diisocyanate (TDI) and hexamethylene diisocyanate (HDI). The number average molecular weights of HTNR and PCL diol were selected: 1700, 2800 and 2900 g/mol for HTNR and 530 and 2000 g/mol for PCL diol. The NCO:OH molar ratio was in the range 0.75:1.00 – 2.85:1.00. PU was prepared by one-shot method. The chemical structure of HTNR, PCL and PU were identified by 1H-NMR FTIR and Raman spectroscopy. Tensile properties and tear resistance of PU were investigated. Characterization of mechanical and thermal properties was carried out using DSC, DMTA and TGA. A preliminary study showed that the molecular weight of PU increased with increasing NCO:OH molar ratio and reaction time, and chloroform was not a good solvent for polymer casting. Tetrahydrofuran was an appropriate solvent as it allowed film formation and it was used in all the other experiments. The NCO:OH molar ratio of 1.25:1.00 was suitable for preparing good PU films. FTIR analysis verified the presence of urethane linkages and crosslinking or chain branching. PU demonstrated excellent mechanical properties, which depended on the chemical composition. Excluding the use of PCL2000 and HDI, the tensile behavior seemed to have typical elastomeric characteristics. PU became amorphous except in the case of HDI, which was able to crystallize leading to the crystalline PU. The crystallinity increased the Young’s modulus, the tear strength, the hardness and the thermal stability of PU. PU showed a phase separation between the PCL and HTNR segments. The longer and more flexible chain and non-polarity of HTNR were responsible of a decrease of the mechanical properties and transition temperatures. The very high molar ratio of NCO:OH (2.85:1.00) changed the tensile characteristics from an elastomer to a plastic. The high crosslinking was attributed to there being no phase separation between the hard and the soft segment. Hydrogen bonding between the PCL diol and the hard segment produced a high Tg. Raman spectra were able to identify the urethane linkage of PU containing different diisocyanates by showing the relative absorbance peaks. Synthesis of PU without isocyanate was successfully obtained via a polyaddition polymerization between a cyclic carbonate telechelic PCL/NR and 1,4-butylenediamine. The cyclic carbonate telechelic NR and cyclic carbonate telechelic PCL were prepared via the modification of the hydroxyl end groups of HTNR and PCL diols to carboxylic acid end groups by reacting with succinic anhydride. Then, the carboxylic acid end groups were changed to the cyclic carbonate end groups by using glycerol carbonate., L’objectif de ce travail de thèse était la synthèse d’un nouveau matériau polyuréthane biorsourcé composé par du caoutchouc naturel modifié chimiquement et par du poly(ε-caprolactone), (PCL), en présence ou absence d’isocyanates. Des oligoisoprènes téléchéliques hydroxylés (HTNR) ont été obtenus après époxidation du caoutchouc naturel et réduction des oligomères carbonyles. Plusieurs paramètres ont été étudiés comme la nature et la quantité relative de diisocyanate, le rapport molaire entre diisocyanate et diol (NCO:OH), l’influence de la masse molaire des diols HTNR et PCL, le pourcentage de 1,4-butane diol (BDO, extenseur de chaîne), et le rapport molaire entre les diols HTNR:PCL. Trois types de diisocyanate ont été employés : isophorone diisocyanate (IPDI), toluène-2,4-diisocyanate (TDI) et hexaméthylène diisocyanate (HDI). Masses molaires différentes ont été utilisées pour les diols HTNR et PCL: 1700, 2800 et 2900 g/mol pour HTNR et 530 et 2000 g/mol pour PCL. Le rapport molaire entre NCO:OH était entre 0,75:1,00 – 2,85:1,00. Les PU ont été préparés par la méthode « one shot » et les structures chimiques des HTNR et PU ont été identifiées par 1H-NMR et FTIR. La résistance à la traction et à la rupture ont été étudiées. La caractérisation a été conduite par DSC, DMTA, ATG et spectroscopie Raman. Une étude préliminaire a montré que la masse molaire du PU augmentait avec le rapport NCO:OH et le temps de réaction, et que le chloroforme n’était pas un bon solvant pour obtenir des films. Le tetrahydrofurane était le solvant le plus approprié et il a été utilisé par la suite pour toutes les polymérisations. Le rapport NCO:OH = 1,25:1,00 s’est révélé optimal pour obtenir des films. L’analyse FTIR a permis de vérifier la présence de liaisons uréthane, de points de réticulation et de branchements. Le polyuréthane a montré des propriétés mécaniques excellentes dépendantes de la composition chimique. Si on exclue l’utilisation de PCL2000 et de HDI, le comportement à la traction était caractéristique des élastomères. Les PU étaient amorphes sauf lorsque le HDI a été employé. Duos ce cos été obtenais un PU semi cristallin. Cette cristallinité augmente le module de Young, la résistance à la rupture, la dureté et la stabilité thermique du PU. Pour ce PU ont observé une séparation de phase entre les segments du PCL et du HTNR. Les chaînes plus longues et plus flexibles du HTNR et leur non polarité sont responsables de la diminution des propriétés mécaniques et des températures de transition. Le materiae pane d’un comportement élastomère a un comportement plastique pour un rapport NCO:OH élevé (2,85 :1,00). Le dégréé de réticulation élevé a été retenu comme la cause pour laquelle il n’y avait pas de séparation de phase entre les segments souples et durs. La liaison hydrogène entre le diol PCL et le segment hard a généré des Tg élevées. Les spectres Raman ont montré la formation de la liaison uréthane du PU contenant différents diisocyanates. La synthèse de PU sans diisocyanate a été obtenue grâce à une réaction de polyaddition entre des carbonates cycliques téléchéliques dérivés du PCL et du caoutchouc naturel, et la 1,4-butylène diamine. Les structures contenant des carbonates cycliques ont été obtenues grâce à la modification des groupes OH sur le HTNR et le PCL à groupes carboxyle, utilisant l’anhydride succinique, et a la réaction successive avec le glycérol carbonate.

Industrially, metal/polymer adhesion is involved in a wide range of industries such as automotive industry, or aeronautic and electronic applications. Polyurethanes (PU) are frequently used as structural adhesives, and are based from polyols obtained from petrochemical products (polyester and polyether polyols). However, these products have some disadvantages as they are non-renewable resources, they may cause environmental pollution, and they tend to be exhausted in the near future. Natural rubber (NR) is an interesting choice to use as a starting material in PU synthesis, due to the fact that they are renewable source, abundant polymer and they have interesting mechanical properties and can be chemically modified. In this work, hydroxytelechelic polyisoprene (HTPI) having a hydroxyl functionality of 2 was successfully performed via controlled epoxidation and cleavage of high molecular weight polyisoprene, following by a selective reduction reaction of the obtained carbonyltelechelicoligoisoprenes. These HTPI with different molecular weights (1000-8000 g mol-1) were reproducible obtained. Chemical modifications on HTPI were performed by various percentage of epoxidation (10-60%, EHTPI). The different microstructures of these oligomers were evidenced by the characterization techniques FT-IR, NMR, SEC. Their thermal properties were also investigated by TGA and DSC.Surface properties (surface energy, optical microscopy) and adhesion properties (wedge test) of different materials have been characterized. To resume adherence results, pure HTPI samples (without any epoxy group) present a very high adhesion level. Epoxidation degrees close to 30-40% allow to obtain interesting adhesive performance. Elsewhere, the effect of molecular weight is slight (nevertheless, a higher Mn of HTPI induces globally a better adherence). The adherence level is similar to whose measured for structural adhesive used in car or aeronautic industry. The wedge test is a severe adherence test, and the low crack propagation observed for some formulations underlines promising industrial developments for this new polymers., Industriellement, les problématiques d‘adhésion polymère/métal se rencontrent dans de nombreux secteurs tels que l'industrie automobile, ou les applications aéronautiques et électroniques. Les polyuréthanes (PU) sont fréquemment utilisés comme adhésifs structuraux, et sont obtenus à partir de polyols provenant de la pétrochimie (polyester et polyéther polyols). Cependant, ces produits ont des inconvénients notables sur le plan écologique car ils sont produits à partir de ressources non renouvelables, ils peuvent également générer une pollution de l'environnement, et leurs matières premières de départ sont d‘une part de plus en plus coûteuses et d‘autres part amenées à se raréfier dans les années à venir. Le caoutchouc naturel (NR) est une alternative intéressante aux polyols de synthèse car il est issu d‘une ressource végétale (hévéa), renouvelable et abondante, et également car il présente des propriétés mécaniques intéressantes. De plus, il peut être facilement modifié chimiquement, afin notamment d‘apporter des groupements hydroxyle capables de réagir ensuite avec des fonctions isocyanate pour former un polyuréthane. Dans ce travail, le polyisoprène hydroxytéléchélique (HTPI) ayant une fonctionnalité en hydroxyle de 2 a été synthétisé avec succès par époxydation contrôlée suivie de coupure oxydante de polyisoprène de hautes masses, puis réduction sélective des oligoisoprènes carbonyltéléchéliques obtenus. Ces HTPI de différentes masses molaires (1000-8000 g mol-1) ont été obtenus de façon reproductible. Des modifications chimiques ont été effectuées par époxydation à différents taux (10-60% EHTPI). Les différentes microstructures de ces oligomères ont été mises en évidence par FT-IR, RMN and SEC. Leurs propriétés thermiques ont été déterminées par ATG et DSC. Les propriétés de surface (énergie de surface, microscopie optique) et les propriétés d‘adhésion (test de clivage) de différents matériaux ont été caractérisées. Les échantillons à base de HTPI pur (sans époxyde) présentent un niveau d‘adhésion élevé. Des taux d‘époxydation proches de 30-40% permettent d‘obtenir des performances adhésives intéressantes. D‘autre part, l‘effet de la masse molaire est faible(cependant, une masse molaire plus élevée entraîne globalement une meilleure adhérence). Le niveau d‘adhérence observé est similaire à ceux mesurés pour des adhésifs structuraux utilisés dans l‘industrie automobile ou aéronautique. Le test de clivage est un test d‘adhérence sévère pour un joint adhésif, et les faibles propagations de fissures observées pour certaines formulations permettent d‘escompter des développements industriels prometteurs pour ces nouveaux polymères.

Industrially, metal/polymer adhesion is involved in a wide range of industries such as automotive industry, or aeronautic and electronic applications. Polyurethanes (PU) are frequently used as structural adhesives, and are based from polyols obtained from petrochemical products (polyester and polyether polyols). However, these products have some disadvantages as they are non-renewable resources, they may cause environmental pollution, and they tend to be exhausted in the near future. Natural rubber (NR) is an interesting choice to use as a starting material in PU synthesis, due to the fact that they are renewable source, abundant polymer and they have interesting mechanical properties and can be chemically modified. In this work, hydroxytelechelic polyisoprene (HTPI) having a hydroxyl functionality of 2 was successfully performed via controlled epoxidation and cleavage of high molecular weight polyisoprene, following by a selective reduction reaction of the obtained carbonyltelechelicoligoisoprenes. These HTPI with different molecular weights (1000-8000 g mol-1) were reproducible obtained. Chemical modifications on HTPI were performed by various percentage of epoxidation (10-60%, EHTPI). The different microstructures of these oligomers were evidenced by the characterization techniques FT-IR, NMR, SEC. Their thermal properties were also investigated by TGA and DSC.Surface properties (surface energy, optical microscopy) and adhesion properties (wedge test) of different materials have been characterized. To resume adherence results, pure HTPI samples (without any epoxy group) present a very high adhesion level. Epoxidation degrees close to 30-40% allow to obtain interesting adhesive performance. Elsewhere, the effect of molecular weight is slight (nevertheless, a higher Mn of HTPI induces globally a better adherence). The adherence level is similar to whose measured for structural adhesive used in car or aeronautic industry. The wedge test is a severe adherence test, and the low crack propagation observed for some formulations underlines promising industrial developments for this new polymers.; Industriellement, les problématiques d‘adhésion polymère/métal se rencontrent dans de nombreux secteurs tels que l'industrie automobile, ou les applications aéronautiques et électroniques. Les polyuréthanes (PU) sont fréquemment utilisés comme adhésifs structuraux, et sont obtenus à partir de polyols provenant de la pétrochimie (polyester et polyéther polyols). Cependant, ces produits ont des inconvénients notables sur le plan écologique car ils sont produits à partir de ressources non renouvelables, ils peuvent également générer une pollution de l'environnement, et leurs matières premières de départ sont d‘une part de plus en plus coûteuses et d‘autres part amenées à se raréfier dans les années à venir. Le caoutchouc naturel (NR) est une alternative intéressante aux polyols de synthèse car il est issu d‘une ressource végétale (hévéa), renouvelable et abondante, et également car il présente des propriétés mécaniques intéressantes. De plus, il peut être facilement modifié chimiquement, afin notamment d‘apporter des groupements hydroxyle capables de réagir ensuite avec des fonctions isocyanate pour former un polyuréthane. Dans ce travail, le polyisoprène hydroxytéléchélique (HTPI) ayant une fonctionnalité en hydroxyle de 2 a été synthétisé avec succès par époxydation contrôlée suivie de coupure oxydante de polyisoprène de hautes masses, puis réduction sélective des oligoisoprènes carbonyltéléchéliques obtenus. Ces HTPI de différentes masses molaires (1000-8000 g mol-1) ont été obtenus de façon reproductible. Des modifications chimiques ont été effectuées par époxydation à différents taux (10-60% EHTPI). Les différentes microstructures de ces oligomères ont été mises en évidence par FT-IR, RMN and SEC. Leurs propriétés thermiques ont été déterminées par ATG et DSC. Les propriétés de surface (énergie de surface, microscopie optique) et les propriétés d‘adhésion (test de clivage) de différents matériaux ont été caractérisées. Les échantillons à base de HTPI pur (sans époxyde) présentent un niveau d‘adhésion élevé. Des taux d‘époxydation proches de 30-40% permettent d‘obtenir des performances adhésives intéressantes. D‘autre part, l‘effet de la masse molaire est faible(cependant, une masse molaire plus élevée entraîne globalement une meilleure adhérence). Le niveau d‘adhérence observé est similaire à ceux mesurés pour des adhésifs structuraux utilisés dans l‘industrie automobile ou aéronautique. Le test de clivage est un test d‘adhérence sévère pour un joint adhésif, et les faibles propagations de fissures observées pour certaines formulations permettent d‘escompter des développements industriels prometteurs pour ces nouveaux polymères.