Françoise Fenouillot

• Professor (Associate) at Institut National des Sciences Appliquées de Lyon

The synthesis of a biobased aliphatic polyester, poly(hexamethylene sebacate) (PE 6-10) via esterification and alcoholysis reactions steps by reactive extrusion is reported. The overall reaction time was decreased down to around 14 minutes instead of roughly 360 minutes in a classical batch reactor. A number average molar mass of 21,100 g.mol⁻¹ has...

The synthesis and properties of amorphous poly(tricyclodecanedimethylene-co-isosorbide terephthalate) (PTIT) with isosorbide (IS) content ranging from 0 to 68 mol% relative to total diols amount were investigated. Surprisingly, it was found that isosorbide enhanced the polycondensation kinetics and was acting as a temporary chain linker. Polymeriza...

This paper presents an investigation of the morphology of growing polyurethane (PU) rigid foams during the very first seconds of the process by cryogenic scanning electron microscopy (cryo-SEM) performed at −150 °C. The heterogeneous nature of the initial mixture has been revealed with the presence of sub-micron size physical blowing agent droplets...

In this paper, the synthesis and properties of poly(1,4-cyclohexanedimethylene-co-isosorbide terephthalate) (PCIT) with isosorbide (IS) content ranging from 16 to 61 mol% relative to the total diols amount were investigated. Amorphous polymers were successfully synthesized without isosorbide ring hydration. Glass transition temperature (T g ) linea...

In the present study, the recycled post-consumption polyethylene terephthalate (PET) flakes were investigated as possible raw materials for the production of food packaging. After heating at 220 °C for 1 h, a steaming stage was conducted as a control test to assess the quality of the product. Different samples were characterized by ¹H-NMR, FT-IR, D...

A particular interest was focused on the recovery of lignocellulosic waste of olive husk flour (OHF) by its incorporation as filler in manufacturing composite materials based on high-density polyethylene (HDPE) matrix. To reduce the hydrophilic nature of the husk flour, a compatibilizer agent, namely polyethylene-graft-maleic anhydride (PE-g-MA) so...

This work analyzes the dispersion conditions of polar liquids with low viscosities into polymer melts. For this purpose, the curve of the critical capillary number in shear as a function of the viscosity ratio for low viscosity liquids dispersed into polymer melts was built. To obtain this curve, the disperse phase and matrix were chosen to have la...

A series of branched poly(butylene succinate) (PBS) were synthesized with several branching agents namely trimethylol propane (TMP), malic acid, trimesic acid, citric acid and glycerol propoxylate. The structure of the branched polymers was analyzed by SEC and 1H-NMR. The effect of branching agent structure on crystallization was also investigated...

The evaluation of the environmental impact of an innovative material at an early stage of development is of fundamental importance during the design phase of a product. In this regard, a full-fledged Life Cycle Assessment presents some major limitations: it can be performed mainly as an ex-post analysis, and it does not account for the intrinsic pr...

The aim of the present work is the chemical modification of microcrystalline cellulose (MCC) by acetic anhydride and using it as reinforcement in poly (vinyl chloride) (PVC). The treatment efficiency was assessed by Fourier Transform Infrared Spectroscopy (FTIR) analysis and contact angle measurements. Likewise, the morphological, mechanical, therm...

Poly(butylene succinate) (PBS) is currently developing due to its biodegradability and the similarity of its mechanical properties to those of polyolefins. Relationships between the number average molar mass,(M) over bar (n), and solution viscosity such as [eta] and eta(red) were derived for this aliphatic polyester. (M) over bar (n) values were de...

The pilot scale synthesis of poly(butylene succinate) copolymers with rigid bio-based comonomers, namely isosorbide and 2,5-furandicarboxylic acid (FDCA) was investigated. The synthesis and properties of these copolymers were compared with aliphatic-aromatic polyesters containing the petrochemical terephthalic acid (PTA), such as poly(butylene succ...

Epoxy-ethylene copolymers were thermally crosslinked by using an amino-acid agent to create covalent cross-links between epoxide functions. Two different systems were studied: a pre-constrained network and a non-constrained one. Samples were aged for 6, 16 and 24 h. The study of the network structure before and during the aging was done by differen...

The melt synthesis of poly(butylene succinate)/silica (PBS/SiO2) nanocomposites is investigated via an in situ approach. The use of two types of nanosilica, fumed (or pyrogenic) silica and colloidal silica, is described. In all cases, the addition of silica favors an increase of the melt viscosity during the polycondensation step. This behavior is...

In this study, gamma irradiation treatments were used to improve the compatibility between polyvinylchloride (PVC) and olive residue flour (ORF). The blends were subjected to gamma irradiation at doses of 10 and 70 kGy. The mechanical, thermal, and morphological behaviors of those blends have been assessed. The irradiated blends exhibit better ther...

The effects of kaolin content and treatments on the thermal and mechanical properties and on the degradation of polypropylene were examined using mechanical tests, differential scanning calorimetry (DSC), and thermogravimetry (TGA). The weak interactions filler/matrix have been reinforced using a modification with urea then with an ammonium salt an...

The reaction in bulk at high temperature of a,x-aminopropyl oligodimethylsiloxane and thermoplastic polyurethane (TPU) allowed observing interesting behavior. Mixing at 200 �C first involved dissociation of urethanes and splitting of polyurethane chains followed by reaction of the released isocyanates with amino end-groups of the oligosiloxane. At...

The reaction in bulk at high temperature of α,ω-aminopropyl oligodimethylsiloxane and thermoplastic polyurethane (TPU) allowed observing interesting behavior. Mixing at 200 °C first involved dissociation of urethanes and splitting of polyurethane chains followed by reaction of the released isocyanates with amino end-groups of the oligosiloxane. At...

The main objective of this research was to investigate the effect on the thermal and mechanical properties of the addition of two different compatibilizing agents, malefic anhydride‐grafted polyethylene (PE) [synthesized in a solution state (MAPE) and commercial (XA255)], to olive husk flour, high‐density polyethylene (HDPE) composites. The composi...

The efficiency of organometal- (Ti, Zr, Sn, Hf, and Bi) and metal oxide- (Ge and Sb) based catalysts was investigated during the transesterification step of the synthesis of poly( butylene succinate) (PBS). PBS was prepared from succinic acid and 1,4-butanediol via a two-stage melt polycondensation process. The catalytic efficiency of the organomet...

New catalytic systems are developed to increase the transesterification efficiency during the synthesis of poly(ethylene terephthalate-co-isosorbide terephthalate) with the aim of compensating for the lack of reactivity of the isosorbide and to reduce the coloration of the polymer. The combination of antimony oxide with a second metal (lithium-, ma...

Communication par affiche

The present review aims at summarizing the current knowledge on how solid nanoparticles organize in polymer blends. First, the behavior of low viscosity fluid emulsions containing solid colloidal particles is briefly exposed. By contrast with polymer blends, they have been the subject of intensive studies for a long time, with both applicative and...

The use of 1,4:3,6-dianhydrohexitols, isosorbide, isomannide and isoidide in polymers is reviewed. 1,4:3,6-Dianhydrohexitols are derived from renewable resources from cereal-based polysaccharides. In the field of polymeric materials, these diols are essentially employed to synthesize or modify polycondensates. Their attractive features as monomers...

Poly(ethylene-co-vinyl acetate) (EVA)/poly(butylene terephthalate) copolymers were synthesized by the in situ polymerization of cyclic butylene terephthalate monomer (cBT) in the presence of molten EVA copolymer.Titanium phenoxide Ti(OPh)4 which leads to the highest degree of grafting compared to the more classical titanium system was used as the i...

a b s t r a c t The present review aims at summarizing the current knowledge on how solid nanoparticles organize in polymer blends. First, the behavior of low viscosity fluid emulsions containing solid colloidal particles is briefly presented. By contrast with polymer blends, they have been the subject of intensive studies for a long time, with bot...

Hydrophilic pyrogenic silica melt mixed in immiscible polypropylene/poly (ethylene-co-vinyl acetate) (PP/EVA) blend was found to migrate from the PP matrix to the EVA dispersed domains and remained confined inside them. Surprisingly, it was shown than silica was also able to migrate from a dispersed PP phase to an EVA matrix but this transfer was s...

The effect of inorganic silica nanoparticles on the morphology and viscoelastic properties of polypropylene/poly(ethylene-co-vinyl acetate) (PP/EVA) immiscible blends has been investigated. Different EVA with different molar masses were used in this study. Virgin and filled blends were prepared by using a twin-screw mini-extruder. Microscopy studie...

This study was performed in order to evaluate the effects of transesterification reactions on the thermal properties of the PC/PET system, as a function of homopolymer and exchange catalyst concentrations. DSC results support well that when transesterification occurs, the glass transition temperature of the PC-rich phase decreases with the increase...

The preparation of poly(2,6-dimethyl-1,4-phenylene ether)-b-poly(ethylene terephthalate) block copolymer was performed by the reaction of the 2-hydroxyethyl modified poly(2,6-dimethyl-1,4-phenylene ether) (PPE-EtOH) with poly(ethylene terephthalate) (PET) by an in situ process, during the synthesis of the polyester. The yield of the reaction of the...

This paper considers an improvement of the emulsion models to take into account concentrated emulsions with no coalescence but with significant interaction between particles. For this purpose, a term proportional to the volume fraction of material in excess to the percolation threshold is added to the dynamic modulus. Its usefulness was tested to m...

A model reactive system was defined for studying experimentally and by simulation the competition between reaction and diffusion of two low molecular weight reactants, 2,3-epoxypropyl-phenylether (EPPE) and dipentylamine (DPA). Both reactants are miscible in a high-viscous molten polymer, poly(ethylene-co-vinyl acetate) (EVA). The comparison of the...

The evolution of the viscoelastic properties of a molten thermoplastic/thermoset system during the course of the isothermal polymerization of the thermoset precursors has been investigated and modeled. Such systems are initially homogenous and phase separate upon polymerization of the monomers. In the present study, atactic polystyrene (85 and 60 w...

Amine and alcohol functional dendritic polymers were used as covalent coupling agents for maleic anhydride grafted polyethylene and their efficiency compared with metallic salt and zinc acetate, acting as an ionic coupling agent. The crosslinking reactions in the molten state were carried out at 150°C in an internal mixer and the resulting modified...

The effect of silica nanoparticles on the morphology and the rheological properties of an immiscible polymer blend (polypropylene/polystyrene, PP/PS 70/30) was investigated. Two types of pyrogenic nanosilica were used: a hydrophilic silica with a specific surface area of 200 m2/g and a hydrophobic silica having a specific surface area of 150 m2/g....

The review is devoted to the fundamental aspects of the reactive processing of thermoplastic polymers. First of all, some reactive processing examples, including polymer grafting (vinyl silane, maleic anhydride) and/or functionalization, bulk polymerization (urethane, lactams, acrylate, ε-capolactone), polyester modification and new copolymers synt...

Deformation-induced modification of the dispersion state of silica nanoparticles in poly(ethylene terephthalate) (PET) has been characterized by means of transmission electron microscopy (TEM) and wideangle X-ray diffraction (WAXD). We focused on the biaxial deformation applied at a temperature just above the glass transition temperature (110°C), d...

This paper addresses two important features of the diffusion of liquids into a molten polymer matrix: the dependence of the mutual diffusion coefficient on the liquid miscibility and molar mass of polymers. In addition, a rheological approach is chosen for its capacity to support modeling, and the mutual diffusion coefficient expressed with the fre...

Diglycidyl ether of bisphenol A (DGEBA) and 4,4′-methylenebis [2,6-diethylaniline] (MDEA) are miscible in polystyrene at 177 °C. We have studied how their diffusion rate in a molten polystyrene matrix influences their polymerization rate and the morphology of the thermoset particles formed at the end of the reaction. The global composition of the b...

Pour les matériaux polymères, la combinaison de l'écoulement et de la réaction chimique dans un outillage de transformation permet de générer in situ des structures ou des morphologies particulières à l'origine de nouvelles propriétés. Le contrôle du procédé requiert alors la connaissance de l'évolution de la rhéologie du système pendant la réactio...

Polystyrene (PS)/epoxy‐amine (DGEBA‐MDEA) is a thermoplastic/thermoset precursor blend which is miscible at high temperature (177 °C), and which phase separates under the polymerization of the epoxy‐amine system. Previous studies have shown that the morphology of this blend polymerized under shear is coarse and irregular because the dispersed epoxy...

Maleic anhydride modified polyethylene (PEgMA) coupling reactions were realized using a dioxazoline coupling agent, (1,3-phenylene)-bis(2-oxazoline), in an internal mixer. In preliminary studies and in model reactions, it was shown that anhydride/oxazoline reactions were very slow or nonexistent compared to acid/oxazoline reactions. The main observ...

A polypropylene/high-density polyethylene blend containing 70 wt % polypropylene was prepared and compatibilized via the addition of maleic anhydride grafted polypropylene and polyethylene. The functionalized polymer chains were coupled with two types of coupling agents. Dodecane diamine formed covalent bonds with the maleic anhydride, whereas two...

A thermoplastic poly(hydroxyl-amino ether) polymer (BLOX) was blended with a diglycidyl ether of bisphenol A monomer (DGEBA). This system may be used as a crosslinkable thermoplastic. It means that it may be processed in an extruder like a classic thermoplastic, and cured by etherification reactions initiated by tertiary amine groups of the BLOX in...

A new mixing device has been designed and developed in order to investigate complex mixing situations encountered in polymer blends and formulations. This mixing device called here rheo-mixer has been adapted on a classical rheometer and calibrated in terms of shear/stress that both permanent and dynamic regimes may be quantitatively run. The abili...

Three reactive polymer systems have been examined with a new mixing device adapted on a classical rheometer in order to investigate reactive mixing situations encountered in polymer blends. After having characterized the bulk polymerization of ε-caprolactone (ε-CL), the polymerization of 40wt% of ε-caprolactone into a copolymer of ethylene and viny...

The relation between the gel point of the thermosetting dispersed phase and the coarsening of the morphology of a thermoplastic/thermoset blend reacted under shear has been investigated. The model system was composed of 60wt% of polystyrene (PS) and 40wt% of an epoxy-amine system (diglycidyl ether of bisphenol A — 4,4′-methylenebis [2,6-diethylanil...

The morphology of a polypropylene/polyethylene (PP/PE) blend and a maleic anhydride modified PP and PE (PPg/PEg) blend was studied. The initial morphology, at the extruder die, after the melt blending into a twin-screw extruder, was first characterized. Then, the evolution of this initial morphology was followed after a injection molding operation,...

An immiscible polymer blend where the dispersed phase is fibrillar was prepared by in situ crosslinking of the minor phase. A model polystyrene/epoxy-amine blend was selected on the basis of rheological (achievement of the fibrillar structure) and reactivity (fast crosslinking) criteria. The system was a polystyrene/diglycidyl ether of bisphenol A...

This study concerns the morphology development of a blend based on a thermoplastic matrix with a reactive system undergoing polymerization. The system consists of 60 weight percent of polystyrene and 40 weight percent of a thermoset precursor with a low reactivity diamine (4,4′-methylenebis(2,6-diethylaniline)). Experiments were carried out in a te...

A thermodynamic simulation of the phase-separation process of an off-critical blend, based on a thermoplastic matrix with a reactive epoxy system undergoing polycondensation at a constant temperature, was performed. The model considered the composition dependence of the interaction parameter, χ(T,Φ2) (where T is the temperature and Φ2 is the volume...

The cloud-point curves of polystyrene (PS) mixed with reactive epoxy monomers based on diglycidyl ether of bisphenol A with stoichiometric amounts of 4,4′-methylenebis(2,6-diethylaniline) were experimentally studied. A thermodynamic analysis of the phase-separation process in these epoxy-modified polymers was performed that considered the compositi...

Properties of thermoplastic modified epoxy network have been studied. The particularity of this work is the use of new thermoplastic epoxies whose structure is close to the final matrix. Blends of thermoset epoxy (Diglycidyl Ether of Bisphenol A/4-4′ methylenebis [3-chloro 2,6-diethylaniline]) with a thermoplastic content from 5 to 40%w have been r...

The bulk polymerization of MMA at high temperature (120–180°C) in a continuous pilot-plant reactor has been studied. The polymerization is initiated by diterbutyle peroxide and the chain transfer agent is 1-butanethiol. A simulation program has been developed to predict the steady state behavior of the reactor. The particular features of the kineti...

The free-radical polymerization of methyl methacrylate (MMA) at high temperature (120 to 180°C) has been studied in the presence of di-tertiobutyle peroxide as an initiator and 1-butanethiol as a chain transfer agent. No solvent was used, and the polymerization was run to high monomer conversion. Based on the experimental data collected with a dila...

Kinetic studies of the bulk polymerization of methyl methacrylate at high temperature have been carried out first without any additives and then in the presence of 1-Butanethiol as a chain transfer agent. A pressurised dilatometric reactor operating at high temperature is used to determine the time-conversion curves at temperatures between 150 and...

Ce module multimédia s'intéresse aux matériaux polymères, plus simplement appelés matières plastiques. Les polymères sont constitués de molécules organiques géantes, dites macromolécules. L'explication de cette notion de macromolécule constitue le premier temps de ce module. Dans un second temps, les polymères sont abordés suivant différentes échel...

L’objectif de cette étude est d’identifier et d’étudier les paramètres gouvernant les morphologies de mélanges de polymères immiscibles en présence de charges inorganique de type silice pyrogénée. Dans ce but, des mélanges de polymères immiscibles PP/PS et PP/EVA chargés des nanoparticules de silice ont été caractérisés par analyse en microscopie é...