Bernard Boutevin

On the versatility of urethane/urea bonds: reversibility, blocked isocyanate, and non-isocyanate polyurethane.

Isocyanate, and Non-isocyanate Polyurethane Etienne Delebecq,† Jean-Pierre Pascault,‡,§ Bernard Boutevin,† and Franco̧is Ganachaud*,†,‡,§ †Institut Charles Gerhardt, UMR 5253 CNRS, Ingeńierie et Architectures Macromolećulaires, Ecole Nationale Supeŕieure de Chimie de Montpellier, 8 rue de l’ećole normale, 34296 Montpellier, Cedex 05, France ‡INSA-Lyon, IMP, UMR5223, F-69621, Villeurbanne, France Universite ́ de Lyon, F-69622, Lyon, France

Biobased thermosetting epoxy: present and future.

Reḿi Auvergne,† Sylvain Caillol,† Ghislain David,*,† Bernard Boutevin,† and Jean-Pierre Pascault‡,§ †Institut Charles Gerhardt UMR CNRS 5253 Laboratoire Ingeńierie et Architecture Macromolećulaire, Ecole Nationale Supeŕieure de Chimie de Montpellier, 8 rue de l’Ecole Normale, 34296 Montpellier Cedex 05, France ‡INSA-Lyon, IMP, UMR5223, F-69621, Villeurbanne, France Universite ́ de Lyon, F-69622, Lyon, France

From Vegetable Oils to Polyurethanes: Synthetic Routes to Polyols and Main Industrial Products

Most of biobased polyols for polyurethanes are synthesized from vegetable oils. In the first part, the present review goes into details of these different synthetic routes to obtain polyols. First, olefinic functionalities of triglycerides could easily be epoxidized, leading to reactive epoxide groups. Second, triglycerides double bonds could undergo a wide ranges of reactions to yield polyols. Finally, the carbonyl group could also be used as a reactive group to yield various polyols. In the second part, the present review is dedicated to the commercial biobased polyols, and, based on the patent literature focuses on the industrial synthetic routes.

Fluoroelastomers: synthesis, properties and applications

Abstract The review seeks to cover recent developments in the area of fluorinated elastomers. It reports that, except for isolated cases, most fluoroelastomers are synthesized by radical co-, ternary or tetrapolymerizations. Hence, after reminding the most known syntheses of fluoroalkenes involved in the preparation of these fluoropolymers and recent achievements of block, graft and alternating copolymers, several academic laws and concepts (e.g. kinetics) of the copolymerization are presented. The section dealing with the synthesis of fluoroelastomers is divided into two parts: the first one covers the preparation of fluorinated copolymers containing tetrafluoroethylene, while the second one extensively describes the preparation of fluoroelastomers based on vinylidene fluoride. This section also points out recent syntheses on novel reactive functional trifluorovinyl or vinyl ether monomers for easy curing of original fluoropolymers. Then, heteroatom-containing fluoroelastomers are briefly summarized. Various methods of curing are reported in the following section while the next one describes ingredients used in formulations of fluoroelastomeric systems. This review also covers compounding and processing of this class of fluoropolymers. Finally, a summary of various properties and applications of fluoroelastomers is presented showing how such products resistant to severe conditions are useful in modern industries.

New plasticizers for wheat gluten films

Abstract Diethanolamine and triethanolamine were selected among several low and high molecular weight polyols and amines tested as potential plasticizers of wheat gluten film. In comparison with glycerol, their use did not significantly affect the solubility in water, the opacity of the film (both increased very slightly) and the water vapor barrier properties. However, significant changes in mechanical properties were observed, i.e., increase in extensibility and elasticity. At 58% relative humidity (RH) and 20 g/100 g dry matter of di or triethanolamine, the elongation was five times higher than film plasticized with glycerol. At 98% RH, water appeared to compete with the amines to act as the plasticizer. Dynamic mechanical thermal analyses showed a glass transition temperature similar to that of the glycerol plasticized film. However, the observed broadening of thermal transition and the decrease in height of tan δ peak in the presence of amines, were related to differences in the type of the interactions with the proteins and to the basicity of the amino compounds.

Study of thermal and mechanical properties of virgin and recycled poly(ethylene terephthalate) before and after injection molding

Abstract In this study, we compared the thermal properties (glass transition, melting point and crystallinity) and mechanical properties (Young’s modulus, elongation at break and impact strength) of post-consumer poly(ethylene terephthalate) (PET) bottles with those of the virgin resin. We studied two types of scraps of recycled PET: one arising from homogeneous deposits of bottles and the other of heterogeneous deposits soiled by contaminants such as PVC and adhesives. The presence of contaminants and residual moisture coming in the shape of scraps facilitate the crystallization of recycled PET compared to virgin PET and induces cleavages of chains during the melt processing. This leads to a reduction in intrinsic viscosity and consequently in molecular weight, and these decreases are more significant when the recycled resin is soiled. Virgin PET exhibited a ductile behavior (>200% of elongation at break),whereas post-consumer PET bottles exhibited a brittle one (

Vanillin, a promising biobased building-block for monomer synthesis

Vanillin was used as a renewable building-block to develop a platform of 22 biobased compounds for polymer chemistry. Vanillin-derived biobased monomers bearing epoxy, cyclic carbonates, allyl, amine, alcohol and carboxylic acid moieties were synthesized. They can be used, among many others, in epoxy, polyester, polyurethanes, and Non-Isocyanate PolyUrethanes (NIPU) polymer synthesis. The epoxy-functionalized compounds were synthesized under solvent-free conditions and are original biobased aromatic epoxy monomers. Cyclic carbonates were prepared through a catalytic reaction between epoxy compounds and CO2. Thiol–ene reactions allowed the functionalization of allylated compounds with amines, acids and alcohols. The amine-functionalized compounds are, to our knowledge, the first non-aliphatic biobased amine hardeners, usable either in epoxy or NIPU materials.

Synthesis and properties of biobased epoxy resins. part 1. Glycidylation of flavonoids by epichlorohydrin

Biobased epoxy resins were synthesized from a catechin molecule, one of the repetitive units in natural flavonoid biopolymers also named condensed tannins. The reactivity of catechin toward epichlorohydrin to form glycidyl ether derivatives was studied using two model compounds, resorcinol and 4-methylcatechol, which represent the A and B rings of catechin, respectively. These model molecules clearly showed differences in reactivity upon glycidylation, explaining the results found with catechin monomer. The reaction products were characterized by both FTIR and NMR spectroscopy and chemical assay. The glycidyl ether of catechin (GEC) was successfully cured in various epoxy resin formulations. The GECs thermal properties showed that these new synthesized epoxy resins displayed interesting properties compared to the commercial diglycidyl ether of bisphenol A (DGEBA). For instance, when incorporated up to 50% into the DGEBA resin, GEC did not modify the glasstransition temperature. Epoxy resins formulated with GEC had slightly lower storage moduli but induced a decrease of the swelling percentage, suggesting that GEC-enhanced crosslinking in the epoxy resin networks. VC 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2261–2270, 2011

Synthesis of fluorinated telomers. Part 1. Telomerization of vinylidene fluoride with perfluoroalkyl iodides

Abstract Thermal and redox-induced telomerizations of vinylidene fluoride (VDF) with linear (n-C 4 F 9 I) or branched (i-C 3 F 7 I) perfluoroalkyl iodides have been performed. In both cases, thermal telomerizations led to telomeric-type distributions of the first five (from linear telogen) or the first three (from branched telogen) adducts produced, with better yields at higher temperatures. The redox-initiated telomerization was more selective since it led to the first two adducts only. For both reactions, mono- and di-adducts were isolated and characterized by 1 H and 19 F NMR spectroscopy. Interestingly, both the diadducts were composed of two isomers (i.e. the expected telomer and R F CH 2 CF 2 CF 2 CH 2 I). Two mechanisms are proposed and it is assumed that the products may be obtained either by chain propagation or by stepwise telomerization. In addition, attack of the electrophilic radical on the nucleophilic side of VDF is discussed.

Copolymerization of fluorinated monomers: recent developments and future trends

Abstract This review summarizes several aspects of the copolymerization of fluoroalkenes with nonhalogenated or fluorinated olefins. According to the amounts of monomers involved, the resulting polymers may fall into various kinds of materials: thermoplastics, elastomers and thermoplastic elastomers. Hence, novel polymers are produced with complementary properties due to functional groups (e.g., solubility, adhesion, curing). In addition, this survey shows how a wide variety of monomers, reactive in copolymerization with fluoroolefins, lead to new products. In most cases, random copolymers are obtained. Regarding the kinetic and basic points of view, the Q and e parameters (linked to the reactivity) of most fluoroalkenes are supplied. Further, the structure of the copolymers is also discussed taking into account theoretical and thermodynamic concepts. Finally, alternating copolymerization based on electron-withdrawing fluorinated monomer with electron-donating hydrogenated comonomer (e.g., vinyl ethers) is presented and illustrated with examples.