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Fatty acid sugar esters represent an important class of non-ionic bio-based surfactants. They can be synthesized from vinyl fatty acids and sugars with enzyme as a catalyst. Herein, the influence of the solvent, the lipase and the temperature on a model reaction between vinyl palmitate and glucose via enzymatic catalysis has been investigated and the reaction conditions optimized. Full conversion into 6-O-glucose palmitate was reached in 40 hours in acetonitrile starting from a reactant ratio 1:1, at only 5%-wt loading of lipase from Candida antarctica B (CALB) without the presence of molecular sieves.

Trehalose diesters exhibiting $\alpha$,$\omega$-unsaturation are glycolipids which can be easily polymerized by ADMET (acyclic diene metathesis) polymerization. In this paper, enzymatic esterification was performed to selectively esterify primary hydroxyl groups of trehalose (6 and 6'-positions) with vinyl undecenoate. The vinyl ester was beforehand obtained by palladium-catalyzed transesterification of undecenoic acid with vinyl acetate. The resulting trehalose diundecenoate was homopolymerized and copolymerized with undecenyl undecenoate in order to obtain random copolymers with different compositions. The synthesis of such copolymers was confirmed by 1 H NMR spectroscopy and size exclusion chromatography (SEC). Their solid-state phase separation were investigated by DSC and X-ray scattering as function of temperature and their solution self-assembly was investigated by dynamic light scattering (DLS) in water.

New bio-based diamines were successfully synthesized from vanillin and fully characterized. These amines, methylated divanillylamine (MDVA) and 3,4-dimethoxydianiline (DMAN), were then used as curing agent with epoxy monomers. Epoxy thermosets obtained from these new bio-based amines exhibited promising thermomechanical properties in terms of glass transition temperature and char residue. These latter could be valuable alternative to conventional amine hardener.

This paper aimed at obtaining cross-linked polymeric materials of biomass origin. For this purpose one-pot polyesterification of methyl ricinoleate and methyl 12-hydroxystearate using titanium isopropoxide as a catalyst has been performed leading to polyesters known as estolides. The obtained estolides were successfully cross-linked using dicumyl peroxide or a sulfur vulcanization system. The so-formed bio-based elastomers appeared to exhibit promising properties. The latter were analyzed by mechanical tensile tests and thermal techniques (TGA, DSC, DMA) and showed high thermal stability (T5% = 205-318 {\textdegree}C) and tailored physico-mechanical properties (low glass transition temperature in the range from-2 69 to-54 {\textdegree}C) and good tensile strength (0.11-0.40 MPa). Networks prepared from high molecular weight estolides appear to be promising bio-based elastomers. Practical applications : The vegetable oil-based estolides described in this contribution, are new fully bio-based precursors for further elastomers synthesis. The resulting estolide networks (obtained by peroxide or sulfur cross-linking) exhibit tailored thermo-mechanical properties.

In the context of the development of bio-refineries, glycerol and its derivatives are co-products of the oleochemistry for which new valorization routes must be found. In this study, the polymerizability of divinylglycol (DVG), a symmetrical C-6 glycerol derivative which bears a vicinal diol and two vinyl functions was studied. The reactivity of the hydroxyl and vinyl functions of DVG through polycondensation and polyaddition reactions was investigated. In a first step, the synthesis of polyesters was carried out by reaction of DVG with various biosourced diesters. In a second route, DVG was polymerized through its vinyl functions by ADMET and thiol-ene addition. Finally, three-dimensional epoxy-amine networks were prepared from a series of diamines and bis-epoxidized DVG, the latter being prepared by oxidation of the DVG double bonds. These different polymerization reactions showed that DVG double bonds were more reactive than the alcohol ones and that a panel of original polymers could be obtained from this bio-sourced synthon.

Widely available vegetable oils were readily derivatized into chemically pure ABn-type monomers (n = 2 or 3). Their polymerization led to unprecedented hyperbranched polyesters. Four different AB2/AB3-type monomers bearing one A-type methyl ester and two or three B-type alcohol functions were purposely synthesized via two elementary steps, i.e. epoxidation of the internal double bond of the vegetable oil precursors followed by ring-opening of the epoxy groups under acidic conditions. The polycondensation of these bio-sourced monomers was performed in bulk, in the presence of an appropriate catalyst, giving access to modular hyperbranched polyesters with tunable properties. Among the catalysts tested, zinc acetate, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and sodium methoxide proved the most effective, allowing the achievement of molar masses in the range 3000--10 000 g mol--1 and dispersities varying from 2 to 15, depending on the initial conditions. The degree of branching, DB, as determined by 1H NMR spectroscopy, was found to be between 0.07 and 0.45. The as-devised hyperbranched polyesters displayed either amorphous or semi-crystalline properties, as a function of the selected AB2/AB3-type initial monomers, with a glass transition temperature, Tg, ranging from --33 to 9 {\textdegree}C and a decomposition temperature at 5 wt% of the sample, Td5%, varying from 204 to 340 {\textdegree}C., Comment: http://lcpo.fr/index.php/research-teams/2-biopolymers-and-bio-sourced-polymers, http://lcpo.fr/index.php/research-teams/1-polymerization-catalyses-and-engineering

As we passed the 20th anniversary of the publication of the 12 principles of green chemistry, the sustainable modification of cellulose, being the most abundant biobased polymer, is certainly worth considering. Many researchers work on an efficient valorization of this renewable resource due to its manifold and promising application possibilities, but very often the use of non-sustainable approaches (i.e., solvents, reactants and modification approaches) only addresses the renewability aspect of cellulose, while neglecting most or all of the other principles of green chemistry. In this review, we have employed the use of E-factors together with basic toxicity information to compare between various approaches for homogeneous cellulose modification. This approach, though simple and certainly not overarching, can provide a quick and useful first sustainability assessment. Therefore, in order to achieve a truly sustainable modification of cellulose, its renewability combined with mild and efficient reaction protocols is crucial in order to obtain sustainable materials that are capable of reducing the overall negative impact of today's fossil-based polymeric materials.