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CNRS patent portfolio related to Biosourced Chemistry

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Patents list for licensing opportunities I - ENERGY: 1 « CATALYST-BASED HIGH-YIELD HYDROGEN PRODUCTION FROM BIOSOURCED ALCOHOL » Ref: 05007-01 – page 4 2 « REFORMING TAR IN THE STEAM GASIFICATION OF BIOMASS » Ref: 02809-01 – page 5 3 « BIOCATALYSED SYNTHESIS OF BIODIESEL » Ref: 02179-01 – page 7 4 « HETEROGENEOUS CATALYTIC PROCESS OF A MIXTURE OF BIOFUELS » Ref: 01855-01 – page 8 II- BIO-BASED POLYMERS: 5 « PROCESS FOR CLEAN MODIFICATION OF POLYSACCHARIDES » Ref: 62972 – page 9 6 « METHOD FOR THE CONTROLLED OXIDATION OF POLYSACCHARIDES » Ref: 64167 – page 10 7 “POLYSACCHARIDES DERIVATIVES INCLUDING AN ALCENE GROUP” Ref: 03851-02 – page 11 8 “CHITOSAN BASED THERMOASSOCIATIVE COPOLYMERS AND AQUEOUS SOLUTIONS DERIVED THEREOF” Ref: 01496-01 – page 12 9 « MICROFIBRILS AND/OR MICROCRISTALS, ESPECIALLY CELLULOSE, DISPERSION IN ORGANIC SOLVENT » Ref: 61757 – page 13 10 « THERMOSETTING EPOXY RESINS FROM RENEWABLE RESOURCES » Ref: 03641-01 – page 14 11 « PHENOLIC RESINS WITHOUT FREE FORMALDEHYDE» Ref: 03641-02 – page 16 12 «FUNCTIONNALISATION OF FATTY SUBSTANCES » Ref: 03622-01 – page 17 13 «A NEW CLEAN PROCESS FOR THE PREPARATION OF VEGETABLE OIL-BASED POLYOLS AND POLYURETHANE RESINS» Ref: 02664-01 – page 18 14 « NEW METHOD TO PREPARE BIO-BASED POLYOLS » Ref: 02664-02 – page 19 15 «NEW BIOBASED POLYOLS PREPARED BY THIOLISATION» Ref: 02664-03 – page 21 16 «POLYURETHANE SYNTHESIS WITHOUT USING ISOCYANATES» Ref: 02664-04 – page 22 17 «BISCARBONATE PRECURSORS, METHOD FOR PREPARING SAME AND THEIR USES» Ref: 02664-05 – page 23 18 «POLY (ESTER-URETHANE)s FROM RENEWABLE RESOURCES» Ref: 03404-01 – page 24 19 « NANOFABRICATION OF SEMICONDUCTORS EMPLOYING SACCHARIDIC DIBLOCK COPOLYMERS LITHOGRAPHY » Ref: 03363-01 – page 25

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20 « MECHANICAL PROPERTIES INTENSIFICATION PROCESS OF A PLANT FIBER » Ref: 03647-01– page 26 21 « NEW BRANCHED AND UNSATURATED COMPOUNDS, PRECURSORS OF NEW BIOBASED POLYMERS » Ref: 04860-01– page 27 III- BIO-BASED MOLECULES: 22 « BIOSOLVENTS COMPOSITIONS OBTENTION ESTERIFICATION PROCESS AND OBTAINED BIOSOLVENTS COMPOSITIONS » Ref: 01855-02 – page 28 23 « METHOD FOR 5-HMF PREPARATION (5-HMF: 5-HYDROXYMETHYLFURFURAL) » Ref: 04381-01 – page 29 24 « FURFURAL PRODUCTION » Ref: 04381-02 – page 30 25 «GLUCOSE-FRUCTOSE ISOMERISATION CATALYZED BY SOLID BASES AND METHOD FOR 5-HMF PRODUCTION» Ref: 04756-01 – page 31 26 « ENVIRONMENTALY FRIENDLY SYNTHESIS OF ACETALDEHYDE FROM LACTIC ACID » Ref: 03216-01 – page 32 27 « METHODS FOR ETHERIFYING GLYCEROL » Ref: 84379-01 – page 33 28 « BIOTECHNOLOGICAL PREPARATION OF FURCELLARAN : AN HYDROCOLLOID WIDELY APPRECIATED IN FOOD INDUSTRY » Ref: 05668-01 – page 34 IV- BIOPROCESSES: - Enzymes 29 « BACILLUS PUMILUS BILIRUBIN OXIDASE AND APPLICATIONS THEREOF » Ref: 03383-01 – page 35 30 « MAGNAPORTHE ORYZAE BILIRUBIN OXIDASE AND APPLICATIONS THEREOF » Ref: 04329-01 – page 36 31 « BACTERIAL IODOPEROXIDASES, METHODS OF PREPARATION AND THEIR USES » Ref: 04207-01 – page 37 - Photobioreactors 32 «THIN PHOTOBIOREACTOR WITH ENHANCED VOLUMETRIC PRODUCTIVITY AND THERMAL MANAGEMENT» Ref: 03079-01; Ref: 03256-01 – page 38 33 «DICOFUV: PHOTOBIOREACTOR WITH CONTROLED MIGHT FLOWVOLUMETRIC PRODUCTIVITY AND THERMAL MANAGEMENT» Ref: 03256-02 – page 40 - Extraction 34 « DEVICE AND METHOD FOR PLACING IMMISCIBLE FLUID PHASES IN CONTACT WITH EACH OTHER BY MEANS OF CENTRIFUGAL FORCE » Ref: 03020-01 – page 41

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I - ENERGY:

Catalyst-based high-yield hydrogen production from biosourced alcohol

CONTEXT Hydrogen has been forcasted as one of the highest energy vector in the near future. However, one cannot get hydrogen naturally. It has to be synthesized from a primary source and then transported, stored and distributed toward the final users. As of right now, Hydrogen is essentially made from natural gas and hydrocarbons by steam reforming. Apart of using fossil ressources, this reaction have other disadvantages such as high temperature operation. There is therefore a demand for a renewable way to supply Hydrogen. As a consequence, biosourced alcohol such as Ethanol has been one of the few sources investigated for Hydrogen synthesis. Investigation has therefore been made toward the use of catalyst for the following reactions: C2H5OH + 3 H2O → 6 H2 + 2 CO2 C2H5OH + 1,5 O2 → 3 H2 + 2 CO2 So far, there is clearly a demand for inexpensive catalyst usable at low temperature for the high-yield synthesis of Hydrogen from alcohol and that avoids the formation of carbon and by-products such as acetaldehyde or methane. TECHNICAL DESCRIPTION In the present work, the inventors have answered the demand by developping a high-yield Hydrogen synthesis process from alcohol (in presence of water) requiring low energy input with an inexpensive catalyst and that has a limited formation of carbon. The catalyst used for the reaction is based on a cerium and nickel oxyhydride. DEVELOPMENT STAGE So far, the catalyst synthesis has been assessed on a large laboratory scale and the synthesis of Hydrogen has been sucessfully assessed with said catalyst: 0,03 g catalyst with C2H5OH / H2O / O2 – Oven temperature 50°C H2 (40% molar), CO2 (40%) and CO (18%) with unsignificant traces of CH4 and CH3CHO. BENEFITS

• Biosourced availability of raw material; • Low temperature; • No carbon formation; • High Hydrogen yield.

INDUSTRIAL APPLICATIONS The present invention aims at providing an alternate way of producing hydrogen for any applications. Among the most promising applications, one can cite fuel cell.

Our Reference 05007-01 Keywords Hydrogen, alcohol, reforming, biogas, fuel cell Status of Patent French priority patent application FR1350218 filed on January 10th, 2013 and entitled « Procédé de production d'hydrogène » Inventors Louise DUHAMEL Sébastien PAUL Franck DUMEIGNIL Wenhao FANG Commercial Status Exclusive or non exclusive license Laboratory Unité de Catalyse et Chimie du Solide (UCCS, UMR8181), Lille, France

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REFORMING TAR IN THE STEAM GASIFICATION OF BIOMASS

CONTEXT

Since the increase in petroleum price, interest in use of biomass as a partial replacement for fossil fuels via biomass to liquid (BTL) or biomass to gas (BTG) processes is increasing. One of the most crucial problems in biomass gasification technology is the removal of tar, which is a mixture of condensable aromatic compounds. Tar can condense or polymerize into more complex structures in exit pipes, heat exchangers or on particulate filters, leading to choking and attrition This can result in a decrease of total efficiency and increase of the cost of the process. Tar elimination from the gasification product is necessary for any industrial application particularly for Fisher Tropsch or hydrogen use in fuel cells.

TECHNICAL DESCRIPTION

The present invention relates to a catalyst including an olivine substrate on which an iron compound layer is deposited, produced by impregnating the olivine substrate with a solution including an iron salt, and then heat-treating same. Said catalyst is useful for steam-reforming tar, in particular in gaseous media from the steam gasification of biomass. Further, the catalyst can be used alone for catalyzing the steam gasification of organic compounds from biomass while limiting the amount of tar produced in the synthesized gases.

BENEFITS

The catalyst can be used both for the reaction of tar reforming and biomass gasification associated with water gas shift reaction (WGSR). It has the same activity on tar reforming than Ni-olivine based catalysts but presents low friability, no toxicity and lower cost of preparation. It helps to reduce by at least a factor of ten the tar contents of biomass gas and to increase hydrogen contents both by tar reforming and WGSR. It is also effective for ammonia (NH3) and some sulfur compounds removal.

INDUSTRIAL APPLICATIONS

Hydrogen and syngas production, biomass gasification

DEVELOPMENT STAGE

Scale-up of the catalyst has been realized from 20g to 1000kg and the prepared catalyst tested in a 1 MWth fluidized bed pilot plant. Both a significant improvement of gas and hydrogen yield and a drastic decrease of tar and methane content compared to olivine have been obtained in similar operating conditions.

Our Reference 02809-01 Keywords Hydrogen, biomass, gasification Status of Patent FR0953376: Priority patent of invention filed on May 20, 2009 entitled: " Catalyseur pour le réformage de goudrons utilisables dans la vapogazéifictaion de la biomasse " EP2432591 National phases : EP, US, CA & JP Inventors KIENNEMANN Alain COURSON Claire VIRGINIE Mirella Commercial Status Research agreement, exclusive or non exclusive licenses Laboratory Laboratoire des Matériaux et surfaces et Procédés pour la catalyse (LMSPC, UMR 7515), Strasbourg France. http://lmspc.alsace.cnrs.fr/

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Table 1: Operating conditions of biomass steam gasification tests and percentage variations of the main gasification parameters, with respect to the blank test I (results obtained with the biomass bubbling fluidized of University of Teramo, Italy).

Gasification test I II IIIBed inventory Olivine Fe/olivine Fe/olivineDuration of test (min) 60 154 80Biomass flow rate (g/min) 8 5 5Nitrogen flow rate (l/min) 11 11 11Steam feeding rate (g/min) 8,50 6 6gasifier bed temperature (°C) 808 828 821Gas yield, % +37 +42Tar content in the producer gas, % -68 -54Tar content per kg biomass daf, % -56 -35H2 yield,% +85 +91CH4 yield, % -25 -23H2 yield mol/kg daf +32 +33

Figure 1: Photographs of the tar recovered after biomass gasification at different temperatures (results obtained with the bech-scale dual fluidized bed gasifier of National Research Council of Zaragossa, Spain).

Gasifier temperature (°C)

Tar (g.Nm-3)

olivine 10Fe/olivine

Photographs of the tar recovered

Table 1: Operating conditions of biomass steam gasification tests and percentage variations of the main gasification parameters, with respect to the blank test I (results obtained with the biomass bubbling fluidized of University of Teramo, Italy).

Gasification test I II IIIBed inventory Olivine Fe/olivine Fe/olivineDuration of test (min) 60 154 80Biomass flow rate (g/min) 8 5 5Nitrogen flow rate (l/min) 11 11 11Steam feeding rate (g/min) 8,50 6 6gasifier bed temperature (°C) 808 828 821Gas yield, % +37 +42Tar content in the producer gas, % -68 -54Tar content per kg biomass daf, % -56 -35H2 yield,% +85 +91CH4 yield, % -25 -23H2 yield mol/kg daf +32 +33

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BIOCATALYSED SYNTHESIS OF BIODIESEL

CONTEXT The industrial production of biodiesel in Europe, USA and Japan is carried out by chemical processes based on transesterification catalysed by strong bases. Such processes show several problems such as the difficulty to recover the by-product glycerol, the necessity to eliminate the base catalyst from the reaction medium by washing with water, which produces large amounts of alkaline wastes. Over the last years,the enzymatic synthesis of biodiesel by transesterification from vegetable oils has been widely described. However the use of volatile organic solvents as reaction media in enzymatic processes shows also several disadvantages such as the necessity of recovery, as a consequence of the high price and environment impact. Ionic liquids have emerged as green solvents due to their capacity to constitute a clean alternative, non pollutant and reusable as compared to volatile organic solvents TECHNICAL DESCRIPTION The invention concerns a process for the production of biodiesel using a recyclable solvent with low environmental impact. The invention relates to the use of a combination of: -at least one ionic liquid which is lipophilic, solid at room temperature but liquid at the reaction temperature (~60°C) and non miscible with water and, -at least one enzyme for the implementation of an esterification and/or transesterification process of a substrate consisting of oils , fats , fatty acids or their mixtures with at least one alcohol in a single homogeneous phase at the temperature at which esterification and/or transesterification process is performed. Very importantly, three phases are formed at the end of esterification and/or transesterification process making them easily separable by a simple decantation: -a first phase containing the ionic liquid and the enzyme, -a second phase consisting of glycerol, excess alcohol and water, -a third phase consisting of fatty acid alkyl esters, i.e., the biodiesel. The invention enables to process a mixture of mono, di and triacyl glycerides and fatty acids into biodiesel

BENEFITS - Improved reaction kinetic - Easy separation of reaction products leading to biodiesel just by decantation - No catalyst poisoning and easy recycling of the catalytic mixture - After four cycles, 99% yields of biodiesel are still obtained. - Presence of water and/or free carboxylic acids in the raw oil or fat do not severely

impair the process The reaction mixture is free from inorganic acid and base. That’s advantageous because no aqueous extraction is required to remove the traces of acid or base as it is the case in the traditional synthesis.

INDUSTRIAL APPLICATIONS This method aims at a green synthesis of biodiesel.

Our Reference 02179-01 Keywords Ionic liquids, Biodiesel, Biocatalysis Status of Patent Patent application EP n° 08 291101 filed on November 21, 2008 entitled "Use of ionic liquids for implementing a process for the preparation of biodiesel” WO2010057996 Inventors Michel VAULTIER Jose Luis IBORRA Teresa DE DIEGO Pedro LOZANO Commercial Status Exclusive or non-exclusive licenses and collaborative research. Laboratory Chimie et Photonique Moléculaires, UMR 6510 a CNRS and Université de Rennes 1 Laboratory, in Rennes, France. http://www.umr6510.univ-rennes1.fr/

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HETEROGENEOUS CATALYTIC PROCESS OF A MIXTURE OF BIOFUELS

TECHNICAL DESCRIPTION This invention describes a process for converting vegetable oils and ethanol into a mixture of biodiesel and glycerol ethers in one heterogeneous catalytic step. The catalytic system used promotes as well the transesterification reaction with ethanol and the etherification of glycerol with ethanol. BENEFITS This invention combines four main advantages compared to the usual processes based on homogeneous or heterogeneous basic catalysts : - Glycerol ethers are obtained using a cheap, non toxic and biosourced alcohol. - Crude or used vegetable oils may be used since the heterogeneous catalyst is not sensitive to free acids. – The difficult step of glycerol separation is avoided since glycerol ethyl ethers are simultaneously produced with biodiesel. - Thus, the biofuel yield produced from vegetable oils and ethanol is increased by 10%. INDUSTRIAL APPLICATIONS Applications include : the conversion of crude or used vegetable oils into a biofuels mixture composed of fatty acid ethyl esters and glycerol ethyl ethers, etherification of crude glycerol to produce oxygenate additives to gasoline or biofuels.

Our Reference 01855-01 Keywords CATALYST; GLYCEROL; BIOFUEL Status of Patent Priority patent of invention FR 08/02491 filed on May 5, 2008 entitled: "Procédé de préparation d’un mélange de biocarburants" WO2009141564 Inventors Nadine ESSAYEM, Rodrigo LOPES DE SOUZA, Berna HAMAD, Gilbert SAPALY, Paulo PRIES DE OLIVEIRA, Wilma GONZALES, Commercial Status Research agreement, exclusive or non exclusive licenses Laboratory Institut de Recherches sur la catalyse et l’environnement de Lyon (IRCE), (UMR 5256), Lyon, France. http://www.ircelyon.univ-lyon1.fr/

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II- BIO-BASED POLYMERS:

PROCESS FOR CLEAN MODIFICATION OF POLYSACCHARIDES

TECHNICAL DESCRIPTION The invention describes a new catalytic process for the clean modification of polysaccharides obtained from renewable cheap raw materials (starch, cellulose, cellulose esters and ethers, inulin, guar gum, etc.) by oxidation with hydrogen peroxide. The conversion of polysaccharides is achieved via a one-pot process easy to scale up. The catalyst is cheap, available commercially and only minute amounts are required. The oxidation converts part of the alcohol functions to carboxylic and carbonyl functions whereby increasing the hydrophilic properties of the natural polysaccharides which make them suitable for various applications. DEVELOPMENT STAGE The oxidation of various polysaccharides has been developed at laboratory pilot scale (Kg), but the scaling up is very easy. The oxidation is run at near-room temperatures and atmospheric pressure and needs only conventional equipment available e.g. in the food industry. The oxidation is easy to control by adjusting the reaction parameters. BENEFITS The one-pot chemical modification of natural polysaccharides leads to tailor-made products that can be used for several applications. This process is simple, flexible and environmentally benign. Differently modified polysaccharides can be prepared in one step with yields close to 100%. The modified natural polymers do not have to undergo REACH registration. INDUSTRIAL APPLICATIONS. Modified polysaccharides are used in several domains such as paper industry, painting and coating industry, adhesives and binders, detergents (phosphates substitutes), water absorbents, pharmaceutical industry (excipients and formulation compounds) and as food ingredients.

Our References 62972 Keywords Modified biopolymers, Status of Patent Priority patent application FR n°0208851 filed on July 12, 2002, entitled “ Procédé pour l'obtention de polysaccharides modifiés” WO2004007560 published on January 22, 2004 National phases : EP, CA (EP03763934) Inventors Alexander SOROKIN, Pierre GALLEZOT, Svetlana SOROKIN Commercial Status non-exclusive licence, Collaborative agreement Laboratory Institut de Recherches sur la Catalyse (UPR 5401), a CNRS laboratory, in VILLEURBANNE, FRANCE. www.ircelyon.univ-lyon1.fr

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METHOD FOR THE CONTROLLED OXIDATION OF POLYSACCHARIDES

CONTEXT The oxidation of polysaccharides by nitrogen dioxide (NO2/N2O4) as oxidizing agent is a well known reaction. The use of NO2 gas has, however, proved to be tricky resulting in particular in heterogeneities. Various methods of oxidation in organic solvents medium have therefore been proposed using as solvent, carbone tetrachloride, freons, perfluoro solvents, hydrofluoroethers... The use of halogenated solvents represents, however a risk to the environment and for numerous applications in particular in the medical field, it is imperative to have products that are oxidised homogeneously. TECHNICAL DESCRIPTION This invention describes a new method for the oxidation of polysaccharides that makes it possible to obtain variable mass % carboxylic acid content ranging, in the case of cellulose, up to approximately 25,5% (which corresponds to 100% oxidation of the primary hydroxyl groups), distributed homogenously, regardless of the degree of oxidation. BENEFITS

- Homogeneously carboxilated polysaccharides - Clean process - High modification level

INDUSTRIAL APPLICATION

- Food industry : thickeners, stabilizers, surfactants for low-calorie food products, - Paint, paper or food industry: steric stabilizers for fillers, - Pharmaceuticals applications: excipients, agents for controlling the release of active

ingredients carriers for ointments or for creams, - Surgery applications : Bioresorbables threads and/or for tissue or organ repair in

human and in animals, - Cosmetic applications: viscosity modifiers and gelling agents, - Agents for the complexing or sequestering of metal ions...

DEVELOPMENT STAGE This patent has already been licensed in the field of medical devices. After studies on a lab reactor, a pilot reactor (V=4l) is now installed and tested satisfactorily at the industrial facilities of the licensee. The production plant (70L vessel) is now designed and under construction. Other development in progress : oxidized konjac glucomannan

Our References 64167 Keywords Polysaccharide, cellulose, oxidation Status of Patent French patent n° FR-04 08402 filed on 29th July 2004 and Entitled “procédé d'oxydation controlée de polysaccharides” WO2006018552 CA2575178; EP1778733; CN101018811; JP20088508387; US2008194805 Inventors Michel Vignon Suzelei Montanari Daniel Samain Jean-Stéphane Condoet Commercial Status Exclusive or non-exclusive license , except in some fields R&D Partnership Laboratories CERMAV, centre de recherche sur les macromolecules végetales http://www.cermav.cnrs.fr/ LGC – Laboratoire de génie chimique http://lgc.inp-toulouse.fr/

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POLYSACCHARIDES DERIVATIVES INCLUDING AN ALCENE GROUP

CONTEXT Biomaterial engineering has undergone an important development during the last fifteen years due to the emergence of new applications in drug delivery and tissue regeneration. These materials have evolved progressively from being bioinert, to biodegradable and now also bioactive. Among polymers which can be used to design such materials, natural polysaccharides appear as promising candidates. They generally exhibit good biocompatibility and biodegradability features and can additionally present biological properties. Moreover, their chemical complexity offers several possibilities in terms of structures and properties and their natural origin makes them attractive in an environmental, toxicologic and commercial point of view. Therefore, it is particularly desirable to obtain new natural modified polymers, such as modified polysaccharides, in order to obtain components with new or improved properties like thickening or gelling ones, which can be used in cosmetic, pharmaceutical or biomedical domains. TECHNICAL DESCRIPTION The invention concerns a polysaccharide, and, in particular, an hyaluronic acid bearing a thioester functionalized alcene moity and its manufacturing process. The invention concerns also a composition including such polysaccharides. BENEFITS Many polysaccharides synthesis have been described in the past, but a lot are unsatisfactory in terms of grafting, yield, implement simplicity, efficiency, cost or harmlessness of the solvant used. Moreover, the described modified polysaccharides can be unsatisfactory in terms of functionality, purity, reactivity or use. A need of a simple, effective, and selective method to realize the active molecules grafting on polysaccharides and their chemical cross-linkage in a aqueous or hydro-organic medium still remains. The present invention aims to propose a new process to modify polysaccharides with active molecules or their cross-linkage, avoiding the previous disadvantages. It aims also to provide new polysaccharides derivatives containing reagents likely to be obtained easily and economicaly at an industrial scale. INDUSTRIAL APPLICATIONS The invention aims to provide new types of material, as hydrogels, with applications in the biological, medical, pharmaceutical and cosmetic domains.

Our Reference 03851-02 Keywords Biomaterial, modified polysaccharides, cosmetic, drug delivery Status of Patent FR 1059465: Priority patent of invention filed on november 18, 2010 and entitled "DERIVES DE POLYSACCHARIDES COMPRENANT UN MOTIF ALCENE ET REACTION DE COUPLAGE PAR CHIMIE THIO-CLIC" Inventors Rachel AUZELY, Jimmy MERGY, Eric BAYMA-PECIT. Commercial Status Research agreement, exclusive or non exclusive licenses Laboratory Centre de Recherches sur les Macromolécules Végétales (CERMAV), (UPR 5301 CNRS), Grenoble, France. http://www.cermav.cnrs.fr/

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CHITOSAN BASED THERMOASSOCIATIVE COPOLYMERS AND AQUEOUS SOLUTIONS DERIVED THEREOF

CONTEXT Hydrogel is a class of material composed of hydrophilic polymer networks with high water retention capacity; its physical properties such as, swelling, permeation, mechanical, surface and optical can be modulated. In the medical field, biocompatible hydrogels have broad potential applications, including tissue substitutes, surgical aids and drug delivery. TECHNICAL DESCRIPTION The invention relates to a thermosensitive (poly(ethylene oxide) poly(propylene oxide))-acetal derivative, which can be used to functionalize chitosan, and to the process for the preparation thereof. The invention therefore also relates to a process for functionalizing chitosan by grafting this thermosensitive copolymer and optionally another thermosensitive polymer, poly(ethylene oxide). A subject of the invention is also a chitosan-(poly(ethylene oxide) poly(propylene oxide))-poly(ethylene oxide) derivative which has the advantage of being water-soluble at physiological pH. The invention therefore also relates to the aqueous compositions comprising this derivative and to the use of this composition for the manufacture of gel by heating DEVELOPMENT STAGE Laboratory scale BENEFITS New water soluble copolymer soluble at pH 4 to physiological pH with thermogelling properties INDUSTRIAL APPLICATIONS Cosmetic ant therapeutic applications

Our References 01496-01 Keywords Hydrogel, copolymers, chitosan Status of Patent Priority patent application FR n°07/57506 filed on September 11, 2007, entitled “ Copolymères thermoassociatifs à base de chitosane et solutions aqueuses dérivées” WO2009034130 National phases : EP, US, CA & JP Inventors Rachel AUZELY, Caroline CREUZET Commercial Status Exclusive or non-exclusive licence, Collaborative agreement Laboratory Centre de recherches sur les macromolécules végétales (C.E.R.M.A.V) (UPR 5301), a CNRS laboratory, in Grenoble, FRANCE. http://www.cermav.cnrs.fr

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MICROFIBRILS AND/OR MICROCRISTALS, ESPECIALLY CELLULOSE, DISPERSION IN ORGANIC SOLVENT

CONTEXT Native cellulose occurs in the form of microcrystals and/or of very elongated microfibrils, often organized as fibres. This cellulose can be found in plants, but also in certain fungi, bacteria, amoebae and even some marine animals. Acid hydrolysis of cellulose in an aqueous medium leads to stable aqueous colloidal suspensions of individual microcrystals. Depending on the origin of the cellulose, the lateral dimensions of the microcrystals and/or microfibrils can vary from 2 nm to 50 nm. The lengths of the said microcrystals and/or microfibrils can greatly exceed one micron. Depending on the origin of the cellulose (for example cotton) and the concentrations used (for example high concentrations, varying between 2 and 10% w/w), stable colloidal dispersions of cellulose in water are organized in the form of a liquid crystal of the cholesteric type the spacing of which can vary from 80 to 10 mu m, depending on the operating conditions employed. All properties and applications of cellulose microcrystals and/or microfibrils are due to the very high form factor of these objects (i.e. the ratio of length to width is high, typically over 10), and to their good dispersion in the usage medium. However, until now it has only been possible to obtain dispersions of cellulose microfibrils and/or microcrystals in water or in very polar solvents (glycerol, ethylene glycol, DMSO etc.)

TECHNICAL DESCRIPTION The present invention supplies suspensions or dispersions of microfibrils and/or of microcrystals, especially of cellulose or of any other fibrillar organic substance selected from the group consisting of cellulose, chitin, and polysaccharides, in the organic solvents for which the said suspensions or dispersions had until now been impossible to produce providing thus stable suspensions or dispersions of cellulose microfibrils and/or microcrystals in organic solvents, especially apolar or slightly polar ones, without chemical modification of the cellulose. Said colloidal dispersion contains in addition, at least one compound possessing a hydrophilic part and a hydrophobic part.

BENEFITS No chemical modification of the fibrils. Furthermore these aqueous dispersions or suspensions of microcrystals and/or microfibrils, especially of cellulose, which once they have been dried can be redispersed in water or in an organic solvent, while preserving their properties connected with dispersion.

INDUSTRIAL APPLICATIONS * Manufacture of composites: most of the synthetic polymers are only soluble in organic solvents; thus, the application of cellulose microcrystals and/or microfibrils is limited to latex or to water-soluble resins , and for example to cellulose acetate in the case of surface-modified microcrystals.

* Thickener: just as in the case of composites, applications as thickener are limited to aqueous media; thus, we may mention the use of cellulose microfibrils and/or microcrystals for the production of oil-field drilling fluid (drilling muds) , or for improving processed foodstuffs .

* Production of paper with variable optical properties ,

* Preparation of cosmetic or dermatological compositions, for the manufacture of descaling formulations

* pharmacy, personal hygiene products

Our Reference 61757 Keywords COLLOIDAL DISPERSION; MICROFIBRILS; CHITIN; CELLULOSE; MICROCRYSTALS; XYLAN; POLYSACCHARIDE; GLUCAN; MANNAN; ORGANIC SOLVENT; SURFACTANT; GEL; LIQUID CRYSTAL; COMPOSITE MATERIAL; WHISKERS Status of Patent Priority patent of invention FR19990614 filed on June14, 1999 and entitled "Dispersion de microfibrilles et /ou microcristaux notamment de cellulose dans un solvant organique" Extensions: US6967027 JP2003528935 EP1192215 Inventors Laurent HEUX, Celine BONINI Commercial Status Research agreement or exclusive licenses Laboratory Centre de Recherches sur les Macromolécules Végétales (CERMAV) UPR 5301, Grenoble , France. http://www.cermav.cnrs.fr/

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THERMOSETTING EPOXY RESINS from RENEWABLE RESOURCES

CONTEXT First, polymers derived from renewable resources are gaining a great interest due in part to the rarefaction of fossil raw materials.

Second, as Bisphenol A, a widely used building block molecule in epoxy resins, is now classified as reprotoxic", substitution of bisphenol A based epoxy resins by materials coming from renewables ressources is a challenging issue. TECHNICAL DESCRIPTION The invention relates to a method for preparing epoxy resins from a mixture of epoxidized phenolic compounds, wherein said epoxidized phenolic compounds are obtained by the epoxidation of natural phenolic compounds selected from the group comprising simple phenol, acid-phenol, coumarin, naphthoquinone, stilbenoid, flavonoid, isoflavonoid, anthocyanin, condensed tannin and hydrolyzable tannin..

This invention presents a way to obtain new aromatic and polyaromatic epoxyde compounds resulting from renewable resources, which are miscible with amine hardeners under usual conditions of formulation and crosslinking, and which make it possible to control the crosslinking of the resulting epoxy resins. This invention presents also new solutions for preparing vinyl ester resins from renewable resources. BENEFITS These aromatic and polyaromatic compounds are natural phenolic compounds resulting from the biomass and more particularly extracted from plants, trees, vine, grape or algae. The epoxidation could be realised using epichlorhydrine obtained by a chemical reaction on glycerol, by-product of biodiesel process. INDUSTRIAL APPLICATIONS Thermoset epoxy resins are widely used in numerous industries, like coatings, adhesives, composites and electronic components encapsulation.

DEVELOPMENT STAGE Biobased epoxy resins were formulated from glycidyl ether of tannin catechin. Their thermal an mechanical are similar to commercial ones from diglycidyl ether of bisphenol A (DGEBA). Pilot-scale studies are in progress.

Our Reference 03641-01 Keywords Biobased polymers, epoxy resins, tannins Status of Patent Priority patent application n° 0902589 filed on May 27,2009 entitled " Nouveau procédé d’élaboration de resines thermodurcissables epoxy" EP2435493 National phases : EP, US, JP Inventors BOUTEVIN, Bernard BURGUIERE, Carine CAILLOL, Sylvain FULCRAND, Hélène NOUAILHAS, Hélène RAPIOR, Sylvie Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory Institut Charles GERHARDT, a CNRS laboratory (UMR 5253) in Montpellier , France. http://www.icgm.fr

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PHENOLIC RESINS WITHOUT FREE FORMALDEHYDE

CONTEXT Phenolic resins are well known and are generally prepared from phenols and formaldehyde. The use of formaldehyde introduces environmental and toxicological problems in the preparation , fabrication and even in the long term use of such materials.

Formaldehyde — a “VOC,” or volatile organic compound — is a widely used chemical in glues and adhesives and is a preservative used in paints and finishes. .The World Health Organisation’s International Agency for Cancer Research (IARC) in 2004 recommended classification of formaldehyde from group 2A -“probably carcinogenic to humans” to group 1 - “carcinogenic to humans”. Under European Union standards, formaldehyde is currently classified as a category 3 chemical - “weak level carcinogenic hazard -”.

This invention could provide new solutions to obtain phenolic resins without free formaldehyde. TECHNICAL DESCRIPTION The present invention relates to a method for preparing a formaldehyde-free phenolic plastic resin, including a step of preparing a hardener by means of careful oxidation of a polyol and a step of reacting said hardener with phenolic compounds. A polymer containing aldehyde fonctions is used as hardener for phenol resins instead of using formaldehyde for phenolic compounds reticulation. It can be obtained either by polymerization of acroleine or by oxidation of a polyol. BENEFITS These hardeners could be mixed in particular with natural aromatic and polyaromatic compounds resulting from the biomass and more particularly extracted from plants, trees, vine, grape or algae. The hardener could be also sourced from biomass either in the case of the polymerization of acroleine as acroleine could be obtained by a catalysed reduction of glycerol, by-product of biodiesel process or in the case of biobased primary polyols. INDUSTRIAL APPLICATIONS Phenolic resins are used in wood products and moulding powders applications. They also have a wide range of applications on the electrical, mechanical and decorative markets, in the automotive industry in building and construction (glass-reinforced composites) or but not last in thermal insulation products (foams and fibre binders). DEVELOPMENT STAGE Formaldehyde free resins were formulated and tested. Mechanical and thermal properties could be adapted owing to starting polyol and regarding the expected properties.

Our Reference 03641-02 Keywords Biobased polymers, phenolic resins, formaldehyde Status of Patent Priority patent application n° 0905594 filed on November 20,2009 entitled " Nouvelles résines de type phénoplastes obtenues à partir de composés phénoliques et de durcisseurs macromoléculaires portant des fonctions aldehydes " WO2011061456 Inventors BOUTEVIN, Bernard BURGUIERE, Carine CAILLOL, Sylvain DAVID, Ghislain Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory Institut Charles GERHARDT, a CNRS laboratory (UMR 5253) in Montpellier , France. http://www.icgm.fr

17

FUNCTIONNALISATION OF FATTY SUBSTANCES

CONTEXT Today with the rising cost of petroleum base products, the environmental concerns, and the rarefaction of fossil raw materials there is a renewed interest in renewable resources. Triglycerides, fatty acids and esters derived from vegetable oils are very interesting renewable susbstances. Indeed, fatty acids have a long tradition as monomers in coating resins or as lubricants. They have been used as received from the plants as air-drying linseed oils or as parts of resins such as alkyds. All these fatty substances can be chemically modified. The thiol-ene coupling has been considered recently as a promising mechanism to functionalize the double bonds of fatty acids. TECHNICAL DESCRIPTION This invention provide a simple, one step and cheap process to functionalize the double bonds of fatty substances with various reactive functions. This process enables to functionalize fatty substances with a high conversion and with a control over their degree of functionalization.

The functionalized fatty substances could be step growth polymerized with different reactive molecules and even with other functionalized fatty substances in order to obtain polymers derived from renewable resources such as polyurethanes, epoxy resins… BENEFITS Thiol-ene reaction could be performed under UV, without any photoinitiator nor solvent, and with recycling of thiol reactant. This reaction allows to obtain easily new biobased reactants such as primary di- and polyols, primary polyamines, polyacids and polycyclocarbonates. INDUSTRIAL APPLICATIONS Polyols could be used in polyurethanes synthesis. Polyacids and polyamines could be used in epoxy resins synthesis. Owing to the broad range of glass transition temperatures obtained, polymers could be used in various applications from coatings to composites. DEVELOPMENT STAGE Functionalized fatty substances were produced at pilot scale to perform pre-industrial application trials in various formulations. Very interesting results were obtained compared to benchmark.

Our Reference 03622-01 Keywords Biobased polymers, Fatty acids , vegetable oils

Status of Patent Priority patent application n° 1002738 filed on June 30,2010 entitled " Procéde de fonctionnalisation de corps gras d’origine naturelle " WO2012001315 Inventors BOUTEVIN, Bernard CAILLOL, Sylvain DESROCHES, Myriam Commercial Status Non-exclusive licenses, Collaborative agreement Laboratory Institut Charles GERHARDT, a CNRS laboratory (UMR 5253) in Montpellier , France. http://www.icgm.fr

18

A NEW CLEAN PROCESS FOR THE PREPARATION OF VEGETABLE OIL-BASED POLYOLS AND POLYURETHANE RESINS

CONTEXT The invention presents mainly a new clean process to obtain polyols, in particularly diols. This patent protects these new polyols and a way for the synthesis of polymers also. Polyols may be produced from petroleum. As the world’s petroleum resources are depleting, scientists wordwide have been looking into renewable raw materials and more precisely into vegetable oil to replace petroleum-based polyols. Vegetable oil molecules must be chemically transformed in order to introduce hydroxyl groups. Nevertheless, many reactions for preparing polyols from vegetable oils are not very selective. By-products, in addition to alcohol groups, are created during the transformation. Furthermore, many conventional methods of preparing polyols from vegetable oil do not produce polyols having a significant content of hydroxyl groups.

TECHNICAL DESCRIPTION The process of the invention relates to three major steps in preparing polyols from mono- or diester of vegetable oil. All of the obtained synthons by this process are at least bifunctional (polyols) with a well-defined structure. This process is performed with a clean catalytic system (heterogeneous catalysis). By this way, it is possible to obtain two kinds of polyols :

BENEFITS The main use of polymeric polyols is as reactants to make other polymers. For example, they can be reacted with isocyanates to make polyurethanes. Here, it is possible to use a clean process from renewable resources and the very well defined structures of polyols make way for an easy synthesis of polyurethane resins. INDUSTRIAL APPLICATIONS Depending on the type of polyol and isocyanate used the generated foam exhibits different properties. By careful selection of the polyol and isocyanate, foam with varying properties can be generated. It could be soft and flexible with totally open cells, which are used in the furniture industry to very hard dense wood like closed cell rigid foam. The various categories are flexible slab stock (like furniture, bedding, accoustic insulation), flexible cold cure moulded, rigid foam (Refrigerators, thermoware, industrial insulations) and elastomeric applications (coating and adhésives). DEVELOPMENT STAGE Products have shown good properties in adhesive and cosmetics applications. The pilot scale (2kg) has been achieved. The scale up is under developpement (50kg).

Our Reference 02664-01 Keywords Polyols, polyurethane, vegetable oil, renewable materials Status of Patent Priority patent application n°FR0956258 filed on September 11th, 2009, entitled " Nouveaux polyols difonctionnels issus d’acides gras d’origine naturelle" PCT n°FR2010051893 filed on September 10th, 2010 - WO2011030075 Inventors CRAMAIL Henri, CLOUTET Eric, BOYER Aurélie, ALFOS Carine, GADENNE Benoit Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory Laboratoire de Chimie des Polymères Organiques (LCPO), a CNRS laboratory (UMR 5629) Pessac, France. http://www.enscpb.fr/lcpo/

O

A2

O

R'A1

OH

OR' O

R'A1

OH

OR' O

1

1

R'A1

OH

OR'

O

O

A2 OH1

19

NEW METHOD TO PREPARE BIO-BASED POLYOLS

CONTEXT

Natural vegetable oils (triglycerides and fatty acid methyl esters) have recently attracted renewed attention as raw materials for the preparation of bio-sourced polymers, appropriate to a multitude of applications.

For example, polyurethanes (PURs) could be prepared by reacting a polyol and an isocyanate. These materials occupy an important position in the world market of high performance synthetic polymers. PURs have a world production of 14 Mt (in 2006) and are the sixth most widely sold plastic in the world,after HDPE, LDPE, PP, PVC and LLDPE, accounting for approximately 6% of total consumption.

TECHNICAL DESCRIPTION This invention describes a new three steps method to prepare polyols from mono esters of vegetable oils or triglycerides. The first step consists in a transesterification of the methylic esters then the second step an epoxidation of the double bond and the last step is an opening of the epoxyde ring with an alcohol. This invention provide access to new synthons , mono esters or diesters, at least bifunctionals (polyols) and having well defined structure. For example, the inventors have used a variety of sunflower oil with high oleic acid content. The various methyl esters of sunflower oil have been separated by fractional distillation. Methyl esters of oleic acid of high purity have been obtained. Starting from this precursor it is then possible to provide a selected number of hydroxyl groups and thus to control the functionality of this 'building block' monomer. A well-defined structure of monomers is essential to the development of polymeric materials with properties controlled and reproducible. As the desired polymers should be linear, the inventors have for example tried to create at least difunctional monomers (di-OH) from oleic sunflower methyl esters. Here under are presented some examples of the diols synthetized :

Our Reference 02664-02 Keywords Polyols, Polyurethanes, vegetable oil, renewable materials Status of Patent - Priority patent application n°FR0956260 filed on September 11th, 2009, entitled " Nouveau procédé de préparation de polyols et produits tels qu'obtenus " - PCT n° FR2010051894 published on March 17th, 2011 under WO2011030076 Inventors CRAMAIL HENRI ALFOS CARINE ; BAKHIYI RACHIDA; BOYER AURELIE; CLOUTET ERIC Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory Laboratoire de Chimie des Polymères Organiques (LCPO), a CNRS laboratory (UMR 5629) Pessac, France. http://www.enscpb.fr/lcpo/

20

…

BENEFITS It is possible to obtain from vegetables oils well defined symetrical diols having two primary hydroxyl functions and assymetrical diols with a primary hydroxyl functions and a secondary hydroxyl function INDUSTRIAL APPLICATIONS Polyurethanes have been synthetised by bulk polymerization of these polyols with isophorone diisocyanate (IPDI). When reacting with isocyanates to form polyurethanes these compounds could be used as flexible foams, rigid foams, elastomers, fibers, molding compositions, surface coatings and adhesives But these diols can also be used to synthetise polymers like polyester, polyethers or polycarbonates.

DEVELOPMENT STAGE Products have shown good properties in adhesive and cosmetics applications. The pilot scale (2kg) has been achieved. The scale up is under developpement (50kg).…

21

NEW BIOBASED POLYOLS PREPARED BY THIOLISATION

CONTEXT Different approaches exist for the synthesis of polymers from vegetable oils. The first and most common is to choose triglycerides as basic materials and to functionalize them for polymerization. But it’s necessary to find new ways to get a better control over the functionalization of vegetable oils

The synthesis of polyols derived from vegetable oil is well described in the literature because they are excellent precursors for the synthesis of polymers. These materials are gaining popularity because the precursors are bio-based and have an interesting structure and composition.

TECHNICAL DESCRIPTION This invention describes a new two-step method to prepare polyols from mono or di esters of vegetable oils or triglycerides. The first step consists in a transesterification of the ester group with diols and the second step is a thiolization. These inventions provide access to new synthons , mono esters or diesters, at least bifunctionnals (polyols) and having well defined structure. Here under are presented some examples of the diols synthetized : BENEFITS It is possible to obtain from vegetable oils well-defined diols having two primary hydroxyl functions. Some synthons present an original symmetrical structure and depending on the alcool used for the transesterification step, this structure could be modified to obtain polymers with different properties. INDUSTRIAL APPLICATIONS Polyurethanes have been synthesized by bulk polymerization of these polyols with isophorone diisocyanate (IPDI). When reacting with polyisocyanates to form polyurethanes the resulting polymers could be used as flexible foams, rigid foams, elastomers, fibers, molding compositions, surface coatings and adhesives.

DEVELOPMENT STAGE Products have shown good properties at lab scale. The scale up is under development (1kg) in order to test the products on real applications.

Our Reference 02664-03 Keyword Polyols, Polyurethanes vegetable oil, renewable materials Status of Patent - Priority patent application n°FR0957146 filed on October 13th, 2009, entitled " NOUVEAU PROCÉDÉ DE PRÉPARATION DE POLYOLS PAR THIOLISATION ET PRODUITS TELS QU’OBTENUS " - PCT n° FR2010052171

published on April 21th, 2011 under WO2011045536 Inventors CRAMAIL HENRI ALFOS CARINE ; BOYER AURELIE; CLOUTET ERIC Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory Laboratoire de Chimie des Polymères Organiques (LCPO), a CNRS laboratory (UMR 5629) Pessac, France. http://www.enscpb.fr/lcpo/

22

POLYURETHANE SYNTHESIS WITHOUT USING ISOCYANATES

CONTEXT In addition to its contribution to the synthesis of several types of polymeric materials such as thermoplastics and IPN (Interpenetrating polymer networks), Polyurethanes are one of the most important polymeric materials which have many useful properties for various applications especially in machinery industry, coating and paints, elastic fibers and flexible medical devices.

Recently, many studies involve their synthesis from natural resources such as vegetable oils seeking to a better compatibility compared to petrochemicals.

Polyurethanes are typically prepared by reacting polyols with isocyanates. Isocyanates are highly reactive and chemically toxic. It is therefore desirable to implement a process for preparing polyurethanes in the absence of isocyanates. The inventors propose a new process of their synthesis by means of self-condensation.

TECHNICAL DESCRIPTION This invention relates to the synthesis of polyurethane by self-condensation. It also relates to novel monomers and processes for their preparation and their use for the synthesis of polyurethane.

More precisely, the invention relates to a compound with the following formula (I) where: R1 is particularly a straight or branched alkyl group, a is a single or double bond; R2 is particularly a hydrogen atom; R3 and R5 are a hydrogen atom when a is a single bond, and absent when a is a double bond; R4 is a hydrogen atom or an ORb group, where Rb is a hydrogen atom or an alkyl group including 1 to 12 atoms of carbon, and A1 is a divalent alkylene radical.

BENEFITS

The new process of polyurethanes’ synthesis is based on self-condensation of sodium azide and hydroxyl groups.

This technique has the following advantages : the reaction proceeds slowly by simply heating the monomer in a one step and without any other optimization.

INDUSTRIAL APPLICATIONS Green chemistry : new process for the synthesis of polyurethanes in the absence of isocyanates.

DEVELOPMENT STAGE Products have shown good properties at lab scale. The scale up is under development (1kg) in order to test the products on real applications.

Our Reference 02664-04 Keywords Polyurethane; self-condensation ; monomers, synthesis Status of Patent - Priority patent application n°FR0957223 filed on October 15th, 2009, entitled " SYNTHÈSE DE POLYURÉTHANE PAR AUTOCONDENSATION " - WO2011045546 published on April 21th, 2011 Inventors CRAMAIL HENRI ALFOS CARINE ; BOYER AURELIE; CLOUTET ERIC PALASKAR DNYANESHWAR Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory Laboratoire de Chimie des Polymères Organiques (LCPO), a CNRS laboratory (UMR 5629) Pessac, France. http://www.enscpb.fr/lcpo/

23

BISCARBONATE PRECURSORS and THEIR USES

CONTEXT In addition to its contribution to the synthesis of several types of polymeric materials such as thermoplastics and IPN (Interpenetrating polymer networks), Polyurethanes are one of the most important polymeric materials which have many useful properties for various applications especially in machinery industry, coating and paints, elastic fibers and flexible medical devices.

The linear polyurethane synthesis is done by the reaction between a diol and a diisocyanate. The isocyanates are toxic compounds which are obtained starting from phosgene, itself very toxic by inhalation and causing burns.

Therefore, alternatives to the polyurethanes synthesis without isocyanates represent major stake. The inventors propose a new process of their synthesis.

TECHNICAL DESCRIPTION The present invention relates to the precursors biscarbonates, their method of preparation and their uses for the preparation of polyurethanes. More precisely, the present invention relates to a compound having the following formula (I): where R1 is H or an alkyl group; A1 is a straight or branched divalent alkylene radical, A2 is a -O- A4-O- radical, and A4 is a straight or branched divalent alkylene radical.

BENEFITS

Contrary to triglyceride carbonation leading to synthons having a badly definite number of cyclic carbonates with functionality higher than 2, the present process provides linear polymer synthesis with synthons presenting a controlled functionality which exactly equal to 2.

INDUSTRIAL APPLICATIONS Green chemistry : new process for the synthesis of polyurethanes in the absence of isocyanates.

DEVELOPMENT STAGE Products have shown good properties at lab scale. The scale up is under development (1kg) in order to test the products on real applications.

Our Reference 02664-05 Keywords Biscarbonates, precursor, synthons, polyurethanes, synthesis Status of Patent - Priority patent application n°FR0958219 filed on November 20th, 2009, entitled " Precurseurs biscarbonates, leur procédé de préparation et leurs utilisations" - WO2011061452 published on May 26th, 2011 Inventors CRAMAIL HENRI ALFOS CARINE ; BOYER AURELIE; CLOUTET ERIC PALASKAR DNYANESHWAR Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory Laboratoire de Chimie des Polymères Organiques (LCPO), a CNRS laboratory (UMR 5629) Pessac, France. http://www.enscpb.fr/lcpo/

24

POLY (ESTER-URETHANE)s FROM RENEWABLE RESOURCES

CONTEXT To anticipate the decrease of petroleum raw materials, also to display environmental concern and to be in accordance with sustainable development, many companies are developing bioplastics. They are interesting especially because bioplastics contain renewable carbon but also because a part of them are biodegradable and/or compostable. So they represent a solution in order to reduce the environmental impact of chemical waste from petroleum chemistry. Several bioplastics are already replacing many objects made with conventional plastics. In the future, growth prospect of world bioplastic production has been estimated at 6% per year (for 2013 to 2020).

TECHNICAL DESCRIPTION The invention describes especially a method to synthesize polyhydroxylated vegetal oils or derivatives that can be used to make specific polyurethanes.

The synthesis of the monomers consists in aerobic epoxidation reaction of an unsaturated compound in the presence of an aldehyde followed by the oxirane ring opening reaction (addition) by the acid generated in situ, in a one-pot process. Then, polyhydroxylated products obtained can polymerize in the presence of a polyisocyanate to generate a polyurethane. So, depending on the nature of the reagents used, we have the possibility to synthesize thermoplastic or thermosetting polyurethanes, respectively, fatty acids esters (mono- or di-unsaturated) or vegetal oils (polyunsaturated).

The process follows the economic and ecological requirements of green chemistry: it is a one-pot reaction and a solvent free synthesis, it uses a recyclable heterogeneous catalyst, the reaction temperature is moderate and atmospheric oxygen is the oxidative reagent.

BENEFITS The process demonstrates a great flexibility. Indeed, by changing the nature of reagents used, we are able to provide different types of biopolymers. The technology differs from the current one on the environmental point of view by several means:

• the use of atmospheric oxygen as oxidant (non-toxic and environment friendly agent); • low energy process through the use of a catalyst (search for energy efficiency); • solvent free technology (processing steps reduction).

INDUSTRIAL APPLICATIONS Polyurethanes can be classified in the following major groups: flexible foams, rigid foams, elastomers, fibers, molding compositions, surface coatings and adhesives. Poly(ester urethane)s have the advantage of being biodegradable and bioabsorbable polymers.

Considering their versatile functional attributes, we understand that plant oil polyols or derivatives have a great potential to yield a variety of polymers with various applications.

DEVELOPMENT STAGE We are able to make thermoplastic polyurethane starting from a diol synthesized by the method which is the subject of the invention. The diol is fully bio-based and made by reaction between methyl oleate and hydroxycitronellal. The resulting product of the process is the source of diol to produce polyurethane, the source of diisocyanate is 1,6-diisocyanatohexane (HDI).

This other example describes the synthesis of polyurethane obtained from polyhydroxylated soybean oil. The polyol obtained by functionalization of soybean oil in the presence of butyraldehyde is used for the manufacture of polyurethane, the diisocyanate is 1,6-diisocyanatohexane (HDI).

Our Reference 03404-01 Keywords Biopolymers, Poly(ester-urethane)s, vegetal oil. Status of Patent Priority patent application n° PCT/EP2011/068824 filed on October 27th, 2010 entitled " Procédé de fonctionnalisation de composés insaturés " Inventors Yannick Pouilloux, Stefano Casciato, et Vincent Dubois Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory Laboratoire de Chimie physique et catalyse de l’Institut Meurice, Bruxelles, Belgique Laboratoire de Catalyse en Chimie Organique, a CNRS laboratory (UMR 06503) in Poitiers, France. http://lacco.labo.univ-poitiers.fr/index.php

25

NANOFABRICATION OF SEMICONDUCTORS EMPLOYING SACCHARIDIC DIBLOCK COPOLYMERS LITHOGRAPHY

CONTEXT Today, the efforts toward developing nanometer scale fabrication methods could be split into two fields. One field seeks to extend the current planar, deposit-pattern-etch paradigm used for complementary metal oxide semiconductors (CMOS). The other seeks new techniques to assemble structures without handling individual particles: self-assembly. Diblock copolymers are a promising class of materials that self-assemble to form ordered nanostructures. These structures include spheres, cylinders, lamellae, hexagonally ordered cylinders, biscontinuous cubic gyroids whose shape and dimensions depend on the molecular weight and composition of the polymer. Diblock copolymer lithography refers to the use of these nanostructures in thin films as templates.

TECHNICAL DESCRIPTION Thin films of rigid-flexible saccharidic diblock copolymers developped by the CERMAV can self-assemble into ordered periodic structures at the molecular period of 10nm (density>1012objects/cm2). They can be used as templates to fabricate NAND flash, memory quantum dots, nanowires, magnetic storage media and nanopores. They are of tremendous interest for the nanofabrication of sub-22 nm ordered structures, such lithographic templates for patterning applications, and complex, three dimensional structures. They self-assemble to form dense arrays of nanostructures with dimensions and spacing that are difficult or impossible to achieve by other means or are prohibitively expensive to fabricate using conventional lithographic materials and processes, membranes with dense arrays of pores, lithographic templates for patterning applications, and complex, three dimensional structures.

Our Reference 03363-01 Status of Patent Priority patent of invention FR1056336 filed on July 30 2010 and entitled " Films minces nanoorganisés à base de copolymères à blocs polysaccharidiques pour des applications en nanotechnologie. " Inventors AÏSSOU Karim HALILA Sami FORT Sébastien BORSALI Redouane BARON Thierry Commercial Status Exclusive or non-exclusive licenses. Laboratory Centre de Recherches sur les Macromolécules Végétales CERMAV Grenoble, France. http://www.cermav.cnrs.fr/

26

MECHANICAL PROPERTIES INTENSIFICATION PROCESS OF A PLANT FIBER

CONTEXT In the context of challenging environmental issues and a global energy crisis, materials from biological origin are attracting increasing levels of research interest because of their numerous advantages. The natural fibers coming from annual plants present in particular numerous assets: renewable resource, abundant, low cost, biodegradability high specific mechanical properties…, justifying their use in composite applications. Composites reinforced with natural fibers are already used in the automotive and construction industries, a rapidly expanding market. Other applications requiring high mechanical performances are envisaged to completely value this plant-based resource. Naturally, the composites mechanical performances particularly depend on the properties of the fibers.

TECHNICAL DESCRIPTION The invention concerns an intensification process of the mechanical properties of natural fibers in the longitudinal direction. The invention is focused on the fiber stiffering, i.e. the increase of the fiber Young’s modulus using a combination of concomitant mechanical and hygrothermal stresses. The process consists in the application of a periodic tensile mechanical stress on the fiber during a definite time with several variations of the environmental relative humidity surrounding the fiber. The Young’s modulus increase level can over-pass 350% according to the fiber specie. This thermo-hydro-mechanical treatment also induces a modification of the damping capacity of the fiber. BENEFITS Intensification of the mechanical properties of a fiber without chemical treatment INDUSTRIAL APPLICATIONS Automotive, aeronautic, construction manufacturing…

Stiffness

Dampingcapacity

Relative humidityTe

nsile

stre

ss

Time

Up to x 3.5

Up to / 3

Fibre

Tensile cyclic loading underhygrothermal control

Our Reference 03647-01 Keywords Plant fiber Composites reinforced with natural fibres Status of Patent Priority patent of invention n° FR1055157 filed on June 28, 2010 entitled: " PROCEDE DE RENFORCEMENT DES PROPRIETES MECANIQUES D’UNE FIBRE VEGETALE " WO2012001268 Inventors PLACET Vincent Commercial Status Research agreement, exclusive or non exclusive licenses Laboratory Franche-Comté Electronique Mécanique Thermique et Optique - Sciences et Technologies (FEMTO-ST, UMR 6174), Besançon, France. http://www.femto-st.fr/

27

NEW BRANCHED AND UNSATURATED COMPOUNDS, PRECURSORS OF NEW BIOBASED POLYMERS

TECHNICAL DESCRIPTION This invention relates to novel branched and unsaturated difunctional compounds, obtained from fatty acids. It also refers to the process for their preparation and their use as monomers. These branched bio-based fatty monomers are original structures which are also precursors of various branched polyamides that are expected to exhibit auto-plasticizing properties. These polymers will bear a long alkyl chain (C6 to C9) in α or β position relative to the original primary functional groups. This branched chain would allow to play on the cristallinity of the polyamides they constitute, and therefore to modulate their thermo-mechanical properties (plasticizing effect). Indeed, branched polyamides exhibit melting points lower than their linear homologues.

BENEFITS Thanks to the versatility of the available vegetable oils in terms of chain length and functional groups, and to the different reaction pathways developed by Laurence LECAMP, a wide panel of chemical structures could be proposed. These new saturated and unsaturated fatty molecules bearing alkyl ramifications can bring some specific properties to the materials they constitute such as plasticizing, crosslinking, cristallinity … These new polymers could also present lower melting temperature and be more easily processed. INDUSTRIAL APPLICATIONS Polymer industry and more specifically polyamides industry.

DEVELOPMENT STAGE Samples are available for tests.

Our Reference 04860-01 Keywords Biobased, polyamides Status of Patent Priority patent application n° FR 12 53513 filed on April 17, 2012 entitled "NOUVEAUX COMPOSES RAMIFIES ET INSATURES POUR LA FABRICATION DE POLYMERES RETICULABLES" Inventors LECAMP Laurence, BUREL Fabrice, KEBIR Nasreddine, DESILLES Nicolas, REJAIBI Majed, BIGOT Sandra Commercial Status Research agreement, exclusive or non exclusive licenses Laboratory Laboratoire Polymères Biopolymères Surfaces, UMR6270, a CNRS, INSA Rouen and Université de Rouen common laboratory, in Rouen, France. http://pbs.labos.univ-rouen.fr/

28

III- BIO-BASED MOLECULES

BIOSOLVENTS COMPOSITIONS OBTENTION ESTERIFICATION PROCESS AND OBTAINED BIOSOLVENTS COMPOSITIONS

TECHNICAL DESCRIPTION The present invention concerns a synthesis process of a biosolvent composition including an ester acid stemming from the biomass and an organic biosolvent. The process is based on an esterification reaction between an acid stemming from the biomass and an alcohol, in the presence of an acid catalyst and a small amount of the ester formed with regard to the initial organic acid biosolvent. The present invention also concerns the biosolvent so obtained and the use of this biosolvent. BENEFITS Operatoring conditions were found to ameliorate the rendement in ethyl-lactate for more than 30% during esterification reaction between lactic acid and ethanol without using usual equilibrium deplacement methods (continuated elimination of water and/or alcohol excess). INDUSTRIAL APPLICATIONS Vegetal oils : printing, painting and surfaces, surface cleaning, phytosanitary, adhesives, customer products … Others (complex regulations): pharmacy and cosmetics, rubbers and plastics, oils extraction, wet cleaning.

Our Reference 01855-02 Keywords Biosolvent, esterification process Status of Patent Priority patent application n° FR10 51570 filed on March 03, 2010, entitled " Biosolvents compositions obtention esterification process and obtained biosolvents compositions" FR2957075 Inventors ESSAYEM N., SAPALY G., VU T., NGUYEN T., NGUYEN T.H. Commercial Status Collaborative agreement Laboratory UMR 5256 (IRCELYON) Lyon, France. http://www.ircelyon.univ-lyon1.fr

29

METHOD FOR 5-HMF PREPARATION (5-HMF: 5-HYDROXYMETHYLFURFURAL)

TECHNICAL DESCRIPTION 5-HMF(5-hydroxymethylfurfural) is a value-added molecule obtained from renewable feedstock since its main derivative, FDCA (Furandicarboxylic acid), presents structural similitude with terephtalic acids, which makes this molecule of high interest to produce bio-polymers. Indeed, FDCA could replace terephtalic acids, the actual monomers used in the synthesis of polyamides and polyesters. The present invention describes a carbon efficient and environmentally friendly process to produce 5-HMF by dehydration of fructose in concentrated solutions of carboxylic acids such as acetic acid or formic acid and in the presence of a solid acid. The process of the invention solves the problems of the poor selectivity of the reaction due to the formation furanic polymers (humins) especially when strong mineral acids such as HCl are employed. The present invention solves also the drawbacks of the alternative recent methods which describe the use of toxic organic solvents to extract 5-HMF and/or complexe reaction mixtures ( ionic liquid or concentrated solutions of transition metallic salts) to get high selectivities in 5-HMF. The process of the invention can provide a total conversion of fructose, and selectivity in 5-HMF higher than 75%. The invention describes also the production of aqueous solutions of carboxylic acid containing more than 10 wt% of 5-HMF, depending only of the hexose solubility in the aqueous solution of carboxylic acid. Aqueous solution of 5-HMF free of carboxylic acid can be easily obtained when a volatile organic acid is used such as acetic acid.

This invention reports a durable and an efficient process to produce 5-HMF since 1) it avoids the use of a fossil and toxic solvent to extract 5-HMF 2) it circumvent the use of complexes media (ionic liquid or concentrated solutions of salts of transition metals 3) the process is selective in 5-HMF and leads to limited carbon losses in humins formation due to the stabilisation of 5-HMF in concentrated aqueous solutions of carboxylic acids by contrast to solutions of mineral acids of equivalent pH 4) the presence of solid acids such as modified carbons improve the HMF selectivity.

INDUSTRIAL APPLICATIONS Applications include: the conversion of biomass containing C6 sugars and of concentrated aqueous solutions of C6 sugars to produce aqueous solutions of HMF. The aqueous solutions of HMF, eventually free of carboxylic acid, can be used as in further transformations in FDCA as example.

Our Reference 04381-01 Keywords hexose dehydration, 5-HMF synthesis, acid catalyzed dehydration of saccharides Status of Patent French patent application: FR 11/54232 filed on May 16, 2011 entitled « Procédé de preparation de 5-hydroxymethylfurfural » in the name of the CNRS and the university of Lyon1 Inventors Nadine Essayem Rodrigo Lopes de Souza Franck Rataboul Commercial Status Non-exclusive licenses, Collaborative agreement Laboratory Institut de Recherches sur la catalyse et l’environnement de Lyon (IRCELYON). a mixed CNRS- Lyon 1 university laboratory (UMR 5256) in Villeurbanne, France. http://www.ircelyon.univ-lyon1.fr

30

FURFURAL PRODUCTION

TECHNICAL DESCRIPTION Furfural is obtained by the acid treatment of lignocellulosic feedstocks containing high quantities of C5 sugars. Nowadays the production of furfural is mainly located in China and the process consists of a treatment of the biomass with sulfuric acid. The process (Quaker oats) is energy consuming and yields in furfural lower than 30% are obtained. The selective production of furfural is a difficult task due the fast formation of furanic polymer (humins) in the conditions of furfural production via acid catalyzed dehydration of pentoses in aqueous solutions. Recent alternative method propose the use of a biphasic media containing a potentially toxic solvent of furfural, insoluble in the aqueous medium which contain a acid catalyst. The present invention solve the problem of humin formation without using a extractive solvent. The present method describe the selective formation of furfural by using concentrated solutions of carboxylic acids in water in the presence of a solid acid catalyst such as a sulfonated carbon. The process permits to pentoses conversion higher than 90% and the furfural selectivity overreaches 75%. The invention reports also the production of aqueous concentrated solutions of furfural which can be free of carboxylic acids especially when a volatile carboxylic acid is used such as acetic acid. These solutions of furfural, free or not of carboxylic acids, can be used for further transformations of furfural in value added derivatives.

INDUSTRIAL APPLICATIONS Applications include: the conversion of a crude solid biomass containing high quantities of pentoses such as annual plants or crude aqueous solutions of pentoses and /or more or less polymerized pentoses, issued from the hemicellulosic part of the annual plant or of the wood.

Our Reference 04381-02 Keywords pentoses dehydration, furfural synthesis, acid catalyzed dehydration of saccharides Status of Patent French patent application: FR 11/57563 filed on August 26, 2011 entitled « Procédé de préparation de furfural» in the name of the CNRS and the University of Lyon1 Inventors Nadine Essayem Rodrigo Lopes de Souza, Franck Rataboul Commercial Status Non-exclusive licenses, Collaborative agreement Laboratory Institut de Recherches sur la catalyse et l’environnement de Lyon (IRCELYON). a mixed CNRS- Lyon 1 university laboratory (UMR 5256) in Villeurbanne, France http://www.ircelyon.univ-lyon1.fr

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GLUCOSE-FRUCTOSE ISOMERISATION CATALYZED BY SOLID BASES AND METHOD FOR 5-HMF PRODUCTION

TECHNICAL DESCRIPTION Fructose finds already various applications in the food industry. The current industrial process is based on immobilized enzymes. For the production of platform molecules from biomass such as 5-HMF, fructose is believed to become an important intermediate, since this ketohexose is more reactive than glucose, an aldohexose. However, glucose is more available and cheaper than fructose, this makes glucose the preferred starting feedstock to produce 5-HMF. Thus, this justifies the search for an alternative glucose-fructose isomerization process which would be as selective as the enzymatic one but faster and more robust. The present invention describes a method to isomerize glucose into fructose in the presence of solid bases and an integrated method to produce 5-HMF from glucose. The more active solid base described in the invention are simple or mixed oxide containing lanthanides. Compositions close to the thermodynamic equilibrium of the glucose-fructose isomerization reaction are achieved in short reaction time. The solid bases of the present invention are efficient to isomerize glucose in fructose in aqueous solution and do not need any pretreatment before the reaction, according to their resistance towards irreversible atmospheric CO2 adsorption.

The present invention reports also an integrated method to produce 5-HMF which combines a first isomerization step performed in water in the presence of the solid base of the invention and a second step where the fructose is dehydrated into 5-HMF after addition of a sufficient amount of carboxylic acid to the reaction medium.

INDUSTRIAL APPLICATIONS Applications include: 1) the conversion of glucose into fructose using alternative process to the enzymatic one, which is more rapid and robust. 2) An economically viable method to produce 5-HMF using glucose as raw material.

Our Reference 04756-01 Keywords glucose-fructose isomerization, dehydration, 5-HMF synthesis from glucose, water resistant solid bases, CO2 resistant solid bases Status of Patent French patent application: FR 1157575 filed on August 26, 2011 entitled « Procédé de preparation de furfural» in the name of the CNRS and the University of Lyon1 Inventors Nadine Essayem Rodrigo Lopes de Souza, Franck Rataboul D.F.Patrick, C.Feche Commercial Status Non-exclusive licenses, Collaborative agreement Laboratory Institut de Recherches sur la catalyse et l’environnement de Lyon (IRCELYON). a mixed CNRS- Lyon 1 university laboratory (UMR 5256) in Villeurbanne, France http://www.ircelyon.univ-lyon1.fr

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ENVIRONMENTALY FRIENDLY SYNTHESIS OF ACETALDEHYDE FROM LACTIC ACID

CONTEXT Aldehydes and especially acetaldehyde are precursors widely-used for the synthesis of numerous intermediates such as acetic acid, peracetic acid, acetic anhydride, etc… Current acetaldehyde synthesis depends on fossil resources and is usually operated through ethylene direct oxidation, acetylene hydration or even C3/C4 alkane gas phase oxidation.

However, these methods do not always give good results in terms of yield and have the disadvantage of producing environmentally unfriendly carbon dioxide (CO2).

As a consequence, there is a demand for acetaldehyde synthesis that counteract the negative effects of the currently used processes.

TECHNICAL DESCRIPTION In the present work, the research team has developed a new way to synthesize aldehydes from alpha-hydroxy acids through a gas-phase catalyzed decarbonylation under controlled conditions releasing carbon monoxide CO and water H2O. More specifically, the team has focused on acetaldehyde synthesis from lactic acid.

DEVELOPMENT STAGE Laboratory-scale efficient acetaldehyde synthesis from lactic acid : high selectivity in

acetaldehyde and high yield.

BENEFITS Numerous benefits are introduced by such method of synthesis:

Environmentally friendly through the use of biomass-based raw materials instead of fossil resources;

No production of carbon dioxide;

Production of carbon monoxide that can be used in downstream reactions;

One-step synthesis in the gas phase;

High selectivity;

High yield.

INDUSTRIAL APPLICATIONS This process directly aims at giving an ecological alternative to current users of competitive and environmental unfriendly aldehyde or acetaldehyde syntheses. These current users are fine chemical companies producing intermediates such as acetic acid, peracetic acid, acetic anhydride, etc… This technology also focuses on lactic acid producers who definitely can use this method as a downstream supplementary process in their installations giving them the opportunity to offer more to their customers.

Our Reference 03216-01 Keywords Acetaldehyde, lactic acid, aldehyde, alpha-hydroxy acid, decarbonylation Status of Patent French patent application FR10553494 filed on May 05, 2010 and entitled « Procédé de production d'acétaldéhyde à partir d'acide lactique » FR 2959740 Inventors Sébastien PAUL Benjamin KATRYNIOK Franck DUMEIGNIL Commercial Status Exclusive or non-exclusive licenses Laboratory Unité de Catalyse et Chimie du Solide, a CNRS and University of Lille I laboratory (UMR8181), Lille, France http://uccs.univ-lille1.fr/

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METHODS FOR ETHERIFYING GLYCEROL

CONTEXT Continuous energy crises and increasing demand for conventional fuels has resulted in the need for biofuels on a commercial scale. Transesterification of oils to biodiesel is coupled with significant production of a glycerol-rich water (so-called “crude” or “raw” glycerol), as an important side-product of the process. The increasing demand for biodiesel leads to abundant quantities of glycerol on the market. Therefore, glycerol valorization has much to offer in the cost reduction of biodiesel production.

Etherification constitutes one of the ways of valorization of glycerol for obtaining glycerol ethers, still indicated polyglycerols. The glycerol ethers have various applications according to their preparation and of their structure. The polyglycerols are also primarily intermediaries of synthesis of the esters of polyglycerols

TECHNICAL DESCRIPTION The invention describes the use of a solid catalyst to synthesize polyglycerol from glycerol.

This new catalyst is mesoporous, heterogeneous, providing basic active sites due to the presence of alkaline compounds. This etherification could reach a polymerization degree of 4, whereas existing products have got a polymerization degree of 9.

BENEFITS This process is selective so that a fraction of di to tetraglycerol is obtained with a yield of 95 %.This process doesn’t use any solvent. Indeed the reaction is performed in a reactor where glycerol is in contact with the solid catalyst in well chosen conditions (atmospheric pressure and temperature around 200 °C)

INDUSTRIAL APPLICATIONS Polyglycerol main applications are: lubricant synthesis, replacing petroleum oils in order to use products less polluting and biodegradable, replacing triglycerides in food industry. The glycerol ethers find also applications like surface-active neutrals, in the depollution of the grounds, the industry of the cosmetic, of pharmacy, in the food industry.Furthermore polyglycerol with weak polymerisation degree may be interesting in cosmetics and detergent industry as active-surface agents.

DEVELOPMENT STAGE Have been also investigated :

- the synthesis of polyglycerols esters in similar conditions either in a 2 steps process or in a single step procedure. It was demonstrated that polyglycerol esters could be obtained directly from glycerol and methyl esters over the same catalysts. - other catalytic materials i.e. with a different porosity in order to get a more important fraction of higher polyglycerols (di to hexaglycerol) in similar conditions.

- the scaling up of the preparation processes as well as the shaping of the materials in order to get extrudates, pellets, balls, … which could be used in real conditions (first in pilot equipment)

- the scaling up of the reactions: preparation of polyglycerol or of polyglycerol esters in a pilot reactor

All these experiments were quite successful at the pilot level (scaling factor 10 to 50).

Our Reference 84379-01 (61902) Keywords Biomass, glycerol, polyglycerol Status of Patent Priority patent application n° 0008078filed on june 23 rd, 2000 entitled " Procédés d'étherification du glycérol, et catalyseurs pour la mise en œuvre de ces procédés " - WO 0198243 published on December 27th ,2002 - EP 1292557 granted on August 23,2006 Inventors Joel BARRAULT Jean-Marc CLACENS Yannick POUILLOUX Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory Laboratoire de Catalyse en Chimie Organique , a CNRS laboratory (UMR 6503) in Poitiers , France. http://lacco.labo.univ-poitiers.fr/index.php

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BIOTECHNOLOGICAL PREPARATION OF FURCELLARAN: AN HYDROCOLLOID WIDELY

APPRECIATED IN FOOD INDUSTRY

CONTEXT Carrageenans are linear sulfated galactans, made of the repetition of disaccharide unit -called carrabiose. The number and the position of sulfate ester groups will modulate the gelling properties of carrageenan. For example, the iota-carrageenan make soft gel (2 sulfate/unit) when kappa-carrageenan make strong gel (1 sulfate/unit). Controlling the amount and the distribution of sulfate ester groups in carrageenans allows designing desired functionalities in food applications. One can expect that the modification of the sulfation of carrageenan extracted from farmed algae could be exploited to higher value applications and low exploited algae having poor functionalities could then be valorized.

The process for making new carrageenans involves carrageenan-sulfatases that hydrolyze specifically the sulfate ester groups on polymeric substrates. Two 4S-carrageenan sulfatases were found to convert the kappa-carrageenan in beta-carrageenan allowing to control the structure of -/-carrageenan.

TECHNICAL DESCRIPTION There are no practical chemical methods to carry out specific desulfatation of carrageenan without lowering the molecular mass of carrageenan that can be transferred advantageously to industry. Alternatively, the only reported carrageenan-sulfatase was active at the non-reducing end of oligo-kappa-carrageenans. Therefore exploring diversity of carrageenan-sulfatase activity aiming at evidencing endo-acting enzymes represented a first challenge. Two endo-kappa-carrageenan-sulfatases were described for the first time. Using these enzymes, we have prepared new series of kappa-/beta-carrageenans starting from kappa-carrageenan extracted from farmed algae. BENEFITS Kappa-/beta-carrageenans also named furcellaran was one of the first hydrocolloids extracted from red algae to have been exploited in industry. However, despite its appreciated functional properties, the intensive harvesting of Furcellaria sp. leads to a decrease of furcellaran resources. Therefore, our invention allows converting farmed and less expensive kappa-carrageenan in series of kappa-/beta-carrageenans having controlled composition of kappa and beta unit. INDUSTRIAL APPLICATIONS Furcellaran provides thermoreversible texture for applications in food industry such as bakery, confectionery, marmalade, jam, yoghurt, meat, water and milk based desserts. Other applications include cosmetology: personal lubricants, shampoo,…

DEVELOPMENT STAGE Carrageenan-sulfatase can be produced recombinantly allowing confirming the catalytic function of the enzyme. The desulfatation of kappa-carrageenan in kappa-/beta-carrageenan was demonstrated by chromatography and 1H NMR at mg scale. The next step wil consist in production of high amount of enzyme aiming at preparation of desulfated carrageenan at gram scale required for physico-chemical investigations.

Our Reference N° DI 05668-01 Keywords Carrageenan, furcellaran, food and cosmetic industry. Status of Patent Priority patent application n° 12306384.4, filed on November, 2012 entitled " Kappa carraghenane sulfatase, procédé de fabrication et utilisation ". PCT filed on November 2013. Inventors HELBERT William PRECHAUX Aurélie Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory Centre de Recherches sur les Macromolécules Végétales (C.E.R.M.A.V), a CNRS laboratory (UPR 5301) in Grenoble, France. http://www.cermav.cnrs.fr/

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IV- BIOPROCESSES - ENZYMES

BACILLUS PUMILUS BILIRUBIN OXIDASE AND APPLICATIONS THEREOF

TECHNICAL DESCRIPTION The present invention relates to a novel bacterial bilirubin oxidase, to the method for preparing this BOD and also to its use, in particular for assaying bilirubin and for its use in enzymatic biofuel cells to reduce oxygen. This new bacterial enzyme would be also helpful for understanding molecular mechanisms involved in oxygen reduction by multicopper oxidase. ADVANTAGES We have shown that this new bacterial Bilirubin oxidase presents 6 main advantages compared to previous commercial enzymes (Myrothecium verrucaria from Sigma-Aldrich, Bacillus subtilis from Sekuisi Diagnostics): Higher stability in physiological conditions Highest activity and stability at high temperature up to 80°C Higher catalytic activity with substrates such as ABTS and Bilirubin Strong tolerance to NaCl, Urea and EDTA Absence of glycosylation (compared to the commercial BOD from Myrothecium verrucaria) Highest electroreduction current of O2 reached on various electrodes surfaces either in Direct electron transfer (DET) or in Mediated electron transfer (MET) at high temperature.

INDUSTRIAL APPLICATIONS Biofuel cells, oxygen biosensors, bilirubin biosensors, commercial enzyme for fundamental and academic research, wood pulp treatment and dyes decolourization.

STATE OF DEVELOPMENT We already demonstrated the concept and the enzyme is available for testing.

Reference 03383-01 keywords bacterial bilirubin oxidase; biofuel cell ; biosensor ; oxygen reduction; dye decolorization; bilirubin detection. Patent French patent application filed on March 24, 2010 under ref. FR 10/01167 (“ NOUVELLE BILIRUBINE OXYDASE DE BACILLUS PUMILUS”). WO2011117839 Inventors Nicolas Mano Fabien Durand Opportunity Exclusive or non exclusive license Research collaboration. Laboratory UPR8641 Centre de recherches Paul Pascal (C.R.P.P) – France http://www.crpp-bordeaux.cnrs.fr

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MAGNAPORTHE ORYZAE BILIRUBIN OXIDASE AND APPLICATIONS THEREOF

TECHNICAL DESCRIPTION The present invention relates to a novel yeast bilirubin oxidase, to the method for preparing this BOD and also to its use, in particular for assaying bilirubin and for its use in enzymatic biofuel cells to reduce oxygen. This new yeast enzyme would be also helpful for understanding molecular mechanisms involved in oxygen reduction by multicopper oxidase. ADVANTAGES We have shown that this new fungal Bilirubin oxidase presents 5 main advantages compared to the previous commercial enzyme from Myrothecium verrucaria (Sigma-Aldrich): Highest stability and activity in physiological conditions (0.14 M NaCl, pH 7) Higher stability and activity at 60°C Large production of enzyme and easiness of production and purification Better catalytic activity with substrates such as ABTS and Bilirubin Highest electroreduction current of O2 reached on various electrodes surfaces either in Direct electron transfer (DET) or in Mediated electron transfer (MET) in physiological conditions.

INDUSTRIAL APPLICATIONS Biofuel cells, oxygen biosensors, bilirubin biosensors, commercial enzyme for fundamental and academic research, wood pulp treatment and dyes decolourization. A new laccase is also isolated. STATE OF DEVELOPMENT We already demonstrated the concept and the enzyme is available for testing.

Reference 04329-01 keywords yeast bilirubin oxidase; biofuel cell ; biosensor ; oxygen reduction; dye decolorization; bilirubin detection Patent Priority patent application filed in on May 24, 2011 under ref. FR 11/54526 “ Nouvelle bilirubine oxydase de Magnaporthe oryzae”. Inventors Nicolas Mano Fabien Durand Opportunity Exclusive or non exclusive license Research collaboration Laboratory UPR8641 Centre de recherches Paul Pascal (C.R.P.P) – France http://www.crpp-bordeaux.cnrs.fr

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BACTERIAL IODOPEROXIDASES, METHODS OF PREPARATION AND THEIR USES

CONTEXT Halogenated compounds are abundantly found in nature, and play various biological functions when produced by an organism, ranging from chemical defense to signaling molecules. Most organisms capable of incorporating halogens into organic compounds are of marine origin, such as algae and bacteria, and have evolved such capacity thanks to specific enzymes, namely, haloperoxidases. These enzymes catalyze, in the presence of hydrogen peroxide, the oxidation of halides which can subsequently react with nucleophilic acceptors generating numerous halocarbons. Chloroperoxidases can catalyze the oxidation of chloride as well as of bromide and iodide, and bromoperoxidases react with bromide and iodide, whereas iodoperoxidases are the most specific as they only react with iodide. Up to now, only chloro- and bromoperoxidases were available for industrial applications. TECHNICAL DESCRIPTION This invention relates to the technical field of iodide oxidation using specific iodoperoxidases from a marine bacteria, as well as methods for purifying these enzymes. More specifically, the present invention provides the first biochemical and structural characterization of this enzyme and is also the first report demonstrating an efficient recombinant expression of iodoperoxidases. The kinetics parameters revealed a Km of 0.2 mM range, and a Kcat around 2 s-1. Upon heating for 10 min up to 40°C, the purified recombinant enzyme remained fully active. BENEFITS/ADVANTAGES Compared to existing haloperoxidases, these iodoperoxidases have a higher activity for iodine oxidation and are also highly specific even in presence of bromide or chloride. Their uses will facillitate a great number of chemical or biochemical processes based on specific iodide oxidation and incorporation. More particularly, in consideration to environmental contraints, these new enzymes provide a practical alternative approach to traditional chemical synthesis of several compounds and in different processes. INDUSTRIAL APPLICATIONS Such iodoperoxydases can be used in a wide range of industrial, pharmaceutical, medical, cosmetics and ecological applications, as well as in the food industry. Interestingly, they allow the obtention of iodinated chemical intermediates and organic compounds of interest which could be used as desinfectants, nutrients, pesticides, drugs, antibiotics, antioxydants, adhesives and radiocontrast agents…etc. DEVELOPMENT STAGE A high production yield at laboratory scale was estimated to be of about 50 to 100 mg of recombinant protein per 1 L of E. coli microbial culture. Samples are available for tests.

Our Reference 04207-01 Keywords Enzyme, iodoperoxidases, iodinated compounds, haloperoxidases, iodide Status of Patents - Priority patent application n° EP 11305864.8 filed on July 5, 2011 entitled "Bacterial iodoperoxidases, methods of preparation and uses thereof ", published under WO2013004783 - Priority patent application n° EP 12306718.3 filed on December 31, 2012 Inventors Catherine LEBLANC Ludovic DELAGE Gurvan MICHEL Etienne REBUFFET Mirjam CZJZEK Philippe POTIN Jean-Baptiste FOURNIER Commercial Status Research agreement, exclusive or non exclusive licenses Laboratory UMR7139 « Végétaux marins et biomolécules » Roscoff, France. http://www.sb-roscoff.fr/UMR7139/en/defense.html

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IV- BIOPROCESSES - Photobioreactors

THIN PHOTOBIOREACTOR WITH ENHANCED VOLUMETRIC PRODUCTIVITY AND THERMAL MANAGEMENT

CONTEXT Photobioreactors (PBR) have been widely researched and used in biomass microalgal culture for more than two decades, but most of them were just used in laboratories or in pilot or experimental bases. There were only few of them being real used in industrial or commercial algal production. Production rate was not economically sufficient due to oxygen built up in the culture medium, overheating inside the closed system, shear force damage to the algal cells, high costs of infrastructures of the whole system, or to the operation complexities… etc. All these limitations had to be faced before scaling up PBR into real commercial production.

TECHNICAL DESCRIPTION The technology is based on the association of an inclined and enlightened plane on which the stream of microorganisms in suspension flows and a transparent tube parallel to the inclined plane in wich the suspension is lifted up upstream to close the loop. Dark volumes are avoided in the system and the angle of said plane with the ground can be raised. The thickness of suspension on the plane can be as small as 1.5 cm or below without loosing in production rate as the rate enlightened surface/culture volume is encreased.(see fig 1)

fig1 : example of the PBR

As any closed system the PBR will see its temperature evolving according to a balance between the flow of heat entering by radiation, the flow of heat consumed, produced and stored within it and the flows exchanged with the outside environment. To obtain such effect a thermal valve (phase change material) is enclosed in the enclined plane (non transparent wall of the PBR) in order to control the temperature evolution in a passive way. To enhance this effect the transparent plane may be chosen in non IR transmitting glasses (such radiations are not used by the microorganism but increase the temperature). In another

Our Reference N° DI 3079-01 N° DI 3256-01 Keywords Photobioreactors, energy management; Status of Patent Priority patent application n° FR 0956870 filed on October 1st, 2009 entitled " Photobio-reacteur couche mince à haute productuivité volumique" WO2011039354 Priority patent application FR 0956870 filed on September 13th, 2010 entitled " dispositif de contrôle de la température d’un photo-bioreacteur solaire a éclairage direct" PCT ° EP2011/065874 filed on September 13th 2011 FR2964666 Inventors J Pruvost ; J Le Grand ; F Le Borgne V Goetz ; J Pruvost ; J Legrand ; Plantard Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory PROMES , a CNRS laboratory (UPR 0000) in Perpignan, France. www.promes.cnrs.fr/

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embodiment a thermal exchanger may be placed in contact with the thermal valve to increase its effect. BENEFITS High enlightened specific surface and gas/liquid surface, no mixing Biomass concentration up to 1g/L has been obtained, , Closed PBR (control of atmosphere) which the external wall is not in contact with the suspension, limiting the biofilm formation No mechanical parts. INDUSTRIAL APPLICATIONS This innovation could be used for bio-energy ( energy production from biomass or hydrogen), agriculture (production of vegetal proteins, biomass for aquaculture) and environment (waste water treatment or C02 capture). Said thermal management system is limited neither to PBR nor to thin PBR. Any reactor of various geometries exposed to thermal problems may be equiped.

DEVELOPMENT STAGE A prototype exists in Nantes and thermal modelisation have shown the real advantages of the different thermal systems proposed. The two teams involved in these developments have very complemetnary skills; PBR on one side and thermal management and solar energy on the other side.

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DICOFUV : PHOTOBIOREACTOR WITH CONTROLED MIGHT FLOWVOLUMETRIC PRODUCTIVITY AND THERMAL MANAGEMENT

CONTEXT Photobioreactors (PBR) have been widely researched and used in biomass microalgal culture for more than two decades, but most of them were just used in laboratories or in pilot or experimental bases. There were only few of them being real used in industrial or commercial algal production. Production rate was not economically sufficient due to oxygen built up in the culture medium, overheating inside the closed system, system complexities or insufficient enlightment… etc. All these limitations had to be faced before scaling up PBR into real commercial production and that is an aim of the present invention to provide an homogeneous enlightment in the volume of the reactor.

TECHNICAL DESCRIPTION The technology concerns a sunlight guide module for a PBR including a chamber of reaction, the module consisting in - a concentrator arranged outside the chamber to concentrate the solar light in a concentrated beam - a diffuser (optical fibers) in the chamber of reaction - and a system between the concentrator and the diffuser to homogenize the concentrated beam before it enters the diffuser. It has been shown that the concentrator can result in a very high solar flow at the center of the concentrator spot where the temperature is too hot for the medium ; homogeneization is necessary to avoid this phenomenon. Said module may be duplicated in a PBR. BENEFITS The problem of the incorporation of enlightening structures inside a reactor indeed presents automatically the double weakness to perturb the flow and to allow possibly the fixation of microalgae. Here the mixing and the mass transfer remain excellent thanks to the design and the gazosiphon (all these points are already characterized and calculated) Dicofluv works with low light densities which limits the adhesion of algae which is often due to the synthesis of polysaccharides generated by the strong densities. INDUSTRIAL APPLICATIONS This innovation could be used for bio-energy (energy production from biomass or hydrogen), agriculture (production of vegetal proteins, biomass for aquaculture) and environment (waste water treatment or C02 capture).

Said thermal management system is limited neither to PBR nor to thin PBR. Any reactor of various geometries exposed to thermal problems may be equiped.

DEVELOPMENT STAGE Various systems have been tested. Modelisation have shown the real advantages of the modules. The two teams involved in these developments have very complementary skills; PBR on one side and thermal management and solar energy on the other side.

Our Reference 03256-02 Keywords Photobioreactors, light density management; Status of Patent Priority patent application FR 1059761 filed on november 25th, 2010 entitled " Photobio-réacteur Solaire à Dilution Controlee du Flux en Volume " PCT ° EP2011/071002 filed on November 25th, 2011 Inventors JF Cornet; V Goetz ;G Plantard; R Garcia; P Lafond; F Joyard Commercial Status Exclusive or non-exclusive licenses, Collaborative agreement Laboratory PROMES , a CNRS laboratory (UPR 0000) in Perpignan, France. www.promes.cnrs.fr/

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IV- BIOPROCESSES – Extraction

DEVICE AND METHOD FOR PLACING IMMISCIBLE FLUID PHASES IN CONTACT WITH EACH OTHER BY MEANS OF CENTRIFUGAL FORCE

TECHNICAL DESCRIPTION The present invention relates to a device and a method for placing immiscible fluid phases in contact with each other by means of centrifugal force, in particular in order to extract compounds from one of said phases by another phase. Said device comprises at least one contacting unit (3*) which is capable of being rotated about an axis (X'X) and which includes a plurality of cells (210, A, D) intended to be passed through consecutively by said phases, in a given flow direction, each cell being provided with two inlet/outlet channels (214 and 215) which fluidly connect the cells together in pairs and which lead into each cell, respectively, via two inlet/outlet openings, which are proximal (214a) and distal (215a) relative to the said axis, respectively. According to the invention, for at least two adjacent cells (A and D) of said at least one unit, the two proximal (214a) or else distal (215a) openings thereof are connected together directly via one of said channels (214 or 215), whereby said phases flow through one of said adjacent cells towards said axis and through the other cell while moving away from said axis.

BENEFITS This device has proven its efficiency in algae oil extraction and liposomal encapsulation. INDUSTRIAL APPLICATIONS Extraction and encapsulation

DEVELOPMENT STAGE A prototype is available for tests.

Our Reference 03020-01 Keywords Algae Extraction, liposomes. Status of Patent Priority patent application n° FR 09 05784 filed on December 01, 2009 entitled "Dispositif et procédé de mise en contact de phases fluides immiscibles par la force centrifuge." WO2011067704 Inventors Alain FOUCAULT, Jack LEGRAND, Luc MARCHAL, Charles AGAISE Commercial Status Research agreement, exclusive or non exclusive licenses Laboratory Génie des Procédés Environnement et Agroalimentaire, UMR6144, a CNRS, Université de Nantes common laboratory, in Nantes, France. http://www.gepea.fr/

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FIST SA in figures FIST SA is the acronym of France Innovation Scientifique et Transfert (France Scientific Innovation and Transfer). It was created in Paris in 1992 as a private company in order to focus on the transfer of innovative patents from French government-funded research organization (CNRS) to industry. Today, it represents € 4.2 millions of sales.

Shareholders

70%

30%

CNRSOséo

A professional and specialized team With the benefit of a large range of technical competences, our team comes along from the protection of the invention to its licensing contract.

The team (Total 45)

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86

5

43 1 1 1

Licensing Managers IP Marketing ManagersLawyers Portfolio ManagersAdministratives AssistantsPartner Search Project Manager Foreign Client Project ManagerEU Project Assistant

A range of services The different services proposed by FIST SA are also available for private and start-up companies:

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Technology Transfer Success: examples Taxotere : Sanofi Aventis Chemotherapy drug approved in treatment of breast cancer, non-small cell lung cancer, advanced stomach cancer, head and neck cancer and metastatic prostate cancer. Sales in 2008: EUR 2,033 million Navelbine : Pierre Fabre Chemotherapy drug approved in treatment of non-small cell lung cancer and also of breast cancer, ovarian cancer, or Hodgkin's disease. Lupuzor : ImmuPharma / Cephalon inc Drug that specifically modulates the immune system of Lupus patients. Lupuzor™ has successfully completed phase I, Phase IIa and Phase IIb studies. Sublicense to Cephalon inc. by ImmuPharma in 2009. Selectiose® : PFDC - AVENE Sélectiose®, amphiphilic derivative of Rhamnose reduces skin hypersensitivity and irritation and controls skin inflammation response. Marketed in cosmetic product line (Trixera+) in 2008 by AVENE. A collaboration success story: CENTRON C1S Fifteen years ago, a collaboration between a laboratory affiliated to the CNRS, the « Groupe d'Etudes des Semi-conducteurs », and RMS, a division of the Schlumberger Company now integrated to the Itron/Actaris group, developed semi conductive straight structure III-V showing a magnetic field high sensibility and a low thermal drift. The magnetic sensor then developed allowed the manufacture of a new generation of residential electricity meter, the CENTRON C1S. This technology was enlarged to all the meters product range by ITRON. At the moment, 30 millions of meters have been fixed up in the USA and other countries. 5 millions of meters are yearly produced.

CNRS in figures Budget for 2011 Euros 3.3 billion of which Euros 677 million come from revenues generated by CNRS Personnel 34,530 permanent employees 11,450 researchers 14,180 engineers and technical staff Organisation 10 institutes (3 of which have the status of national institutes) 19 regional offices, ensuring decentralized direct management of laboratories 1,100 research units (95 % are joint research laboratories with universities and industry) 40 International Associated Laboratories (LEA+LIA)

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FIST SA always seeks industrial partners to develop and commercialize technologies held by CNRS within the framework of licenses or research agreements. We look forward to discussing any opportunity with you.

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