FR3041966B1

FR3041966B1 - COMPOSITION COMPRISING A PLANT BROYA, MALTODEXTRIN AND SILICONE

Info

Publication number: FR3041966B1
Application number: FR1559347A
Authority: FR
Inventors: Aurelie Morel; Fabrice Garrigue
Original assignee: Ass F I D O P; Evertree SAS
Current assignee: Evertree SAS
Priority date: 2015-10-01
Filing date: 2015-10-01
Publication date: 2019-07-05
Anticipated expiration: 2035-10-01
Also published as: WO2017055557A1; FR3041966A1

Abstract

La présente invention concerne une composition comprenant un broyat de plantes contenant des protéines, de la maltodextrine, et du silicone. Elle vise également une composition adhésive et des articles la comportant, leurs procédés de préparation et leurs utilisations.The present invention relates to a composition comprising a crushed plant containing proteins, maltodextrin, and silicone. It also relates to an adhesive composition and articles comprising it, their methods of preparation and their uses.

Description

The present invention relates to a composition based on ground meal, and more particularly milled oleaginous and / or proteinaceous plants, its method of production and its uses.

In recent years, the exploitation of oleaginous and protein crops has greatly increased, to meet the needs of society.

Oleaginous and protein crops are generally grown and grown for their seeds or fruits, which are particularly rich in fat and protein, respectively.

The oleaginous plants include sunflower, rapeseed, peanut, sesame, cotton, flax, castor oil, olive oil, oil palm, hazelnut, walnut, almond or the coconut tree. However, although classified as "oleaginous", these plants also have a significant content of proteins.

Soybean, which is a protein crop, is sometimes referred to as oilseed crop because it also produces oil. As a result, it is often classified separately among oilseed crops because it is rich in both fat and protein.

Protein crops include peas (chickpeas, split peas), faba beans and lupins, but also lentils, fenugreek and beans.

The oilseeds are mainly grown for their oil, used in various sectors, such as food and feed, lubricants, cosmetics, agronomy, especially in the phytosanitary field, oil exploitation, materials and the environment. energy industry, for the production of biofuels such as biodiesel.

The transformation of the seeds or fruits of oleaginous plants into oil is generally done according to three main operations, that are: - the preparation of the raw material to be extracted (seeds or fruits of an oleaginous plant): during its preparation, the raw material may undergo one or more of the following steps: cleaning or dusting, sieving, dehulling or lamination. - Trituration: this operation may include several steps depending on the raw material to grind. This operation includes in all cases a step of grinding and extraction of the oil contained in the raw material. the refining of the oil, which consists in eliminating all or part of the compounds contained in an oil rendering it unfit for its use or its subsequent transformation. For example, the refining of an oil for human consumption will generally include steps of taste neutralization, discoloration, deodorization, etc. The crushing operation is a crucial transformation operation because it aims at extracting the oil contained in the seeds or the fruits of the oleaginous plants.

This trituration operation therefore depends on the raw material from which the oil is to be extracted. By way of example, in the case of oilseed seeds, the extraction carried out during the crushing is mainly based on two traditional techniques: the so-called "rich" seeds in oil (> 35%, for example sunflower or rapeseed) are crushed by pressure and then by chemical extraction while seeds considered as "poor" in oil ( <35%, soybean for example) usually undergo chemical extraction.

By chemical extraction, it is more particularly a solvent extraction, such as extraction with water or with an organic solvent. When the extraction is carried out with an organic solvent, this step may be followed by a desolventization step (step for removing solvents from a substrate, such as a plant cake).

For example, in the case of rapeseed or sunflower, the trituration operation comprises the following steps: flattening: it is a step of grinding the seeds. In general, they pass between two smooth cylinders and come out crushed, in the form of "flakes". cooking: this step aims to facilitate the extraction of the oil contained in the seeds. In general, the flakes from flattening are heated to about 80 ° C. the extraction of the oil contained in the seeds: this step is generally carried out by pressing (or pressing) in presses.

All these steps can be carried out using a single machine performing a continuous hot pressure, that is to say that the seeds are preheated to about 90 ° C, crushed / flattened and then pressed into a worm where the temperature will reach up to about 120 ° C.

Two products are recovered at the end of this pressing step: on the one hand oil, generally referred to as "crude" or "pressure", and - on the other hand, a first solid residue, namely press scales or a fat cake.

The fat cake usually comprises between 10 and 20% of residual oil.

In order to extract this residual oil present in the fatty cake, the trituration may comprise at the end of the pressing, a chemical extraction step by solvent. The solvent usually used for this extraction is hexane. The solvent extraction step thus gives on the one hand the "residual" oil coming from the oily meal, and on the other hand a second residue of the seeds, called deoiled cake. The deoiled cake generally comprises between 0.1 and 10%, preferably from 1 to 4% of non-extracted oil.

In contrast, in the case of soybeans, the crushing operation essentially comprises the following steps: flattening, and the extraction of the oil contained in the seeds: this step is generally carried out by chemical extraction with solvent. At the end of the soybean crushing, two products are recovered: oil and soybean meal.

The cake is therefore a co-product of vegetable oil production. However, the valorization of oilcakes by the oleaginous and / or oléoprotéagineuse sector has greatly increased in recent decades. Indeed, the plant meal is very rich in good quality protein, the latter was quickly used as a source of vegetable protein in animal feed, in substitution or in addition to animal protein. But the use of plant cakes has not been limited to these specific value chains and has developed more recently in other areas, particularly in the field of chemistry.

In this field, much research has focused in recent decades on what has been called "green chemistry", the main objective of which is the use of more environmentally friendly products such as, for example, the use of of products of renewable origin and the valorization of co-products. However, plant cakes represent a bio-sourced product of the future because of their specific properties derived in particular from their remarkable levels of protein and pectin. For example, it is known to use plant cakes in the formulation of adhesive compositions for the manufacture in particular of composite wood panels. Application WO 2011/156380 discloses in particular a protein-based adhesive composition comprising a pre-polymer such as a polyisocyanate-based prepolymer, and a protein component, which may be a milled seed cake, in an amount sufficient to dispersing the prepolymer in an aqueous medium.

There is still a need for composite wood panels based on environmentally friendly material such as crushed plant cake with improved properties.

The work of the inventor has made it possible to demonstrate that the use of a particular plant grind composition makes it possible to improve the properties of the wood panels comprising the said composition. The invention therefore relates to a composition comprising: a crushed plant containing at least 3% of proteins, maltodextrin, and silicone.

It will be noted that throughout the application, and unless otherwise stated, the ranges of values indicated are included limits.

"Crushed plant material containing at least 3% protein" (hereinafter also referred to as "ground vegetable material") is intended to mean a vegetable material in the form of particles, after grinding and containing at least 3% of protein . Preferably, the crushed plant contains at least 10% of proteins, more preferably at least 20%.

The plant meal referred to by the invention may comprise particles insoluble in water.

Preferably, the ground meal containing at least 3% protein is: - a cake of one or more species of ground oleaginous plants (hereinafter referred to as "milled vegetable meal"), - a fruit mash and / or seeds of one or more crushed protein crop species (hereinafter referred to as "crushed protein plants"), or - their mixture.

More preferably still, the crushed plant is a crushed plant cake.

The composition according to the invention makes it possible in particular to improve the properties of an adhesive composition and / or an article comprising it. In particular, the inventors have demonstrated that the adhesive compositions and articles based on lignocellulosic materials, comprising a composition according to the invention have improved properties such as the gel time for the adhesive composition or the mechanical strength properties and swelling with water for the items. The advantages of the composition according to the invention will be more fully presented later in the application, and in the examples.

By "grinding" is meant any step to obtain a plant powder, and more particularly a plant meal powder. The grinding may comprise a pre-grinding and / or one or more fractionations of the grind.

Pre-grinding is a step aimed primarily at making a first reduction in the form of coarse particles. This pre-grinding is generally followed by a fractionation step.

The purpose of the fractionation is to select part of the particles according to their size and / or chemical composition and can be carried out by various techniques such as sieving to a particular particle diameter, or tribo separation.

According to the invention, "plant cake" denotes a fat cake or deoiled obtained at the end of an extraction step (trituration, chemical extraction such as solvent) of the oil contained in the seeds or the fruits of oleaginous plants. Preferably, the cake is a deoiled cake derived from a trituration step followed by a solvent extraction step.

Advantageously, the plant cake comprises a percentage of oil of 0.1 to 20%, preferably 1 to 4% by weight of the total dry weight of plant cake.

By "maltodextrin" is meant a polysaccharide derived from the hydrolysis of starch. Derivatives of the hydrolysis of starch are generally defined by their dextrose equivalent (DE).

DE is the amount of reducing sugars expressed as a percentage of dextrose, also called D-glucose, relative to the total dry weight of product. Generally, the DE is indicated by a number or a number without indication of the unit (%). For example, dextrose, which corresponds to the product resulting from the total hydrolysis of the starch, will be characterized by a DE equal to 100%, or 100. On the contrary, the unhydrolyzed starch will be characterized by a DE equal to 0. Maltodextrin is defined as a derivative of the hydrolysis of starch having a DE between 0 and 20. The starch derivatives having a DE in the range] 20; 100 [are, for their part, called glucose syrups.

Advantageously, the maltodextrin will have an DE of between 0 and 13, preferably between 0.5 and 10 and more preferably between 1 and 6.

In addition to DE, maltodextrins can also be distinguished by their sugar composition, that is the nature and the number of sugars that compose them. In fact, depending on the source of starch used (potato, corn, wheat), the type of hydrolysis used (chemical or enzymatic hydrolysis) or according to the conditions of the hydrolysis, this sugar composition may vary. .

Advantageously, the maltodextrin used in the composition according to the invention will have good characteristics of dispersion and solubility in water. Maltodextrins that can be used in the context of the present invention are, for example, the maltodextrins marketed by ROQUETTE® under the tradename GLUCIDEX®.

By "silicone" (also referred to as "polysiloxane" or "siloxane") is meant oligomers, polymers or co-polymers having an inorganic skeleton comprising one or more silicon-oxygen chain (s) alternately, each chain being optionally be substituted on the silicon atoms by organic groups. Reactive or non-reactive organic groups may thus be grafted at the end of the chain and / or laterally on the main backbone.

Advantageously, the silicone is a polymer based on polydimethyl siloxane. Preferably, the silicone is a polyether-polydimethyl siloxane copolymer.

Preferably, the amount of maltodextrin in the composition is between 0.1 and 20%, more preferably between 0.5 and 10%, more preferably between 1 and 4% by dry weight on the total dry weight of cake.

Advantageously, the amount of silicone in the composition is between 0.5 and 30%, preferably between 5 and 20%, more preferably between 8 and 15% by dry weight on the total dry weight of cake.

According to a first embodiment of the invention, the ground material of the composition is one or more crushed plant meal (s) chosen from the group consisting of rapeseed, canola, sunflower meal, soy, cotton, flax, walnut, olive, mustard, hemp, carnation, safflower, kapok, corn germ, rape, safflower, shea, sesame, castor , camelina, jatropha, peanut, oil palm, hazelnut, almond and copra kernels. The carnation is also known as the black poppy. Copra is the dried raw material used for the extraction of coconut oil. At the end of this extraction, a copra cake is obtained.

Advantageously, the (s) cake (x) of crushed plants is (are) chosen (s) from the group consisting of rapeseed cake, canola, sunflower, soy and castor oil.

Preferably, the crushed plant meal is rapeseed or canola meal.

According to a second embodiment, the grind of plants in the composition is obtained by grinding fruit and / or seeds of proteinaceous plants selected from the group consisting of pea, faba bean, lupine, lentils, fenugreek and beans.

Preferably, the protein crops are selected from the group consisting of pea, faba bean and lupine.

According to the first embodiment of the invention, the crushed plant cake in the composition is in the form of a powder having a median volume diameter D50 of between 1 and 250 μm.

The median volume diameter D50 is a characteristic known to those skilled in the art. This diameter makes it possible to characterize a size distribution of the particles of a powder and corresponds to the diameter for which 50% of the total volume of the particles has a diameter less than the D50.

Preferably, the crushed plant meal is in the form of a powder having a median volume diameter D50 of between 5 and 100 μm, more preferably between 10 and 75 μm, more preferably between 15 and 50 μm, more preferably still between 20 and 40 μm. .

D99 volume diameter can also be used to characterize a particle size distribution of a powder. The diameter D99 is defined similarly to the volume median diameter D50 powder and corresponds to the diameter for which 99% of the total volume of the particles to a diameter less than D99.

Preferably, the crushed plant meal is in the form of a powder having a volume diameter D99 of between 40 and 300 μm, preferably between 70 and 180 μm, more preferably between 80 and 140 μm.

This particle size is also the one preferred for all the other types of ground material envisaged according to the invention.

Whatever the embodiment, the composition according to the invention is advantageously in the form of granules. When the pellet is prepared from a cake, it can also be called "coated cake". The invention also relates to a process for the preparation of a composition according to the invention comprising the following steps: (i) the grinding of the seeds and / or fruits of oleaginous and / or proteinaceous plants, (ii) the addition of maltodextrin and of silicone to the ground vegetable obtained in step (i)

By "grinding" is meant any step to obtain a plant powder, and more particularly a plant meal powder. More particularly, the powder resulting from this grinding has a median volume diameter D50 of between 1 and 250 μm.

Preferably, the grinding is carried out so as to obtain a powder whose volume median diameter D50 is between 5 and 100 μm, preferably between 10 and 75 μm, more preferably between 15 and 50 μm, and even more preferably between 20 and 40 pm.

Alternatively, the grinding may be performed so as to obtain a powder whose volume median D99 is between 40 and 300 μm, preferably between 70 and 180 μm, more preferably between 80 and 140 μm.

A grinder particularly suitable for carrying out the grinding step according to the process of the invention is a chopper type chipper.

Preferably, the grinding is performed on a cake of plants and is made so as to limit the heating of said cake. For this, the grinding is carried out at a temperature below 100 ° C., preferably below 80 ° C., more preferably below 60 ° C.

Throughout the application, temperatures and pressures are indicated under normal temperature and pressure (CNTP) conditions.

The grinding may, optionally, be preceded by a pre-grinding.

Pre-grinding is a step mainly aimed at making a first reduction in the form of particles. More particularly, by pre-grinding, it is intended any step to obtain a powder, such as a plant meal powder, having a median volume diameter D50 of between 250 and 450 pm.

This pre-grinding is preferably followed by a fractionation step. In general, this fractionation is a sieving (also referred to in this particular case by the term "blutage"). This sieving is preferably carried out at a diameter approximately equal to the volume median diameter D50 as defined during the pre-grinding step for recovering the fines having a diameter less than the median volume diameter and the refusal having a diameter greater than the diameter. median volume.

In the case of a plant meal, this pre-grinding followed by blutage (or sieving) makes it possible to separate a fraction rich in proteins ("the fines" used for the preparation of the ground meal) of a fraction depleted in proteins (ie the refusal). At the end of the pre-grinding and the possible blutage, grinding is carried out. This grinding can also be followed by a fractionation step. Such a fractionation can be achieved by a cyclone. Other dry or wet fractionation technologies may also be applied such as tribo-separation. By way of example, the application WO2015 / 097290 describes a process for tribo-separation of a plant cake.

According to a preferred embodiment of the process according to the invention, the addition of maltodextrin and silicone carried out in step (ii) is carried out by the preparation of at least one aqueous solution comprising maltodextrin and / or silicone.

The aqueous solution can be prepared from any type of water, such as tap water, demineralized, deionized and / or distilled water.

Advantageously, the aqueous solution comprises maltodextrin. This solution comprises maltodextrin at a content of between 1 and 40% by dry weight of maltodextrin on the total weight of water, preferably between 10 and 30% by dry weight of maltodextrin on the total weight of water, plus preferentially still between 15 and 25% by dry weight on the total weight of water.

The aqueous solution of maltodextrin may further comprise silicone. This solution then comprises the silicone at a content between 30 and 80% by dry weight of silicone on the total weight of water, preferably between 40 and 70% by dry weight of silicone on the total weight of water, plus preferably still between 55 and 65% by dry weight on the total weight of water.

The total water weight of the aqueous solution is defined as the total weight of water introduced into the solution, without taking into account the water inherently included in the ground vegetable, maltodextrin or any other ingredient introduced into the solution. solution other than water.

The aqueous solution may also include other ingredients, such as urea. For example, the urea content in the aqueous solution is between 0.01 and 40% by weight relative to the total weight of water.

According to a first variant of the preferred embodiment, the aqueous solution is sprayed on the ground material obtained in step (i).

Preferably, the spraying is carried out with an aqueous solution comprising both maltodextrin and silicone.

Alternatively, two sprays can be carried out on the one hand with the aqueous solution of maltodextrin and on the other hand with the silicone. In this case, the silicone is preferably sprayed before the aqueous solution of maltodextrin.

Advantageously, the spraying is carried out under vacuum. Preferably, the spraying system is provided with a solid cone nozzle to ensure better dispersion of the drops.

Drying of the plant meal can then be carried out at a temperature of the order of 20 to 70 ° C, preferably of the order of 40 to 60 ° C. At the end of this drying, a granulate of ground mills (coated with maltodextrin and / or silicone) is obtained, having a moisture content of about 1 to 12% by weight, preferably of the order from 5 to 7%.

According to a second variant of the preferred embodiment, the ground material obtained in step (i) is suspended in the aqueous solution.

Preferably, the ground material obtained in step (i) is suspended at a content of between 30 and 80%, more preferably between 40 and 70%, even more preferably between 55 and 65% by dry weight relative to the total weight. of water and ground.

More particularly, the ground material obtained in step (i) is suspended in an aqueous solution containing maltodextrin.

This aqueous solution containing maltodextrin may advantageously comprise urea.

In this case, the silicone is added to the aqueous suspension containing the ground material obtained in step (i), maltodextrin and optionally urea. The invention also relates to an adhesive composition comprising a composition according to the invention, and to one or more precursors of a resin chosen from the group consisting of polymethylene diphenyl 4,4'-diisocyanate, urea-formaldehyde, phenol- formaldehyde and / or melamine-urea-formaldehyde.

The term "precursor of a resin" is intended to mean a component or mixture of components which, after a polymerization step, makes it possible to obtain said resin. The use of a composition according to the invention makes it possible to reduce the gel time of the adhesive composition according to the invention, as described in Examples 2 and 3 and in FIG. 2.

Polymethylene diphenyl 4,4'-diisocyanate is also known as pMDI, urea-formaldehyde under the name UF, phenol-formaldehyde under the name PF and melamine-urea-formaldehyde under the name MUF .

Preferred resin mixtures are pMDI and UF on the one hand and pMDI and PF on the other hand.

The adhesive composition according to the invention may further comprise urea, a hydrophobic agent such as wax.

By "hydrophobing agent" is meant any substance whose function is to prevent or reduce the contact or penetration of water in a material.

More generally, the adhesive composition according to the invention may comprise one or more agents chosen from the group consisting of: formaldehyde entrapping agents or crosslinking agents such as urea, phenol, catalysts, tackifiers, fillers such as calcium carbonate, clay, thickeners or texturizing agents or gelling agents, surfactants such as siloxanes, adhesion promoters such as a polyol, for example in the case where the resin introduced in the composition is isocyanate-based, antioxidants such as polyphenols, antifoaming agents, antimicrobial agents such as oxidants, antibacterial agents such as nitrogen derivatives, fungicides such as sulfur products, preservatives such as citric acid, paraben, pigments such as titanium dioxide, moisture-enhancing agents or hydrophobing agents such as such as wax, pH modulators such as urea, and composite release or release agents, fire retardants.

A solid binder can also be prepared from the adhesive composition according to the invention by polymerization thereof. Advantageously, the polymerization is carried out by hot curing. The curing temperature is generally between 100 and 300 O, more preferably between 140 and 250 ° C. The invention also relates to an article comprising an adhesive composition according to the invention and a lignocellulosic material.

By "lignocellulosic material" is meant more particularly paper, cardboard, strips of wood, wood veneer, wood particles, wood fibers. Wood particles can be chips, sawdust or other wood waste from a sawmill. The use of a composition or an adhesive composition according to the invention makes it possible to improve the properties of articles based on lignocellulosic material (s) comprising them. In particular, these articles have an increased resistance to stress and a decreased swelling rate, as compared to articles comprising a composition or an adhesive composition based on crushed sole plants, crushed plants and maltodextrin, or ground grinds. of plants and silicone. These advantages are more fully presented in Example 3 and Figure 3.

Advantageously, the article according to the invention is a lignocellulosic composite panel. A lignocellulosic composite panel is a combination of lignocellulosic materials and an adhesive composition called matrix, in which the lignocellulosic materials and the matrix retain their identity, do not dissolve or do not mix completely. As a result, they can be physically identifiable on a macroscopic scale.

More particularly, the article is glue-laminated wood, plywood or a composite wood panel such as a slat or oriented particle board (OSB), particle board or chipboard, or a wood fiber board. The invention also relates to a method of manufacturing an article according to the invention. Advantageously, the method comprises the following steps: (i) contacting a lignocellulosic material with the adhesive composition according to the invention, and (ii) heating the adhesive composition so as to cure it.

The curing temperature is generally between 100 and 300 ° C, more preferably between 140 and 250 O. The curing time is less than 10 min, preferably less than 5 min. Preferably, the heating of the adhesive composition so as to cure it is effected by thermopressing (concomitant heating and pressing step).

Advantageously, the lignocellulosic material is wood particles. These are then brought into contact with the adhesive composition according to the invention. This contacting can be carried out by mixing the wood particles with the composition according to the invention or alternatively by spraying the composition according to the invention on the wood particles. The wood particles thus brought into contact with the adhesive composition according to the invention are then placed in a mold, pressed and heated to harden the adhesive composition.

More particularly, a wood particle board is usually manufactured according to the following method:

Preparation of the lignocellulosic raw material (grinding, classification, drying), mixing with the adhesive composition,

Formation of the particle mattress,

Thermopressing, and possibly

Finishing panels. The invention finally relates to the use of a composition according to the invention for the preparation of an adhesive composition, a polyurethane foam, a cosmetic composition, a phytosanitary composition or a food composition.

Preferably, the adhesive composition is an adhesive composition for lignocellulosic material, such as wood-based materials. By way of example, the characteristics of these wood-based materials, such as wood panels, and their method of manufacture are more fully described above and in Example 3.

By "phytosanitary composition", it is more particularly a composition for the protection of crops.

Preferably, the food composition is an animal feed composition, such as a feed composition for aquaculture. The invention will be better understood from the following examples, given by way of illustration, with reference to:

Figure 1, which represents the typical profile of particle size distribution measured in the dry state on the powder of a milled cake of plants (for example, rapeseed, sunflower, soy ...);

FIG. 2, which represents a diagram illustrating the effect of the introduction of maltodextrin and / or silicone on the gel time of an adhesive composition,

FIG. 3 which represents diagrams illustrating the effect of the introduction of maltodextrin and / or silicone on the properties of an agglomerated wood panel, in particular, the mechanical strength (maximum flexural stress 3 points (MPa), Fig. 3A) and the water swelling rate of a chipboard (as a% increase in thickness) after 24h of immersion (Fig. 3B); and

Figure 4, which presents diagrams illustrating the effect of the chemical nature of the silicone on the properties of a chipboard, in particular, the mechanical strength (maximum flexural stress 3 points (MPa), Fig. 4A) and the water swelling rate of a chipboard (in% increase in thickness) after 24 hours of immersion (Fig. 4B). Other features and advantages of the invention will become apparent in the examples which follow, given by way of illustration.

Example 1 Composition According to the Invention in Granule Form 1. Material 1.1. oilcake

The rapeseed cake used in this example was supplied by Saipol (Grand Couronne site, France). This cake was obtained by a hot pressing step, followed by a step of extraction by organic solvent (ie hexane) pressure flakes (which designate the product obtained at the end of the pressure step hot) to extract the vegetable oil.

By hot pressing step is meant a step comprising a preheating of rapeseeds up to 90 ° C, then grinding said seeds and pressing in a worm where the temperature can reach up to 120 ° C. A fat meal is then obtained comprising 12% to 14% of residual oil.

Finally, the organic solvent extraction step is followed by a desolvation step.

The rapeseed cake thus obtained generally contains 1 to 2% residual oil for 10 to 12% moisture. 1.2. maltodextrin

Maltodextrin is of the brand Glucidex® 1 (DE <6%) from Roquette®. This maltodextrin is in the form of a white powder with a maximum moisture content of 6% by weight. 1.3. Silicone

Silicone is a polydimethyl siloxane-based polymer supplied by Evonik® (Germany), namely Tegostab B8460 (polyether-polydimethyl siloxane copolymer). 1.4. Water Water is demineralized water. However, tap water could be used. Indeed, a test was carried out with tap water and no effect was observed on the properties of the compositions, compared to a test using demineralised water. 2. Method 2.1. Grinding rapeseed cake

The rapeseed cake supplied by Saipol was crushed using an 11 kW ATTRIMILL (Poittemill) mill which allowed flow rates between 10 and 300 kg / h of fine particles. The flow obtained with the mill is the result of a regulation activating the feed screw of the mill according to the intensity consumed. The screw is in operation until the power consumption of the crusher exceeds the limit of 19 Ampere (A). Once this limit is exceeded, the screw stops automatically, and restarts as soon as the amperage goes below the limit of 18 A. This system of "ping pong" lasts as long as there is product in the feed hopper of the grinder. This mill is equipped with a dynamic cyclone allowing a particle size classification and a selection of particles according to their size.

In practice, the adjustments made are as follows: o milling speed of 4880 revolutions / minute, o dynamic cyclone at 10 Hz.

During grinding, it was ensured that the heating of the cake was limited. For this, the outlet air temperature of the mill filter has been controlled so that it does not exceed 60 ° C. Air passing through the mill was drawn from the test hall at a temperature of 20 ° C throughout the milling period. The plant (mill and cyclone) was cleaned between each grinding.

The yield of this operation (grinding and cyclone) is greater than 99%.

The obtained rapeseed meal then has the following particle size distribution profile: D50 (median volume diameter) <40pm D99 <140pm.

More particularly, the grinding and the selection of the particles by cyclone of the cake are intended to obtain a granulometric profile shown in FIG. 1. The grinding step described above may, optionally, be preceded by a step of pre-grinding the cake. at a coarse grain size having a median volume diameter D50 of about 250 to 450 μm. This pre-grinding is followed by a sieving step (or blotting) at a diameter corresponding to the D50 to separate the fines having a diameter smaller than the refusal diameter (ie particles with a diameter greater than D50). This upstream process makes it possible to separate a protein-rich fraction (ie particles with a diameter less than D50) from a protein-depleted fraction (ie particles with a diameter greater than D50). Other particle selection technologies can also be applied. For example, dry fractionation such as tribo-separation or wet such as precipitation in a solvent under given physicochemical conditions can also be carried out. 2.2. Measurement of particle size of rapeseed meal particles obtained

The median volume diameter D50 of the rapeseed cake obtained at the end of the milling step was measured in the dry state. The particle size of the milled rapeseed meal particles was characterized using a HELOS type WINDOX 5 laser granulometer. The measurement range is 0.5 to 875pm.

The characteristics of the grain size measurement are as follows: o Feed rate of 50%, o Measuring cycle of 100 ms, o Pressure of 1 bar. 3. Preparation of a composition according to the invention, by granulation

The crushed cake is incorporated at room temperature in a De Dietrich blender with a jacket and spray system. This mixer is stirred at 140 rpm.

A solution of maltodextrin in water at 10% by dry weight of maltodextrin on the total weight of water and maltodextrin (ie 11.11% of maltodextrin by dry weight on the total weight of water) is prepared with stirring. mechanically using a four-blade helix (about 400 rpm) in about 1 minute.

The silicone is added to the aqueous solution of maltodextrin at a content of 55% by dry weight on the total weight of water and maltodextrin (ie 61.11% of silicone by dry weight on the total weight of water).

The solution containing the maltodextrin and the silicone is then tempered preferably at a temperature between 45 and 51 ° C to ensure better solubilization, then pumped and sprayed into the stirrer at atmospheric pressure. The vacuum is then applied to the stirred mixer and reached in two to three minutes (70-100 mmHg). Then, the set temperature of the double jacket of the mixer is gradually raised to 60 ° C. The test is terminated when the moisture content of the powder is between 3 and 6% by weight (corresponding to a temperature of the powder between 52 and 57 ° C). The water content is monitored during the drying process. A maximum water content of the 6% granulated cake was chosen to maintain the specification given for that of maltodextrin alone.

The granulate thus obtained can be easily suspended in water. To facilitate this suspension, the granulate can undergo a sieving operation, for example at 250pm, prior to its introduction into the water.

Example 2 Preparation of a Composition According to the Invention and Comparative Compositions 1. Materials 1.1. oilcake

The rapeseed meal used in this example is identical to that of Example 1. 1.2. maltodextrin

Maltodextrin is that described in Example 1. 1.3. Silicone

Silicone is the polydimethyl siloxane-based polymer described in Example 1. 1.4. Water The water is that described in Example 1. 1.5. Petrochemical resins

The resin used for the preparation of the adhesive composition is a urea-formaldehyde resin, DYNEA®, having a solids content of 65%. Three types of resins were tested: pMDI (polymethylene diphenyl 4,4'-diisocyanate, BAYER, purity of 99%), UF (Urea-Formol, DYNEA, dry extract of 65%) and PF (Phenol-Formol, DYNEA, PF molar ratio / hardener = 1.67, 100% solids). 1.6. Urea Urea is urea U5378 from Sigma Aldrich, USA. 1.7. Wax

The wax used is the MS27 Hydrofugant supplied by ICABOIS. Its dry extract is 58%. 2. Method 2.1. Grinding rapeseed meal and measuring the particle size of rapeseed meal particles obtained

The grinding of the rapeseed cake and the measurement of the particle size of the obtained rapeseed cake particles are carried out as indicated in Example 1. 2.2. Preparation of compositions

The adhesive compositions were prepared at room temperature. Their mixing was carried out mechanically using a four-blade propeller at a variable speed of 400 to 1200 revolutions / minute. a) Composition according to the invention 4c (with maltodextrin and silicone)

Urea and maltodextrin are added to water at a concentration of 1 μL -1 and 57 μL respectively, and then solubilized with stirring (about 400 rpm) in about 1 minute.

Crushed rapeseed meal is then added to the water-urea-maltodextrin mixture in about 3 minutes by successive addition of small amounts, at a stirring rate ranging from 400 to 500 rpm depending on the increase in viscosity ( that is to say that at the time of adding a new quantity of crushed cake, the stirring speed is increased to 500 revolutions / min), until a homogeneous suspension is obtained. The amount of cake added by weight relative to the total weight of water and cake is 25% w / w.

Then, the silicone is added at 500 rpm, 11% by weight relative to the total weight of ground cake.

This suspension of milled cake in an aqueous medium is then mixed with a urea-formaldehyde resin, added continuously under very vigorous stirring (approximately 1200 revolutions / minute), to a quantity of 93.92 g per 100 g of adhesive composition, the weights being given in dry weight. Stirring is maintained for 2 to 3 minutes to thoroughly homogenize the mixture.

The solids content of the adhesive composition is finally adjusted so that the viscosity of the adhesive formulation remains constant with respect to that measured on an adhesive formulation without cake. b) Comparative composition 4d (with silicone only)

Urea is added to water at a concentration of about 1 gL -1 and solubilized with stirring (about 400 rpm) in about 1 minute.

Crushed rapeseed cake is then added to the water-urea mixture in about 3 minutes by successive addition of small amounts, at a stirring rate ranging from 400 to 500 rpm as a function of the viscosity increase. that is to say that at the time of adding a new quantity of crushed cake, the stirring speed is increased to 500 revolutions / min), until a homogeneous suspension is obtained. The amount of cake added by weight relative to the total weight of water and cake is 25% w / w.

Then, the silicone is added at 500 rpm, at an amount of 11% by dry weight relative to the total weight of cake. This suspension of the milled cake in an aqueous medium is then mixed with a urea-formaldehyde resin, added continuously under very vigorous stirring (about 1200 rpm), to a quantity of 94.01 g per 100 g of adhesive composition, the weights being indicated in dry weight. Stirring is maintained for 2 to 3 minutes to thoroughly homogenize the mixture.

The solids content of the adhesive composition is finally adjusted so that the viscosity of the adhesive formulation remains constant with respect to that measured on an adhesive formulation without cake. c) Comparative composition 4th (with maltodextrin only)

Urea and maltodextrin (DE <6) are added to water at respective concentrations of 1 g.L'1 and 57 gL "1 and solubilized with stirring (about 400 rpm) in about 1 minute.

This suspension of cake milled in aqueous medium is then mixed with a urea-formaldehyde resin, added gradually with very vigorous stirring (about 1200 revolutions / minute). The quantity of resin added is 94.43 g per 100 g of adhesive composition, the weights being indicated in dry weight. Stirring is maintained for 2 to 3 minutes to thoroughly homogenize the mixture.

The solids content of the adhesive composition is finally adjusted so that the viscosity of the adhesive formulation remains constant with respect to that measured on an adhesive formulation without cake. d) Comparative composition 4b (without maltodextrin or silicone)

Urea is added to water at a concentration of about 1 μl -1 and solubilized with stirring (about 400 rpm) in about 1 minute.

Crushed rapeseed cake is then added to the water-urea mixture in about 3 minutes by successive addition of small amounts, at a stirring rate ranging from 400 to 500 rpm as a function of the viscosity increase. that is to say that at the time of adding a new quantity of crushed cake, the stirring speed is increased to 500 rpm), until a homogeneous suspension is obtained. The amount of cake added by weight relative to the total weight of water and cake is 25% w / w.

This homogeneous suspension of ground cake in water is then mixed with a urea-formaldehyde resin, added gradually with very vigorous stirring (about 1200 revolutions / minute). The quantity of resin added is 89.35 g per 100 g of adhesive composition, the weights being indicated in dry weight. Stirring is maintained for 2 to 3 minutes to thoroughly homogenize the mixture.

The solids content of the adhesive composition is finally adjusted so that the viscosity of the adhesive formulation remains constant with respect to that measured on an adhesive formulation without cake.

When using this composition as an adhesive composition, wax is added to this composition. e) Summary table of compositions

Table 1: Summary of compositions 4b to 4e expressed in percentage by dry weight of each ingredient on the total dry weight of composition. 2.3. Characterization of the compositions obtained

The compositions 4b to 4e can be used as adhesive compositions and have been characterized by:

The measurement of the dry extract using a halogenated balance (105 ° C, stabilization time of 20 seconds),

The measurement of a flow time using the viscosity section

Lory Elcometer 2215 (non-standard test),

The measurement of the gel time by monitoring the evolution of the viscosity

Trombomat (test temperature 180 to 200 ° C, this temperature range corresponding to those implemented during the heat transition of a composite wood panel). 3. Results

The results of the viscosity measurements and the gel time of the compositions are shown in Table 2 below and in FIG.

Table 2: Viscosity and gel time of the compositions (without the wax for test 4b).

As can be seen in Figure 2, the gel time of the adhesive composition is significantly reduced with the introduction of maltodextrin and little affected with the introduction of silicone. However, a synergistic effect of reducing the gel time of the composition is observed with the introduction of maltodextrin and silicone.

Reduction of the gel time can result in premature pre-hardening of the resin. An expected benefit of this accelerated hardening of the resin is a limitation of the temperature drop encountered during the drying in temperature. This effect makes it possible in particular to reduce the filtration of the adhesive composition through the material coated with this composition, for example through the pores of the wood particles. The adhesive composition thus remains more on the surface, for example wood particles and can better ensure its role as a binder.

Example 3: Preparation of chipboard

Sintered wood panels were prepared on a laboratory scale from adhesive compositions prepared in a manner similar to that of Example 2. For reasons of dimensioning, the panels were prepared in a layer, based on chips. fine (corresponding to the inner layer of a conventional panel). 1. Material 1.1. Adhesive compositions

The adhesive compositions 1c to 1f used in this Example are prepared in identical ways to the compositions 4b to 4e respectively, prepared in Example 2.

Compositions 1a and 1b are prepared from UF resin and optionally water and milled rapeseed cake as described in the material of Example 2. The preparation of these compositions is more fully detailed below. 1.2. Particles of wood

The particles (in this case, chips) of fine wood come from Kronofrance. 2. Method 2.1. Preparation of the composition 1a

UF resin is mixed with wood chips. To do this, it is usually sprayed on the wood chips in a mixer. However, during these tests, the resin was manually mixed with the wood chips.

When using this composition as an adhesive composition, wax is added to this composition. This addition is done manually after mixing the resin and wood chips. 2.2. Preparation of the composition 1b

Crushed rapeseed meal is added to water in about 3 minutes by successive addition of small amounts, at a stirring rate ranging from 400 to 500 rpm as a function of the increase in viscosity (ie that is, when adding a new quantity of ground cake, the stirring speed is increased to 500 rpm), until a homogeneous suspension is obtained. The amount of cake added by weight relative to the total weight of water and cake is 25% w / w.

This suspension of cake milled in aqueous medium is then mixed with a urea-formaldehyde resin, added gradually with very vigorous stirring (about 1200 revolutions / minute). Stirring is maintained for 2 to 3 minutes to thoroughly homogenize the mixture.

When using this composition as an adhesive composition, wax is added to this composition. This addition is done manually after mixing the resin and wood chips. 2.3. Summary table of adhesive compositions 1a to 1f

Table 3: Summary of adhesive compositions 1a to 1f expressed as a percentage by dry weight of each ingredient on the total dry weight of composition.

2.4. Characterization of the compositions obtained

The adhesive compositions 1a to 1f have been characterized by:

The measure of the dry extract,

Measuring a flow time,

The measurement of the freezing time, as described in Example 2. 2.5. Steaming wood chips The oven used is a conventional oven with ventilation.

The chips are placed in an oven at 60 ° C in aluminum trays with a capacity of about 100 g (which facilitates the placement of chips in the oven). They are left at least 6 hours at this temperature. The dry extract of chips used for wood panels composition is 97% (measured on a dry-matter scale).

The chips are left in the oven until use. They came out of the oven shortly before the completion of the wood panel (about 10 to 15 minutes, maximum to avoid a recovery in moisture of the particles, and which correspond to the cooling time). 2.6. Preparation of chipboard

The panels were prepared as follows: (i) Manual mixing of the wood chips (after cooling after leaving the oven) with one of the adhesive compositions 1a to 1f at a temperature of 30 to 35 ° C and for 2 min; (ii) For the adhesive compositions 1a to 1c, adding the wax to the mixture obtained in step (i) and manual mixing for 1 min; (iii) Incorporation of the mixtures obtained in steps (i) (mixing from adhesive compositions 1d to 1f) and (ii) (mixing from adhesive compositions 1a to 1c) in a mold whose dimensions have been calculated in order to be able to set the density of the panel at 650kg / m3 (the panels obtained measure approximately 250 x 350 mm2 for a final thickness of 7-8 mm); (iv) Incorporation of the molds containing the mixtures in an MI41 press from TechniHispania at 200 ° C. for 4 minutes. 2.7. Summary table of wood panels obtained from adhesive compositions 1a to 1f

*% by dry weight relative to the total dry weight of the chipboard Table 4: Summary of the compositions of the wood panels obtained from the adhesive compositions 1a to 1f 2.8. Characterization of chipboards The chipboard panels are characterized by two parameters:

The swelling with water: the measurement of swelling in thickness of the wood panel after total immersion in water (according to standard NF EN 317) is carried out at ambient temperature, the measurements of the thickness being carried out at tO, t + 2h, t + 24h, on average on 3 test tubes,

The mechanical resistance: the measurement is carried out by a 3-point bending test to evaluate the maximum stress, and the bending modulus (MPa) This measurement is inspired by the NF EN 310 standard and is performed on MTS Criterion type traction machine (model43), with a 2 kN sensor, a test speed of 2 mm / min, averaged over 5 test pieces.

The standards as indicated in this application are those in effect on the filing date. 3. Results 3.1. Results on the adhesive compositions The results of the viscosity measurements and the gel time of the compositions are shown in Table 5 below.

* Vcu: Viscous Coupling Unit

Table 5: Viscosity and gel time of adhesive compositions 1a to 1f (without the wax for tests a, b and c).

The gel time of the adhesive composition is: significantly reduced with the introduction of cake and maltodextrin, and little affected with the introduction of urea.

A synergistic effect of reducing the gel time of the composition is also observed with the introduction of maltodextrin and silicone. 3.2. Results on chipboard

The results in terms of water swelling and mechanical strength are shown in Table 6 below and in Figure 3.

Table 6: Mechanical properties and water resistance of chipboard prepared using adhesive compositions 1a to 1f

The mechanical properties of the chipboard are significantly improved when it is prepared with the adhesive composition 1 d, ie with the adhesive composition comprising in combination a maltodextrin and a silicone, namely maltodextrin and a siloxane, respectively.

Indeed, as can be seen in Figure 3A, the stress resistance is the best for the wood panel prepared with a composition comprising both ground rapeseed cake, urea, maltodextrin and a siloxane.

It is more particularly noted that the addition of cake and, to a lesser extent, the addition of urea significantly increase the resistance to stress, while the addition of maltodextrin or siloxane alone slightly reduces this resistance.

However, unexpectedly, the combined addition of maltodextrin and siloxane significantly increases the stress resistance.

Regarding the swelling with water, as can be seen in Figure 3B, the addition of cake significantly degrades the resistance of the wood panel swelling when immersed in water. This degradation is totally offset by the addition of urea. However, the addition of maltodextrin or siloxane

each causes a very slight increase in the rate of swelling with water while, unexpectedly, the combined addition of maltodextrin and siloxane makes it possible to reduce this rate of swelling. The best result in terms of resistance to water swelling is thus obtained with an agglomerated wood panel prepared with a composition comprising both ground rapeseed cake, urea, maltodextrin and a siloxane.

EXAMPLE 4 Effect of the Chemical Nature of Silicone on the Properties of the Chipboard 1. Material 1.1. Silicone

Two polymers based on polydimethyl siloxane were tested, both provided by Evonik (Germany):

Tegostab B8460: polyether - polydimethyl siloxane copolymer, and Tegoprotect 5000: hydroxyl functionalized polydimethyl siloxane. 1.2. Adhesive compositions

The adhesive compositions 3a and 3b used in this Example are prepared identically to the composition 4c of Example 2, the only difference between the compositions 3a and 3b being the nature of the silicone introduced into the composition. 1.3. Wood panels

The chipboard is prepared as in Example 3. 1.4. Summary table of wood panels obtained from adhesive compositions 3a and 3b

*% by dry weight relative to the total dry weight of the chipboard Table 7: Summary of the compositions of the wood panels obtained from the adhesive compositions 3a and 3b 2. Method 2.1. Characterization of the compositions obtained

The adhesive compositions 3a and 3b have been characterized by:

The measure of the dry extract,

Measuring a flow time,

The measurement of the freezing time, as described in Example 2. 2.2. Characterization of chipboard

Sintered wood panels are characterized by two parameters:

Swelling with water,

Mechanical strength, as described in Example 3. 3. Results 3.1. Results on adhesive compositions

The results of the viscosity measurements and the gel time of the compositions are shown in Table 8 below.

* Vcu: Viscous Coupling Unit

Table 8: Viscosity and gel time of the adhesive compositions 3a and 3b 3.3. Results on chipboard

The results in terms of water swelling and mechanical strength are shown in Table 9 below and in Figure 4.

Table 9: Mechanical properties and water resistance of chipboard prepared using adhesive compositions 3a and 3b

As can be seen in Figure 4A, the mechanical properties of the chipboard obtained with the two surfactants are similar. In contrast, the water resistance of the chipboard is improved when the wood panel is prepared with an adhesive composition comprising Tegostab B8460 relative to a wood panel is prepared with an adhesive composition comprising Tegoprotect 5000. However , the water resistance of the latter remains within the acceptable upper limit.

Claims

A composition comprising: a crushed plant containing at least 3% protein, maltodextrin, and silicone.

2. Composition according to claim 1, wherein the amount of maltodextrin in the composition is between 0.1 and 20% by dry weight on the total dry weight of ground vegetable.

3. Composition according to one of claims 1 or 2, wherein the amount of silicone in the composition is between 0.5 and 30% by dry weight on the total dry weight of ground vegetable.

4. Composition according to any one of claims 1 to 3, wherein the crushed plant is one or more crushed plant meal (s) selected (s) from the group consisting of rapeseed, canola, sunflower cake , soy, cotton, flax, walnuts, olive, mustard, hemp, carnation, corn germ, rape, safflower, shea, sesame, castor oil, camelina, jatropha, peanut, oil palm, hazelnut, almond and copra kernels.

5. Composition according to any one of claims 1 to 3, wherein the crushed plant is obtained by grinding fruit and / or seeds of protein crops selected from the group consisting of pea, faba bean, lupine, lentils, fenugreek and beans.

6. A composition according to any one of claims 1 to 4, wherein the crushed plant cake is in the form of a powder having a median volume diameter D50 of between 1 and 250 μm.

7. Composition according to any one of claims 1 to 6, in the form of granules.

8. Process for the preparation of a composition according to one of claims 1 to 7 comprising the following steps: (i) the grinding of seeds and / or fruits of oleaginous and / or proteinaceous plants, (ii) the addition of maltodextrin and silicone milled plant obtained in step (i).

9. Preparation process according to claim 8, wherein the addition of maltodextrin and silicone carried out in step (ii) is carried out by the preparation of at least one aqueous solution comprising maltodextrin and / or silicone.

10. Preparation process according to claim 9, wherein the aqueous solution is sprayed on the ground material obtained in step (i).

11. Preparation process according to claim 9, wherein the ground material obtained in step (i) is suspended in the aqueous solution.

12. Adhesive composition comprising a composition according to one of claims 1 to 7, and one or more precursors of a resin selected from the group consisting of polymethylene diphenyl 4,4'-diisocyanate, urea-formaldehyde, phenol -formaldehyde and / or melamine-urea-formaldehyde.

An article comprising an adhesive composition according to claim 12 and a lignocellulosic material.

14. Use of a composition according to one of claims 1 to 7 for the preparation of an adhesive composition, a polyurethane foam, a cosmetic composition, a phytosanitary composition or a food composition.