EP3634649A1 - Hydrophobic treatment of wood - Google Patents

Hydrophobic treatment of wood

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Publication number
EP3634649A1
EP3634649A1 EP18729650.4A EP18729650A EP3634649A1 EP 3634649 A1 EP3634649 A1 EP 3634649A1 EP 18729650 A EP18729650 A EP 18729650A EP 3634649 A1 EP3634649 A1 EP 3634649A1
Authority
EP
European Patent Office
Prior art keywords
oil
wood
esterification
pressure
fluid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP18729650.4A
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German (de)
French (fr)
Other versions
EP3634649B1 (en
Inventor
Aur lien AUGER
Nicolas Bedouin
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Publication of EP3634649A1 publication Critical patent/EP3634649A1/en
Application granted granted Critical
Publication of EP3634649B1 publication Critical patent/EP3634649B1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
    • B27K3/086—Impregnating by pressure, e.g. vacuum impregnation using supercritical or high pressure fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/346—Grafting onto wood fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/70—Hydrophobation treatment

Definitions

  • the present invention relates to a method particularly useful for carrying out a hydrophobic treatment of a wood-type material and / or its by-products in order to block its recovery in water and thus improve its durability.
  • wood Used as a material for building or heating, wood is extremely present in our society. In the field of construction, the wood is used for the interior (parquet, decoration, etc.) or outside (doors, cladding, etc.). In addition, there are many reasons to choose wood as a building material: appearance, thermal insulation, cost, environmentally friendly. Like other materials (concrete, bricks, polymers, plastics, etc.), wood for building is subject to drastic weather conditions (rain, wind, UV exposure, etc.) and fungal attacks (molds).
  • Wood is a hygroscopic material.
  • the dimensions and composition of a wood substrate are likely to change depending on its moisture content.
  • this type of transformation is undesirable insofar as these modifications tend to alter the integrity of the material and therefore its life or its durability.
  • this phenomenon of hygroscopy is more pronounced with woods such as pines, fir trees and more generally spruces, which are widely used woods given their moderate costs.
  • "species" of wood or "species” of wood or even “varieties” of wood such as Douglas fir, which are expensive woods have lower sensitivities to humidity (use class 4).
  • the esterification of the hydroxyl functions of wood is the method conventionally considered to make the wood hydrophobic and thus considerably improve its durability and thus its chemical or dimensional stability.
  • fluids under supercritical conditions have been used as preferential vectors of antifungal and antimicrobial compounds for impregnating the wood, as well as for the extraction of undesirable substances.
  • the invention relates to a process for esterification of all or part of the hydroxyl functions of a wood-type material and / or of one of its derived products, characterized in that it brings said material into contact with a fluid in a supercritical state carrying at least one natural unsaturated vegetable oil, preferably drying, under conditions conducive to carrying out said esterification, comprising at least the steps of:
  • i) have, within a chamber, a wood-type material, preferably having a water content of less than 20% by weight relative to its total weight, and at least one unsaturated natural vegetable oil conveyed , preferably solubilized, in a liquid fluid capable of evolving under pressure in a supercritical state.
  • step iii) exposing said impregnated material with said oil obtained in step ii) under conditions of pressure and temperatures effective to make said fluid evolve to a supercritical state and carry out said esterification reaction.
  • the method according to the invention comprises a step of diffusion of said oil, conveyed by said supercritical fluid, within said material, and therefore in depth of said material, prior to said esterification.
  • the process according to the invention makes it possible to access a hydrophobic treatment at depth of the treated wood, unlike processes without such a stage as those described in CN 104 985 653 A and WO 2013/070196 A2.
  • this preliminary step is carried out at a pressure of between 15.0 and 25.0 MPa, preferably around 20.0 MPa, at room temperature and for a time sufficient to promote an effective impregnation of the material by said oil.
  • step ii) requires pressurizing the chamber to a pressure of at least 15.0 MPa or even at least 20.0 MPa.
  • Step iii) comprises the diffusion of said oil carried by the fluid in the supercritical state within said material and its interaction, by esterification, with the free hydroxyl functions of said material. It is advantageously carried out at a pressure greater than that considered in step ii) preferably to about 30.0 MPa, and under heating, preferably at a temperature ranging from 100 ° C to 150 ° C and preferably about 130 ° C and for a sufficient time for carrying out said esterification.
  • the invention also relates to the use of a method as defined above, for the hydrophobic treatment of a wood-type porous material and / or its derived products and in particular for the purpose of increasing its durability.
  • wood will be used generically to designate all the porous materials containing free hydroxyl functions within their structures and formed in whole or in part of wood, that is to say wood as such, but also products derived from wood.
  • wood-based products is used to cover materials such as, for example, wood particles and composite products, for example agglomerated panels.
  • the method according to the invention is particularly suitable for the treatment of a type of wood chosen from hardwoods such as beech and softwoods such as red cedar and those of the family Pinaceae such as fir, pine and spruce.
  • the process according to the invention makes it possible to confer on woods with a lower cost than the species of wood species with slower growth, comparable properties in terms of environmental sustainability and in particular comparable weather resistance properties.
  • the wood treatment method according to the invention implements at least one unsaturated natural vegetable oil.
  • Vegetable oils are often divided into three categories, depending on their quality, and these categories are non-drying, semi-drying and drying. In contrast to non-drying oils, drying oils have the advantage of rapidly oxidizing and then becoming solid. They thus form a more resistant protective film.
  • oil will be used to denote either a single oil or a mixture of oils.
  • the oil considered according to the invention comprises unsaturations, preferably at least two unsaturations, and more preferably at least three unsaturations.
  • the oil suitable for the implementation of the present invention contains carboxylic acid functions capable of reacting with hydroxyl functions commonly present in woods.
  • these functions are in contrast inert with respect to supercritical fluids including carbon dioxide type.
  • the oil suitable for the implementation of the present invention may be in particular a modified oil by chemical reaction.
  • it can be refined and / or partially polymerized.
  • blown oils and standolies there may be mentioned blown oils and standolies, maleinized oils, epoxidized or cooked.
  • the oil considered according to the invention may also contain additives and in particular cobalt salt, zirconium salt and 2-ethylhexanoic acid (between 0.1 and 1%) which makes it more siccative.
  • the oil considered according to the invention is a drying unsaturated vegetable oil.
  • the drying oil of the invention may be advantageously chosen from among the follicle oil, linseed oil, pomegranate oil, castor oil, walnut oil, cotton, their derivatives and in particular their esters.
  • the drying unsaturated vegetable oil according to the invention is linseed oil or raw and preferably raw.
  • drying oils are commercially available.
  • flaxseed oil marketed by RECOCHEM Inc.
  • the oil considered according to the invention is used in sufficient quantity to obtain the expected hydrophobic treatment.
  • the adjustment of this quantity falls clearly the skills of the skilled person.
  • the implementation of an excess of oil is possible. It is then possible to consider in parallel its recycling.
  • the oil (or mixture of oils) considered according to the invention is implemented at a weight equivalent to the weight of the material to be treated.
  • the fluid in the supercritical state according to the invention is inert with respect to the vegetable oil with which it is used.
  • a supercritical fluid is a fluid having a critical temperature, below which it is in the liquid state and a fluid in the supercritical state is a fluid which has been exposed, generally under pressure, to a temperature above its critical temperature.
  • the supercritical fluid suitable for the present invention may be any suitable fluid such as, but not limited to, carbon dioxide, nitrous oxide (N 2 0).
  • It is preferably carbon dioxide.
  • Carbon dioxide is a solvent that is considered “green”. Carbon dioxide has a relatively low critical temperature (31.1 ° C). It is virtually non-toxic, non-flammable, relatively inert and has little impact on the environment compared to the other supercritical solvents listed above.
  • the fluid in the liquid state dissolves the lipophilic compounds that are unsaturated vegetable natural oils and is therefore effective for efficiently conveying them.
  • the fluid loaded with oil and having evolved in the supercritical state diffuses efficiently within the material and thus guarantees efficient and uniform esterification of the latter.
  • the pressure conditions conditioning the transition from the fluid state to the supercritical state are variable depending on the fluid in question and their adjustment is clearly within the skill of the skilled person.
  • this conversion is carried out from 31 ° C. and under a pressure of the order of 20.0 MPa.
  • the supercritical fluid is carbon dioxide and unsaturated natural vegetable oil is a drying oil and preferably a linseed oil.
  • the process according to the invention does not require the obligatory presence of a catalyst for carrying out esterification.
  • the process is carried out in the absence of an esterification catalyst.
  • Such a catalyst has the advantage of accelerating the interaction between the free cellulosic hydroxyl groups and the carboxylic functions of the fatty acids of the oil and thus contributing to a faster retention of the latter in the wood.
  • Such catalysts may especially be H 2 SO 4 or pyridine.
  • the method according to the invention comprises at least the steps of:
  • i) have, in a chamber, a wood-type material and preferably having a water content of less than 20% by weight relative to its total weight and at least one unsaturated natural vegetable oil conveyed, preferably solubilized, in a liquid fluid capable of evolving under pressure to a supercritical state
  • esterification reaction exposing said material impregnated with said oil obtained in stage ii) to conditions of pressure and temperatures that are effective for changing said fluid to a supercritical state and carrying out said esterification reaction.
  • the esterification reaction is carried out under anhydrous conditions. Indeed, in the absence of water, the yield of the esterification is considerably increased.
  • the wood-type substrate advantageously undergoes, prior to being brought into contact with the supercritical fluid carrying the oil, a drying operation so as to significantly reduce its water content which could interfere with the smooth running of the chemical esterification reaction.
  • the elimination of water may in particular be sanctioned by weighing the substrate before and after drying.
  • this drying step is performed under conditions conducive to the reduction of about 10% of the initial weight of the wood-type substrate, which corresponds to a removal of water.
  • the material considered in stage i) is advantageously a material having previously undergone a drying step intended to remove from 8% to 10% by weight of water relative to its total weight, preferably 9.4%. to 9.5% by weight of water relative to its total weight.
  • Such drying can in particular be carried out by heating the material at a temperature of 100 ° C. in an oven.
  • the material is then impregnated with said oil conveyed by said fluid in the liquid state.
  • This step ii) or impregnation step is advantageously carried out under pressure so as to homogenize the system and bring the oil conveyed by the liquid supercritical fluid to and into the porosities of the wood.
  • step ii) is carried out at a pressure of between 15.0 and 25.0 MPa, preferably about 20.0 MPa, at room temperature and therefore not supercritical and for a time sufficient to promote the reaction. impregnation of the entire material with said oil.
  • an ambient temperature is of the order of 20 ° C to plus or minus 5 ° C, and preferably less than 30 ° C.
  • the reactor containing the substrate to be treated can advantageously be pressurized at ambient temperature and under a CO 2 atmosphere, the pressure of which is equal to or less than 20.0 MPa.
  • the esterification consisting in the functionalization at least in part of the free hydroxyl functions of the constituent cellulose of the substrate to be treated, with carboxylic functions of the fatty acids constituting the oil, can then intervene.
  • Step iii) relating to this esterification is carried out at a pressure greater than that considered in step ii) and in the case of CO2 at a pressure, of the order of 30.0 MPa. and under heating preferably, at a temperature ranging from 100 ° C to 150 ° C and preferably about 130 ° C.
  • the temperature within the chamber is adjusted to generate the supercritical form of the fluid in question, for example at a value greater than 31 ° C. for CO2, and to promote the esterification reaction.
  • this temperature is greater than 70 ° C and is preferably of the order of 130 ° C.
  • esterification can be carried out between 0.5 and 24 hours.
  • An example of such a spectrum is shown in Figure 1.
  • the uniformity of the esterification reaction carried out according to the invention can be in turn controlled by a measurement of wetting angle. Results of this type for a sample of red cedar treated with linseed oil are shown in Table 1 below. It can thus be observed that Theta (M) angle values are increased for a treated sample compared to the same wood sample before treatment.
  • the process can advantageously be carried out within a device that can be closed, put under high pressure and heated. It may in particular be composed of a supercritical fluid supply in the liquid state, for example liquid C0 2 , a reaction chamber, a pump for pressurizing this fluid and a heating device.
  • a supercritical fluid supply in the liquid state for example liquid C0 2 , a reaction chamber, a pump for pressurizing this fluid and a heating device.
  • the process according to the invention uses linseed oil and supercritical CO2.
  • the weight of the material treated according to the invention is increased from 0.1% to 10%, preferably from 0.3% to 5%, relative to its original weight.
  • from 0.1% to 10%, preferably from 0.3% to 5%, of its weight in oil has been esterified within its structure.
  • the method according to the invention is particularly interesting for performing a hydrophobic treatment of a wood-type material and / or its derivatives.
  • Figure 1 Infrared spectrum of a 740N red cedar sample before treatment and after treatment 740.
  • Figure 2 Infrared spectrum of a 74 IN fir sample before treatment and after treatment 741.
  • Figure 3 Infrared spectrum of two samples of treated wood according to Example 4.
  • a sample of red cedar (width 280 mm, height 200 mm, length 910 mm) is dried at 100 ° C in an oven for 24 hours to remove traces of moisture and traces of water likely to displace the chemical equilibrium of esterification.
  • the initial mass of the red cedar sample prior to the process treatment is 12.578 g.
  • the sample is placed in a 250 ml volume reactor equipped with safety devices, needle valves, manometer, and heating cord.
  • the mass of linseed oil considered at the beginning of the esterification process is 11.396 g.
  • the temperature of the reactor is then adjusted to 130 ° C., and the pressure to 30.0 MPa, for 6 hours.
  • the equipment used is: K USS DSA10 Contact Angle Measuring System.
  • Untreated red cedar wood (740N) gives the following water wetting angles: 81.2 ⁇ 8.6 ° and 87.8 ⁇ 4.6 °.
  • the red cedar wood treated according to the process of the invention shows a clear increase in the measures of wetting angle indicating that the treated wood is more hydrophobic, and therefore has less affinity for water: 109.5 ⁇ 5.4 ° and 111.0 ⁇ 2.6 °.
  • IR spectrometric analyzes were also performed on both samples.
  • Figure 1 shows the results obtained.
  • the hydrogen bonds generated by the carboxylic acids are responsible for the displacement of this signal. In contrast, this peak is not present for the untreated sample (see Figure 1).
  • a fir sample (width 198 mm, height 199 mm, length 860 mm) is dried under the conditions detailed in Example 1.
  • the initial mass of the fir sample before the treatment according to the process is 12.047 g.
  • the mass of the fir sample after a drying step thereof is 10.898 g or 9.5% by weight of water removed.
  • Supercritical carbon dioxide esterification treatment CO2SC
  • the mass of linseed oil considered at the beginning of the process is 10.898 g.
  • the sample thus esterified is then characterized.
  • a sample of beech (diameter 197 mm, length 840 mm) is dried under the conditions detailed in Example 1.
  • a sample of spruce (width 15 mm, height 25 mm, length 50 mm) is dried under the conditions detailed in example 1.
  • the initial mass of the spruce sample before treatment according to the method is 8,110 g.
  • the mass of the sample of spruce after a drying step thereof is 7.258g is 10.5% by weight of water removed.
  • CO2SC Supercritical Carbon Dioxide Esterification Treatment
  • Example 1 The protocol is in accordance with that detailed in Example 1 except that the linseed oil is introduced into the reactor with the sample of spruce and the liquid fluid and is directly exposed to pressure conditions and temperatures effective to make evolve the fluid to a supercritical state, as described in Example 1.
  • a first sample is taken from the surface of the wood sample and a second sample is taken from the center of the sample.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a process for the esterification of all or some of the hydroxyl functions of a wood-type material and/or of one of the products derived therefrom, characterized in that said material is brought into contact with a fluid in a supercritical state carrying at least one natural unsaturated plant oil under conditions suitable for carrying out the esterification, and comprising at least the steps of: i) depositing, within a chamber, a wood-type material preferably having a water content of less than 20% by weight relative to its total weight and at least one natural unsaturated plant oil carried, preferably dissolved, in a liquid fluid capable of changing to a supercritical state under pressure; ii) subjecting the mixture to pressure conditions that are effective for the impregnation of the material by the oil; and iii) exposing the material impregnated by the oil obtained in step ii) to pressure and temperature conditions that are effective for causing the fluid to change to a supercritical state and carrying out the esterification reaction.

Description

TRAITEMENT HYDROPHOBE DU BOIS  HYDROPHOBIC TREATMENT OF WOOD
La présente invention concerne un procédé notamment utile pour réaliser un traitement hydrophobe d'un matériau de type bois et/ou de ses produits dérivés afin de bloquer sa reprise en eau et ainsi améliorer sa durabilité. The present invention relates to a method particularly useful for carrying out a hydrophobic treatment of a wood-type material and / or its by-products in order to block its recovery in water and thus improve its durability.
Utilisé comme matériau pour le bâtiment ou bien le chauffage, le bois est extrêmement présent dans notre société. Dans le domaine du BTP, le bois est utilisé pour l'intérieur (parquet, décoration, etc) ou l'extérieur (portes, bardages, etc). De plus, il y a de nombreuses raisons de choisir le bois comme matériau de construction : apparence, isolation thermique, coût, « environmentally friendly ». Comme d'autres matériaux (béton, briques, polymères, plastiques, etc), le bois pour le bâtiment est sujet aux conditions météorologies drastiques (pluie, vent, exposition UV, etc) et aux attaques fongiques (moisissures). Used as a material for building or heating, wood is extremely present in our society. In the field of construction, the wood is used for the interior (parquet, decoration, etc.) or outside (doors, cladding, etc.). In addition, there are many reasons to choose wood as a building material: appearance, thermal insulation, cost, environmentally friendly. Like other materials (concrete, bricks, polymers, plastics, etc.), wood for building is subject to drastic weather conditions (rain, wind, UV exposure, etc.) and fungal attacks (molds).
Or, le bois est un matériau hygroscopique. En conséquence, les dimensions et la composition d'un substrat en bois sont susceptibles d'évoluer en fonction de sa teneur en humidité. Pour des raisons évidentes, ce type de transformation est indésirable dans la mesure où ces modifications tendent à altérer l'intégrité du matériau et donc sa durée de vie ou encore sa durabilité. Par ailleurs, ce phénomène d'hygroscopie est plus particulièrement prononcé avec des bois comme les pins, sapins et de manière plus générale les épicéas, qui sont des bois largement utilisés compte-tenu de leurs coûts modérés. En effet des « essences » de bois ou « espèces » de bois ou encore « variétés » de bois comme le Douglas, qui sont des bois onéreux, présentent des sensibilités moindres à l'humidité (classe d'emploi 4).  Wood is a hygroscopic material. As a result, the dimensions and composition of a wood substrate are likely to change depending on its moisture content. For obvious reasons, this type of transformation is undesirable insofar as these modifications tend to alter the integrity of the material and therefore its life or its durability. Moreover, this phenomenon of hygroscopy is more pronounced with woods such as pines, fir trees and more generally spruces, which are widely used woods given their moderate costs. In fact, "species" of wood or "species" of wood or even "varieties" of wood such as Douglas fir, which are expensive woods, have lower sensitivities to humidity (use class 4).
II est donc important d'améliorer les performances en termes de durabilité des bois de coût modéré, en utilisation extérieure.  It is therefore important to improve the durability performance of medium-cost woods in outdoor use.
L'estérifïcation des fonctions hydroxyles du bois, est la méthode conventionnellement considérée pour rendre le bois hydrophobe et améliorer ainsi considérablement sa durabilité et donc sa stabilité chimique ou dimensionnelle.  The esterification of the hydroxyl functions of wood, is the method conventionally considered to make the wood hydrophobic and thus considerably improve its durability and thus its chemical or dimensional stability.
Plusieurs modes d'estérifïcation et en particulier d'acétylation sont déjà proposés. Ainsi, Pacétylation des fonctions hydroxyles du bois a déjà été décrite par de l'anhydride acétique (WO 2005/077626). Cependant, ce composé chimique d'acétylation présente un certain nombre de désavantages, tels que son caractère corrosif fort, et le fait qu'il soit hautement inflammable et toxique. Several modes of esterification and in particular of acetylation are already proposed. Thus, acetylation of the hydroxyl functions of wood has already been described by acetic anhydride (WO 2005/077626). However, this chemical acetylation compound has a number of disadvantages, such as its strong corrosive nature, and the fact that it is highly flammable and toxic.
L'utilisation d'huiles végétales naturelles siccatives pour le traitement d'un bois a également été décrite dans le document WO 2014/002008. Cependant celle-ci y est limitée à un traitement de surface, à l'air libre, de ce type de matériau. Une réaction de polymérisation est en outre à réaliser consécutivement au dépôt. Ce procédé a donc notamment pour inconvénient de ne pas être efficace en profondeur du bois.  The use of natural drying vegetable oils for the treatment of a wood has also been described in WO 2014/002008. However, it is limited to a surface treatment, in the open air, of this type of material. A polymerization reaction is also to be performed subsequent to the deposition. This method has the particular disadvantage of not being effective in depth of the wood.
Par ailleurs, des fluides en conditions supercritiques ont été utilisés comme vecteurs préférentiels de composés antifongiques et antimicrobiens pour imprégner le bois, ainsi que pour l'extraction de substances indésirables.  In addition, fluids under supercritical conditions have been used as preferential vectors of antifungal and antimicrobial compounds for impregnating the wood, as well as for the extraction of undesirable substances.
Ainsi, pour un traitement en profondeur du bois, il a été proposé de mettre à profit un véhicule de type dioxyde de carbone (C02) en conditions supercritiques pour véhiculer un certain nombre de composés dans du bois. En particulier, le document J. Mater. Sci., 2011, 46, 5406-5411 met à profit cette technologie pour l'introduction de sels de calcium (CaCb) et de sodium (NaCl), les documents Wood Sci. Technol, 2012, 46, 643-656, WO 00/27601 et WO 03/095165, pour l'imprégnation de composés antifongiques, le document DE 4202320 Al pour l'imprégnation d'une huile de silicone et le document WO 2011/066830 pour une diffusion de copolymères blocs comportant une partie grasse saturée ainsi qu'une fonction acide carboxylique avec réalisation consécutive d'une acétylation catalytique des fonctions hydroxyles natives du bois par ces dits polymères. Enfin, les documents J. Wood Sci., 2010, 56, 293-298 et JP 4686775 B2 2011. 5. 25 décrivent, dans des conditions supercritiques, Pacétylation à l'aide d'anhydride acétique d'un bois ayant subi au préalable un traitement d'extraction éthanoPbenzène ainsi qu'un « bouillage ». Ce procédé implique une mise en œuvre complexe avec ce prétraitement préalable du bois. Thus, for an in-depth treatment of wood, it has been proposed to use a carbon dioxide (C0 2 ) type vehicle under supercritical conditions to convey a certain number of compounds in wood. In particular, the document J. Mater. Sci., 2011, 46, 5406-5411 uses this technology for the introduction of calcium (CaCb) and sodium (NaCl) salts, Wood Sci documents. Technol, 2012, 46, 643-656, WO 00/27601 and WO 03/095165, for the impregnation of antifungal compounds, DE 4202320 A1 for the impregnation of a silicone oil and WO 2011/066830 for a diffusion of block copolymers comprising a saturated fatty part as well as a carboxylic acid function with subsequent realization of a catalytic acetylation of the native hydroxyl functions of the wood by said polymers. Finally, the documents J. Wood Sci., 2010, 56, 293-298 and JP 4686775 B2 2011. 5. 25 describe, under supercritical conditions, acetylation using acetic anhydride of a wood that has previously undergone ethanoPbenzene extraction treatment as well as "boiling". This process involves a complex implementation with this pretreatment of the wood.
En conséquence, et à la connaissance des inventeurs, il n'existe pas à ce jour de procédé de traitement hydrophobe du bois qui soit simple de mise en œuvre, c'est à dire ne requérant pas la mise en œuvre d'étape de prétraitement obligatoire et qui repose par ailleurs sur l'emploi de produits non corrosifs, d'origine naturelle. La présente invention a précisément pour objectif de répondre à ce besoin. Consequently, and to the knowledge of the inventors, there is currently no hydrophobic wood treatment process that is simple to implement, that is to say not requiring the implementation of pretreatment step mandatory and based on the use of non-corrosive products of natural origin. The present invention precisely aims to meet this need.
Ainsi, l'invention concerne, selon l'un de ses aspects, un procédé d'estérifïcation de tout ou partie des fonctions hydroxyles d'un matériau de type bois et/ou de l'un de ses produits dérivés caractérisé ce en qu'il met en contact ledit matériau avec un fluide à un état supercritique véhiculant au moins une huile végétale naturelle insaturée de préférence siccative, dans des conditions propices à la réalisation de ladite estérifïcation, comprenant au moins les étapes consistant à : Thus, according to one of its aspects, the invention relates to a process for esterification of all or part of the hydroxyl functions of a wood-type material and / or of one of its derived products, characterized in that it brings said material into contact with a fluid in a supercritical state carrying at least one natural unsaturated vegetable oil, preferably drying, under conditions conducive to carrying out said esterification, comprising at least the steps of:
i) disposer, au sein d'une enceinte, d'un matériau de type bois, possédant de préférence une teneur en eau inférieure à 20% en poids par rapport à son poids total, et d'au moins une huile végétale naturelle insaturée véhiculée, de préférence solubilisée, dans un fluide liquide apte à évoluer sous pression à un état supercritique.  i) have, within a chamber, a wood-type material, preferably having a water content of less than 20% by weight relative to its total weight, and at least one unsaturated natural vegetable oil conveyed , preferably solubilized, in a liquid fluid capable of evolving under pressure in a supercritical state.
ii) imposer à l'ensemble des conditions de pression efficaces à l'imprégnation dudit matériau par ladite huile et  ii) impose on all the pressure conditions effective to impregnation of said material with said oil and
iii) exposer ledit matériau imprégné par ladite huile obtenu en étape ii) à des conditions de pression et températures efficaces pour faire évoluer ledit fluide à un état supercritique et réaliser ladite réaction d'estérifïcation.  iii) exposing said impregnated material with said oil obtained in step ii) under conditions of pressure and temperatures effective to make said fluid evolve to a supercritical state and carry out said esterification reaction.
Plus précisément, le procédé selon l'invention comprend une étape de diffusion de ladite huile, véhiculée par ledit fluide supercritique, au sein dudit matériau, et donc en profondeur dudit matériau, préliminairement à ladite estérifïcation.  More specifically, the method according to the invention comprises a step of diffusion of said oil, conveyed by said supercritical fluid, within said material, and therefore in depth of said material, prior to said esterification.
A ce titre, le procédé selon l'invention permet d'accéder à un traitement hydrophobe en profondeur du bois traité, contrairement aux procédés dépourvus d'une telle étape comme ceux décrits dans CN 104 985 653 A et WO 2013/070196 A2.  In this respect, the process according to the invention makes it possible to access a hydrophobic treatment at depth of the treated wood, unlike processes without such a stage as those described in CN 104 985 653 A and WO 2013/070196 A2.
Selon une variante préférée, cette étape préliminaire est réalisée à une pression comprise entre 15,0 et 25,0 MPa, de préférence d'environ 20,0 MPa, à température ambiante et durant un délai suffisant pour promouvoir une imprégnation efficace du matériau par ladite huile.  According to a preferred variant, this preliminary step is carried out at a pressure of between 15.0 and 25.0 MPa, preferably around 20.0 MPa, at room temperature and for a time sufficient to promote an effective impregnation of the material by said oil.
Selon une variante préférée, l'étape ii) requiert une mise sous pression de l'enceinte à une pression d'au moins 15,0 MPa voire d'au moins 20,0 MPa.  According to a preferred variant, step ii) requires pressurizing the chamber to a pressure of at least 15.0 MPa or even at least 20.0 MPa.
L'étape iii) comprend la diffusion de ladite huile véhiculée par le fluide à l'état supercritique au sein dudit matériau et son interaction, par estérifïcation, avec les fonctions hydroxyles libres dudit matériau. Elle est avantageusement réalisée à une pression supérieure à celle considérée en étape ii) de préférence à environ 30,0 MPa, et sous chauffage, de préférence, à une température variant de 100°C à 150°C et de préférence d'environ 130°C et durant un délai suffisant pour la réalisation de ladite estérifïcation. Step iii) comprises the diffusion of said oil carried by the fluid in the supercritical state within said material and its interaction, by esterification, with the free hydroxyl functions of said material. It is advantageously carried out at a pressure greater than that considered in step ii) preferably to about 30.0 MPa, and under heating, preferably at a temperature ranging from 100 ° C to 150 ° C and preferably about 130 ° C and for a sufficient time for carrying out said esterification.
L'invention concerne également l'utilisation d'un procédé tel que défini ci- dessus, pour le traitement hydrophobe d'un matériau poreux de type bois et/ou de ses produits dérivés et notamment à des fins d'en accroître sa durabilité. The invention also relates to the use of a method as defined above, for the hydrophobic treatment of a wood-type porous material and / or its derived products and in particular for the purpose of increasing its durability.
MATERIAU DE TYPE BOIS MATERIAL OF WOOD TYPE
Dans la description qui suit, le terme « bois » sera utilisé de manière générique pour désigner tous les matériaux poreux contenant des fonctions hydroxyles libres au sein de leurs structures et formés en tout ou partie de bois, c'est-à-dire du bois en tant que tel, mais également les produits dérivés du bois. In the description which follows, the term "wood" will be used generically to designate all the porous materials containing free hydroxyl functions within their structures and formed in whole or in part of wood, that is to say wood as such, but also products derived from wood.
Au sens de l'invention, sont notamment couverts sous la qualification « produits dérivés du bois » les matériaux comme par exemple des particules de bois et de produits composites comme par exemple, des panneaux agglomérés.  For the purposes of the invention, the term "wood-based products" is used to cover materials such as, for example, wood particles and composite products, for example agglomerated panels.
Le procédé selon l'invention convient tout particulièrement au traitement d'un type de bois choisi parmi les bois durs tel que le hêtre et les bois résineux tel que le cèdre rouge et ceux de la famille des pinacées tels que le sapin, le pin et l'épicéa.  The method according to the invention is particularly suitable for the treatment of a type of wood chosen from hardwoods such as beech and softwoods such as red cedar and those of the family Pinaceae such as fir, pine and spruce.
Avantageusement, le procédé selon l'invention permet de conférer à des bois de coût plus modiques que les essences d'espèces de bois à la croissance plus lente, des propriétés comparables en termes de durabilité environnementale et notamment des propriétés de résistance aux intempéries comparables.  Advantageously, the process according to the invention makes it possible to confer on woods with a lower cost than the species of wood species with slower growth, comparable properties in terms of environmental sustainability and in particular comparable weather resistance properties.
HUILE VEGETALE INSATUREE UNSATURATED VEGETABLE OIL
Comme précisé ci-dessus, le procédé de traitement du bois selon l'invention met en œuvre au moins une huile végétale naturelle insaturée. As stated above, the wood treatment method according to the invention implements at least one unsaturated natural vegetable oil.
Les huiles végétales sont souvent divisées en trois catégories, suivant leur qualité, et ces catégories sont non siccatives, semi- siccatives et siccatives. Par opposition aux huiles non siccatives, les huiles siccatives ont pour intérêt de s'oxyder rapidement et de devenir alors solides. Elles forment donc un film protecteur plus résistant. Vegetable oils are often divided into three categories, depending on their quality, and these categories are non-drying, semi-drying and drying. In contrast to non-drying oils, drying oils have the advantage of rapidly oxidizing and then becoming solid. They thus form a more resistant protective film.
Dans la description qui suit le terme « huile » sera utilisé pour désigner indifféremment une unique huile ou un mélange d'huiles.  In the following description the term "oil" will be used to denote either a single oil or a mixture of oils.
L'huile considérée selon l'invention comporte des insaturations, de préférence au moins deux insaturations, et plus préférentiellement au moins trois insaturations.  The oil considered according to the invention comprises unsaturations, preferably at least two unsaturations, and more preferably at least three unsaturations.
L'huile convenant à la mise en œuvre de la présente invention contient des fonctions acides carboxyliques capables de réagir avec des fonctions hydroxyles communément présentes dans des bois. Avantageusement, ces fonctions s'avèrent en revanche inertes à l'égard des fluides supercritiques notamment de type dioxyde de carbone.  The oil suitable for the implementation of the present invention contains carboxylic acid functions capable of reacting with hydroxyl functions commonly present in woods. Advantageously, these functions are in contrast inert with respect to supercritical fluids including carbon dioxide type.
Elle est ainsi composée plus particulièrement de triglycérides.  It is thus composed more particularly of triglycerides.
L'huile convenant à la mise en œuvre de la présente invention peut être notamment une huile modifiée par réaction chimique. En particulier, elle peut être raffinée et/ou partiellement polymérisée. A ce titre, on peut citer les huiles soufflées et les standolies, les huiles maléinisées, époxydées ou cuites.  The oil suitable for the implementation of the present invention may be in particular a modified oil by chemical reaction. In particular, it can be refined and / or partially polymerized. As such, there may be mentioned blown oils and standolies, maleinized oils, epoxidized or cooked.
L'huile considérée selon l'invention peut contenir également des additifs et notamment, du sel de cobalt, du sel de zirconium et de l'acide 2-éthylhexanoïque (entre 0,1 et 1 %) qui la rend plus siccative.  The oil considered according to the invention may also contain additives and in particular cobalt salt, zirconium salt and 2-ethylhexanoic acid (between 0.1 and 1%) which makes it more siccative.
Selon une variante préférée, l'huile considérée selon l'invention est une huile végétale insaturée siccative. According to a preferred variant, the oil considered according to the invention is a drying unsaturated vegetable oil.
L'huile siccative de l'invention peut être avantageusement choisie parmi l'huile d'œillette, l'huile de lin, l'huile de grenade, l'huile de ricin, l'huile de noix, l'huile de graine de coton, leurs produits dérivés et notamment leurs esters.  The drying oil of the invention may be advantageously chosen from among the follicle oil, linseed oil, pomegranate oil, castor oil, walnut oil, cotton, their derivatives and in particular their esters.
De préférence, l'huile végétale insaturée siccative selon l'invention est de l'huile de lin cuite ou crue et de préférence crue.  Preferably, the drying unsaturated vegetable oil according to the invention is linseed oil or raw and preferably raw.
De telles huiles siccatives sont disponibles commercialement. A titre d'exemple, on peut citer l'huile de lin commercialisée par la société RECOCHEM Inc.  Such drying oils are commercially available. By way of example, mention may be made of flaxseed oil marketed by RECOCHEM Inc.
L'huile considérée selon l'invention est mise en œuvre en quantité suffisante pour obtenir le traitement hydrophobe attendu. L'ajustement de cette quantité relève clairement des compétences de l'homme du métier. La mise en œuvre d'un excès d'huile est envisageable. Il est alors possible de considérer parallèlement son recyclage. The oil considered according to the invention is used in sufficient quantity to obtain the expected hydrophobic treatment. The adjustment of this quantity falls clearly the skills of the skilled person. The implementation of an excess of oil is possible. It is then possible to consider in parallel its recycling.
Classiquement, l'huile (ou encore mélange d'huiles) considérée selon l'invention est mis en œuvre à une quantité pondérale équivalente au poids du matériau à traiter.  Conventionally, the oil (or mixture of oils) considered according to the invention is implemented at a weight equivalent to the weight of the material to be treated.
Selon un mode de réalisation particulier de l'invention, elle est mise en présence du matériau à traiter préliminairement à la mise en œuvre du fluide supercritique à l'état liquide. FLUIDE SUPERCRITIQUE  According to a particular embodiment of the invention, it is brought into contact with the material to be treated in advance of the implementation of the supercritical fluid in the liquid state. SUPERCRITICAL FLUID
Comme énoncé précédemment, le fluide à l'état supercritique selon l'invention est inerte vis-à-vis de l'huile végétale avec laquelle il est mis en œuvre. As stated above, the fluid in the supercritical state according to the invention is inert with respect to the vegetable oil with which it is used.
Au sein de l'invention, un fluide supercritique est un fluide possédant une température critique, en deçà de laquelle il est à l'état liquide et un fluide à l'état supercritique est un fluide qui a été exposé, généralement sous pression, à une température supérieure à sa température critique.  Within the invention, a supercritical fluid is a fluid having a critical temperature, below which it is in the liquid state and a fluid in the supercritical state is a fluid which has been exposed, generally under pressure, to a temperature above its critical temperature.
Le fluide supercritique convenant à la présente invention peut être tout fluide approprié tel que, mais sans s'y limiter : le dioxyde de carbone, le protoxyde d'azote (N20). The supercritical fluid suitable for the present invention may be any suitable fluid such as, but not limited to, carbon dioxide, nitrous oxide (N 2 0).
Il s'agit de préférence du dioxyde de carbone.  It is preferably carbon dioxide.
Le dioxyde de carbone est un solvant que l'on considère comme « vert ». Le dioxyde de carbone a une température critique relativement basse (31,1°C). Il est pratiquement non-toxique, ininflammable, relativement inerte et ne présente que peu d'impact sur l'environnement par rapport aux autres solvants supercritiques cités ci-dessus. Carbon dioxide is a solvent that is considered "green". Carbon dioxide has a relatively low critical temperature (31.1 ° C). It is virtually non-toxic, non-flammable, relatively inert and has little impact on the environment compared to the other supercritical solvents listed above.
En outre, le dioxyde de carbone est relativement peu coûteux. In addition, carbon dioxide is relatively inexpensive.
Plus précisément, le fluide à l'état liquide, et en particulier le CO2 dissout les composés lipophiles que sont les huiles naturelles végétales insaturées et donc est efficace pour les véhiculer efficacement.  More precisely, the fluid in the liquid state, and in particular the CO2, dissolves the lipophilic compounds that are unsaturated vegetable natural oils and is therefore effective for efficiently conveying them.
Après imprégnation, le fluide chargé en huile et ayant évolué à l'état supercritique diffuse efficacement au sein du matériau et garantie ainsi une estérifîcation efficace et uniforme de ce dernier. Pour des raisons évidentes, les conditions de pression conditionnant le passage de l'état fluide à l'état supercritique sont variables selon le fluide considéré et leur ajustement relève clairement des compétences de l'homme du métier. After impregnation, the fluid loaded with oil and having evolved in the supercritical state diffuses efficiently within the material and thus guarantees efficient and uniform esterification of the latter. For obvious reasons, the pressure conditions conditioning the transition from the fluid state to the supercritical state are variable depending on the fluid in question and their adjustment is clearly within the skill of the skilled person.
Dans le cas du CO2, cette conversion est réalisée à partir de 31°C et sous une pression de l'ordre de 20,0 MPa.  In the case of CO2, this conversion is carried out from 31 ° C. and under a pressure of the order of 20.0 MPa.
Selon un mode préféré de l'invention, le fluide supercritique est le dioxyde de carbone et l'huile végétale naturelle insaturée est une huile siccative et de préférence une huile de lin.  According to a preferred embodiment of the invention, the supercritical fluid is carbon dioxide and unsaturated natural vegetable oil is a drying oil and preferably a linseed oil.
Avantageusement, le procédé selon l'invention ne requiert pas la présence obligatoire d'un catalyseur pour la réalisation d'estérification.  Advantageously, the process according to the invention does not require the obligatory presence of a catalyst for carrying out esterification.
En conséquence, selon une variante de réalisation avantageuse, le procédé est mis en œuvre en absence d'un catalyseur d'estérification.  Accordingly, according to an advantageous variant embodiment, the process is carried out in the absence of an esterification catalyst.
Bien entendu, il est néanmoins possible de considérer la présence d'un tel catalyseur. La présence de ce dernier a pour avantage d'accélérer l'interaction entre les groupements hydroxyles libres cellulosiques et les fonctions carboxyliques des acides gras de l'huile et donc de contribuer à une rétention plus rapide de ces derniers dans le bois. De tels catalyseurs peuvent notamment être H2SO4 ou la pyridine.  Of course, it is nevertheless possible to consider the presence of such a catalyst. The presence of the latter has the advantage of accelerating the interaction between the free cellulosic hydroxyl groups and the carboxylic functions of the fatty acids of the oil and thus contributing to a faster retention of the latter in the wood. Such catalysts may especially be H 2 SO 4 or pyridine.
DESCRIPTION DETAILLEE DU PROCEDE DETAILED DESCRIPTION OF THE PROCESS
Comme énoncé précédemment, le procédé selon l'invention comprend au moins les étapes consistant à : As stated above, the method according to the invention comprises at least the steps of:
i) disposer, au sein d'une enceinte, d'un matériau de type bois et possédant de préférence une teneur en eau inférieure à 20% en poids par rapport à son poids total et d'au moins une huile végétale naturelle insaturée véhiculée, de préférence solubilisée, dans un fluide liquide apte à évoluer sous pression à un état supercritique  i) have, in a chamber, a wood-type material and preferably having a water content of less than 20% by weight relative to its total weight and at least one unsaturated natural vegetable oil conveyed, preferably solubilized, in a liquid fluid capable of evolving under pressure to a supercritical state
- ii) imposer à l'ensemble des conditions de pression efficaces à l'imprégnation dudit matériau par ladite huile et  ii) impose on all the pressure conditions that are effective at impregnation of said material with said oil and
- iii) exposer ledit matériau imprégné par ladite huile obtenu en étape ii) à des conditions de pression et températures efficaces pour faire évoluer ledit fluide à un état supercritique et réaliser ladite réaction d'estérification. Selon un mode de réalisation préféré, la réaction d'estérification est réalisée dans des conditions anhydres. En effet, en l'absence d'eau, le rendement de l'estérifïcation est considérablement accru. iii) exposing said material impregnated with said oil obtained in stage ii) to conditions of pressure and temperatures that are effective for changing said fluid to a supercritical state and carrying out said esterification reaction. According to a preferred embodiment, the esterification reaction is carried out under anhydrous conditions. Indeed, in the absence of water, the yield of the esterification is considerably increased.
Pour ce faire, le substrat de type bois, subit avantageusement et préalablement à sa mise en contact avec le fluide supercritique véhiculant l'huile, une opération de séchage de manière à réduire signifîcativement sa teneur en eau qui pourrait interférer sur le bon déroulement de la réaction chimique d'estérification.  To do this, the wood-type substrate advantageously undergoes, prior to being brought into contact with the supercritical fluid carrying the oil, a drying operation so as to significantly reduce its water content which could interfere with the smooth running of the chemical esterification reaction.
L'élimination de l'eau peut notamment être sanctionnée par pesage du substrat avant et après séchage.  The elimination of water may in particular be sanctioned by weighing the substrate before and after drying.
D'une manière générale, cette étape de séchage est réalisée dans des conditions propices à la réduction d'environ 10% du poids initial du substrat de type bois, ce qui correspond à une élimination d'eau.  In general, this drying step is performed under conditions conducive to the reduction of about 10% of the initial weight of the wood-type substrate, which corresponds to a removal of water.
La réalisation de cette étape de séchage relève clairement des compétences de l'homme de l'art. Elle est bien entendu réalisée dans des conditions ajustées pour ne pas altérer l'intégrité du substrat de type bois considéré.  The achievement of this drying step is clearly within the skill of those skilled in the art. It is of course carried out under conditions adjusted to not alter the integrity of the wood-type substrate considered.
Ainsi, le matériau considéré en étape i) est avantageusement un matériau ayant subi au préalable une étape de séchage destinée à éliminer de 8% à 10%> en poids d'eau par rapport à son poids total, de préférence de 9,4% à 9,5% en poids d'eau par rapport à son poids total. Un tel séchage peut notamment être réalisé par chauffage du matériau à une température de 100 °C à l'étuve.  Thus, the material considered in stage i) is advantageously a material having previously undergone a drying step intended to remove from 8% to 10% by weight of water relative to its total weight, preferably 9.4%. to 9.5% by weight of water relative to its total weight. Such drying can in particular be carried out by heating the material at a temperature of 100 ° C. in an oven.
Le matériau est ensuite imprégné par ladite huile véhiculée par ledit fluide à l'état liquide. The material is then impregnated with said oil conveyed by said fluid in the liquid state.
Cette étape ii) ou encore étape d'imprégnation est avantageusement réalisée sous pression de manière à homogénéiser le système et amener l'huile véhiculée par le fluide supercritique liquide, vers et dans les porosités du bois.  This step ii) or impregnation step is advantageously carried out under pressure so as to homogenize the system and bring the oil conveyed by the liquid supercritical fluid to and into the porosities of the wood.
Selon une variante préférée, l'étape ii) est réalisée à une pression comprise entre 15,0 et 25,0 MPa, de préférence d'environ 20,0 MPa, à température ambiante donc pas supercritique et durant un délai suffisant pour promouvoir l'imprégnation de la totalité du matériau par ladite huile.  According to a preferred variant, step ii) is carried out at a pressure of between 15.0 and 25.0 MPa, preferably about 20.0 MPa, at room temperature and therefore not supercritical and for a time sufficient to promote the reaction. impregnation of the entire material with said oil.
Au sens de l'invention, une température ambiante est de l'ordre de 20 °C à plus ou moins 5 °C, et de préférence inférieure à 30 °C. Dans le cas du C02, le réacteur contenant le substrat à traiter peut avantageusement être pressurisé à température ambiante et sous une atmosphère de CO2, dont la pression est égale ou inférieure à 20,0 MPa. Within the meaning of the invention, an ambient temperature is of the order of 20 ° C to plus or minus 5 ° C, and preferably less than 30 ° C. In the case of CO 2 , the reactor containing the substrate to be treated can advantageously be pressurized at ambient temperature and under a CO 2 atmosphere, the pressure of which is equal to or less than 20.0 MPa.
Bien entendu, il est également possible d'ajuster ces paramètres de pression et le cas échéant de températures pour moduler l'amplitude de l'imprégnation du matériau en huile(s) et sa vitesse de réalisation.  Of course, it is also possible to adjust these pressure parameters and optionally temperature to modulate the amplitude of the impregnation of the oil material (s) and its speed of realization.
A partir du moment où l'huile est imprégnée dans le matériau, Pestérifïcation, consistant en la fonctionnalisation au moins en partie des fonctions hydroxyles libres de la cellulose constitutive du substrat à traiter, avec des fonctions carboxyliques des acides gras constitutifs de l'huile, peut alors intervenir. From the moment the oil is impregnated into the material, the esterification, consisting in the functionalization at least in part of the free hydroxyl functions of the constituent cellulose of the substrate to be treated, with carboxylic functions of the fatty acids constituting the oil, can then intervene.
L'étape iii) relative à cette estérification est réalisée à une pression supérieure à celle considérée en étape ii) et dans le cas du CO2 à une pression, de l'ordre de 30,0 MPa. et sous chauffage de préférence, à une température variant de 100°C à 150°C et de préférence d'environ 130°C.  Step iii) relating to this esterification is carried out at a pressure greater than that considered in step ii) and in the case of CO2 at a pressure, of the order of 30.0 MPa. and under heating preferably, at a temperature ranging from 100 ° C to 150 ° C and preferably about 130 ° C.
En particulier, la température au sein de l'enceinte est ajustée pour générer la forme supercritique du fluide considéré, par exemple à une valeur supérieure à 31°C pour le CO2, et promouvoir la réaction d'estérification.  In particular, the temperature within the chamber is adjusted to generate the supercritical form of the fluid in question, for example at a value greater than 31 ° C. for CO2, and to promote the esterification reaction.
De préférence, cette température est supérieure à 70°C et est de préférence de l'ordre de 130°C.  Preferably, this temperature is greater than 70 ° C and is preferably of the order of 130 ° C.
Bien entendu, il est également possible d'ajuster ces paramètres de pression et de températures pour moduler l'amplitude de la réaction d'estérification et sa vitesse. Ces ajustements relèvent clairement des compétences de l'homme de l'art.  Of course, it is also possible to adjust these pressure and temperature parameters to modulate the amplitude of the esterification reaction and its speed. These adjustments are clearly within the skill of those skilled in the art.
D'une manière générale, Γ estérification peut être réalisée entre 0,5 et 24 heures.  In general, the esterification can be carried out between 0.5 and 24 hours.
Avantageusement, elle peut être considérée comme accomplie au terme de 6 heures dans les conditions précitées avec du CO2 supercritique.  Advantageously, it can be considered as completed after 6 hours under the above conditions with supercritical CO2.
Le suivi de la réaction peut être effectué par une analyse de spectrométrie infra-rouge du matériau traité, en caractérisant sur le spectre correspondant la présence d'un pic caractéristique d'une liaison C=0 d'une fonction ester à 1745 cm"1. Un exemple d'un tel spectre est présenté en figure 1. L'uniformité de la réaction d'estérifîcation réalisée selon l'invention peut être quant à elle contrôlée par une mesure d'angle de mouillage. Des résultats de ce type pour un échantillon de cèdre rouge traité par de l'huile de lin sont représentés dans le tableau 1 ci-après. Il peut ainsi être observé que les valeurs d'angle Theta(M) sont accrues pour un échantillon traité comparativement au même échantillon de bois avant traitement. The reaction can be monitored by infra-red spectrometry analysis of the treated material, characterizing on the corresponding spectrum the presence of a characteristic peak of a C = O bond of an ester function at 1745 cm -1. An example of such a spectrum is shown in Figure 1. The uniformity of the esterification reaction carried out according to the invention can be in turn controlled by a measurement of wetting angle. Results of this type for a sample of red cedar treated with linseed oil are shown in Table 1 below. It can thus be observed that Theta (M) angle values are increased for a treated sample compared to the same wood sample before treatment.
Le procédé peut être avantageusement réalisé au sein d'un dispositif pouvant être clos, mis sous forte pression et chauffé. Il peut notamment être composé d'une alimentation en fluide supercritique à l'état liquide par exemple en C02 liquide, d'une enceinte de réaction, d'une pompe de mise sous pression de ce fluide et d'un dispositif de chauffage. The process can advantageously be carried out within a device that can be closed, put under high pressure and heated. It may in particular be composed of a supercritical fluid supply in the liquid state, for example liquid C0 2 , a reaction chamber, a pump for pressurizing this fluid and a heating device.
Selon une variante de réalisation avantageuse, le procédé selon l'invention met en œuvre de l'huile de lin et du CO2 supercritique. En fin de réaction d'estérifîcation le poids du matériau traité selon l'invention est augmenté de 0,1% à 10%, de préférence de 0,3%> à 5% comparativement à son poids d'origine. Autrement dit, de 0,1 % à 10%>, de préférence de 0,3%> à 5% de son poids en huile a été estérifié au sein de sa structure. Comme énoncé précédemment, le procédé selon l'invention s'avère tout particulièrement intéressant pour réaliser un traitement hydrophobe d'un matériau de type bois et/ou de ses produits dérivés.  According to an advantageous embodiment variant, the process according to the invention uses linseed oil and supercritical CO2. At the end of the esterification reaction, the weight of the material treated according to the invention is increased from 0.1% to 10%, preferably from 0.3% to 5%, relative to its original weight. In other words, from 0.1% to 10%, preferably from 0.3% to 5%, of its weight in oil has been esterified within its structure. As stated above, the method according to the invention is particularly interesting for performing a hydrophobic treatment of a wood-type material and / or its derivatives.
Il s'avère également efficace pour bloquer la reprise en eau d'un matériau de type bois et/ou de ses produits dérivés.  It is also effective in blocking the water uptake of a wood-type material and / or its by-products.
II est également avantageux pour accroître la durabilité temporelle, la stabilité chimique et/ou la stabilité dimensionnelle d'un matériau de type bois et/ou de ses produits dérivés.  It is also advantageous for increasing the temporal durability, chemical stability and / or dimensional stability of a wood-type material and / or its by-products.
Dans la suite du texte, les expressions « compris entre ... et ... », « allant de ... à ... » et « variant de ... à ... » sont équivalentes et entendent signifier que les bornes sont incluses, sauf mention contraire. Sauf indication contraire, l'expression « comportant/comprenant un(e) » doit être comprise comme « comportant/comprenant au moins un(e) ». In the remainder of the text, the expressions "between ... and ...", "ranging from ... to ..." and "varying from ... to ..." are equivalent and mean to mean that terminals are included unless otherwise stated. Unless otherwise indicated, the expression "comprising / including a" shall be understood as "comprising / including at least one".
D'autres avantages et caractéristiques de l'invention ressortiront mieux à la lecture de la description détaillée d'exemples de mise en œuvre de l'invention soumis à titre illustratif et non limitatif de l'invention et par référence aux figures suivantes :  Other advantages and characteristics of the invention will emerge more clearly on reading the detailed description of exemplary embodiments of the invention which are presented as non-limiting illustrations of the invention and with reference to the following figures:
Figure 1 : Spectre infrarouge d'un échantillon de cèdre rouge 740N avant traitement et après traitement 740. Figure 1: Infrared spectrum of a 740N red cedar sample before treatment and after treatment 740.
Figure 2 : Spectre infrarouge d'un échantillon de sapin 74 IN avant traitement et après traitement 741.  Figure 2: Infrared spectrum of a 74 IN fir sample before treatment and after treatment 741.
Figure 3 : Spectre infrarouge de deux échantillons de bois traités selon l'exemple 4.  Figure 3: Infrared spectrum of two samples of treated wood according to Example 4.
Exemple 1: TRAITEMENT D'UN ECHANTILLON DE CEDRE ROUGE a) Traitement préalable à l'estérification Example 1: TREATMENT OF A SAMPLE OF RED CEDAR a) Pretreatment with esterification
Un échantillon de cèdre rouge (largeur 280 mm, hauteur 200 mm, longueur 910 mm) est séché à 100 °C dans une étuve pendant 24 h pour éliminer les traces d'humidité et les traces d'eau susceptibles de déplacer l'équilibre chimique d'estérifïcation.  A sample of red cedar (width 280 mm, height 200 mm, length 910 mm) is dried at 100 ° C in an oven for 24 hours to remove traces of moisture and traces of water likely to displace the chemical equilibrium of esterification.
La masse initiale de l'échantillon de cèdre rouge avant le traitement selon le procédé est de 12,578 g.  The initial mass of the red cedar sample prior to the process treatment is 12.578 g.
La masse de l'échantillon de cèdre rouge après une étape de séchage de celui-ci est de 11,394 g soit 9,4% en poids d'eau éliminée. b) Traitement d'estérification en conditions dioxyde de carbone supercritique (CO2SC) :  The mass of the red cedar sample after a drying step thereof is 11.394 g or 9.4% by weight of water removed. b) Supercritical Carbon Dioxide Esterification Treatment (CO2SC):
L'échantillon est placé dans un réacteur de 250 mL de volume muni d'organes de sécurités, vannes pointeaux, manomètre, et cordon chauffant.  The sample is placed in a 250 ml volume reactor equipped with safety devices, needle valves, manometer, and heating cord.
La masse d'huile de lin considérée au début du procédé d'estérification est de 11,396 g.  The mass of linseed oil considered at the beginning of the esterification process is 11.396 g.
Elle est également introduite dans le réacteur qui est également alimenté en CO2 à l'état liquide. La pression au sein du réacteur est ajustée à une valeur de 20,0 MPa, à température ambiante, durant 1 heure, afin de promouvoir la diffusion de l'huile dans l'échantillon. It is also introduced into the reactor which is also fed with CO2 in the liquid state. The pressure within the reactor is adjusted to 20.0 MPa at room temperature for 1 hour to promote diffusion of the oil into the sample.
La température du réacteur est ensuite ajustée à 130°C, et la pression à 30,0 MPa, durant 6 heures.  The temperature of the reactor is then adjusted to 130 ° C., and the pressure to 30.0 MPa, for 6 hours.
L'échantillon ainsi estérifîé est ensuite caractérisé. c) Caractérisation de l'échantillon traité selon le procédé de l'invention. i) Sa masse finale est de 13.1160 g, ce qui correspond à un gain en masse de 4%.  The sample thus esterified is then characterized. c) Characterization of the sample treated according to the method of the invention. i) Its final mass is 13.1160 g, which corresponds to a mass gain of 4%.
ii) Une intensité de la coloration après traitement au C02 supercritique en présence d'huile de lin est observée visuellement. La découpe transversale de l'échantillon permet de contrôler cette modification de teinte dans toute l'épaisseur de l'échantillon 740. ii) An intensity of the staining after supercritical CO 2 treatment in the presence of linseed oil is observed visually. The transverse cut of the sample makes it possible to control this change in hue throughout the thickness of the sample 740.
iii) Des mesures d'angles de mouillage ont été réalisées, dans le but de montrer l'uniformité lipophile du matériau traité.  iii) Wetting angle measurements were made in order to show the lipophilic uniformity of the treated material.
L'équipement utilisé est : K USS DSA10 Contact Angle Measuring System. The equipment used is: K USS DSA10 Contact Angle Measuring System.
Le volume des gouttes d'eau est de 1.5 μί. Le tableau 1 ci-après rend compte des résultats obtenus. A titre comparatif, il y est également indiqué les valeurs obtenues avec un échantillon de mêmes spécificités mais non traité selon l'invention (740N). The volume of drops of water is 1.5 μί. Table 1 below shows the results obtained. By way of comparison, the values obtained with a sample of the same specificities but not treated according to the invention (740N) are also indicated.
Tableau 1 Table 1
Le bois de cèdre rouge non-traité (740N) donne les valeurs suivantes d'angles de mouillage à l'eau : 81.2±8.6° et 87.8±4.6°. Untreated red cedar wood (740N) gives the following water wetting angles: 81.2 ± 8.6 ° and 87.8 ± 4.6 °.
En revanche, le bois de cèdre rouge traité selon le procédé de l'invention montre une nette augmentation des mesures d'angle de mouillage indiquant que le bois traité est plus hydrophobe, et présente donc moins d'affinité à l'eau : 109.5±5.4° et 111.0±2.6°. iv) Des analyses par spectrométrie IR ont également été réalisées sur les deux échantillons. La figure 1 rend compte des résultats obtenus. Dans le cas de 740, ce dernier présente un pic caractéristique à 1745 cm"1 typique de la liaison C=0 d'un ester. Ce pic se trouverait vers 1700-1710 cm"1 pour un acide carboxylique. Les ponts hydrogène générés par les acides carboxyliques sont responsables du déplacement de ce signal. En revanche, ce pic n'est pas présent pour l'échantillon non-traité (voir la figure 1). On the other hand, the red cedar wood treated according to the process of the invention shows a clear increase in the measures of wetting angle indicating that the treated wood is more hydrophobic, and therefore has less affinity for water: 109.5 ± 5.4 ° and 111.0 ± 2.6 °. iv) IR spectrometric analyzes were also performed on both samples. Figure 1 shows the results obtained. In the case of 740, the latter has a characteristic peak at 1745 cm -1 typical of the C = O bond of an ester, which peak would be around 1700-1710 cm -1 for a carboxylic acid. The hydrogen bonds generated by the carboxylic acids are responsible for the displacement of this signal. In contrast, this peak is not present for the untreated sample (see Figure 1).
Exemple 2: TRAITEMENT D'UN ECHANTILLON DE SAPIN a) Traitement préalable à l'estérification EXAMPLE 2 TREATMENT OF A FIR SAMPLE a) Pretreatment with esterification
Un échantillon de sapin (largeur 198 mm, hauteur 199 mm, longueur 860 mm) est séché dans les conditions détaillées en exemple 1. La masse initiale de l'échantillon de sapin avant le traitement selon le procédé est de 12,047 g. La masse de l'échantillon de sapin après une étape de séchage de celui-ci est de 10,898 g soit 9,5% en poids d'eau éliminée. b) Traitement d'estérification en conditions dioxyde de carbone supercritique CO2SC :  A fir sample (width 198 mm, height 199 mm, length 860 mm) is dried under the conditions detailed in Example 1. The initial mass of the fir sample before the treatment according to the process is 12.047 g. The mass of the fir sample after a drying step thereof is 10.898 g or 9.5% by weight of water removed. b) Supercritical carbon dioxide esterification treatment CO2SC:
Le protocole est conforme à celui détaillé en exemple 1.  The protocol is consistent with that detailed in Example 1.
La masse d'huile de lin considérée au début du procédé est de 10,898 g. L'échantillon ainsi estérifîé est ensuite caractérisé. c) Caractérisation de l'échantillon traité selon le procédé de l'invention. i) Sa masse finale est de 12.7366 g, ce qui correspond à un gain en masse de The mass of linseed oil considered at the beginning of the process is 10.898 g. The sample thus esterified is then characterized. c) Characterization of the sample treated according to the method of the invention. i) Its final mass is 12.7366 g, which corresponds to a mass gain of
5%. 5%.
ii) Une intensité de la coloration après traitement au CO2 supercritique en présence d'huile de lin est observée visuellement et caractérisée également dans toute l'épaisseur de l'échantillon.  ii) An intensity of the coloration after supercritical CO2 treatment in the presence of linseed oil is observed visually and also characterized throughout the thickness of the sample.
iii) Des analyses par spectrométrie IR ont également été réalisées sur les deux échantillons. La figure 2 rend compte des résultats obtenus. L'estérification est ainsi contrôlée. Exemple 3: TRAITEMENT D'UN ECHANTILLON DE HETRE a) Traitement préalable à l'estérification iii) IR spectroscopic analyzes were also performed on both samples. Figure 2 shows the results obtained. Esterification is thus controlled. EXAMPLE 3 TREATMENT OF A BEECH SAMPLE a) Pretreatment with Esterification
Un échantillon de hêtre (diamètre 197 mm, longueur 840 mm) est séché dans les conditions détaillées en exemple 1.  A sample of beech (diameter 197 mm, length 840 mm) is dried under the conditions detailed in Example 1.
La masse initiale de l'échantillon de hêtre avant le traitement selon le procédé est de 19,961 g puis de 18,207 g, après séchage soit 9,5% en poids d'eau éliminée. b) Traitement d'estérification en conditions dioxyde de carbone supercritique CO2SC :  The initial mass of the beech sample before the treatment according to the process is 19.961 g and then 18.207 g, after drying is 9.5% by weight of water removed. b) Supercritical carbon dioxide esterification treatment CO2SC:
Le protocole est conforme à celui détaillé en exemple 1.  The protocol is consistent with that detailed in Example 1.
La masse d'huile de lin considérée au début du procédé d'estérification est de 18,207 g. L'échantillon ainsi estérifié est ensuite caractérisé. c) Caractérisation de l'échantillon traité selon le procédé de l'invention The mass of linseed oil considered at the beginning of the esterification process is 18.207 g. The thus esterified sample is then characterized. c) Characterization of the sample treated according to the process of the invention
Sa masse finale est de 20.0221 g, ce qui correspond à un gain en masse de 0.3%) et une intensité de la coloration après traitement au CO2 supercritique est visuellement observée en surface et dans l'épaisseur de l'échantillon 742. Its final mass is 20.0221 g, which corresponds to a mass gain of 0.3%) and an intensity of the coloration after supercritical CO2 treatment is visually observed on the surface and in the thickness of the sample 742.
La réaction d'estérification est donc vérifiée.  The esterification reaction is therefore verified.
Exemple 4: TRAITEMENT HORS INVENTION D'UN ECHANTILLON D'EPICEA a) Traitement préalable à l'estérification EXAMPLE 4 TREATMENT OUTSIDE THE INVENTION OF A SAMPLE OF EPICEA a) Pretreatment prior to esterification
Un échantillon d'épicéa (largeur 15 mm, hauteur 25 mm, longueur 50 mm) est séché dans les conditions détaillées en exemple 1.  A sample of spruce (width 15 mm, height 25 mm, length 50 mm) is dried under the conditions detailed in example 1.
La masse initiale de l'échantillon d'épicéa avant le traitement selon le procédé est de 8.110 g. La masse de l'échantillon d'épicéa après une étape de séchage de celui-ci est de 7.258g soit 10.5% en poids d'eau éliminée. b) Traitement d'estérification en conditions dioxyde de carbone supercritique (CO2SC) : The initial mass of the spruce sample before treatment according to the method is 8,110 g. The mass of the sample of spruce after a drying step thereof is 7.258g is 10.5% by weight of water removed. b) Supercritical Carbon Dioxide Esterification Treatment (CO2SC):
Le protocole est conforme à celui détaillé en exemple 1 à la différence que, l'huile de lin est introduite dans le réacteur avec l'échantillon d'épicéa et le fluide liquide et est directement exposée à des conditions de pression et températures efficaces pour faire évoluer le fluide à un état supercritique, telles que décrites dans l'exemple 1.  The protocol is in accordance with that detailed in Example 1 except that the linseed oil is introduced into the reactor with the sample of spruce and the liquid fluid and is directly exposed to pressure conditions and temperatures effective to make evolve the fluid to a supercritical state, as described in Example 1.
L'étape préalable d'imprégnation prévue selon l'invention n'est donc pas reproduite dans le cadre de ce procédé.  The prior impregnation step provided according to the invention is therefore not reproduced in the context of this process.
La masse d'huile de lin considérée au début du procédé d'estérification est de 8.110g. L'échantillon ainsi estérifié est ensuite caractérisé. c) Caractérisation de l'échantillon traité selon un procédé différent de l'invention  The mass of linseed oil considered at the beginning of the esterification process is 8.110 g. The thus esterified sample is then characterized. c) Characterization of the Sample Treated by a Different Method of the Invention
Un premier échantillon est prélevé en surface de l'échantillon de bois et un second est prélevé au centre de celui-ci.  A first sample is taken from the surface of the wood sample and a second sample is taken from the center of the sample.
Des analyses par spectrométrie IR ont été réalisées sur ces deux échantillons (voir la figure 3).  IR spectroscopic analyzes were performed on these two samples (see Figure 3).
Dans le cas de l'échantillon pris en surface, un pic caractéristique à 1745 cm"1 typique de la liaison C=0 d'un ester a été observé. La présence de ce pic permet de conclure que l'estérification a bien eu lieu en surface de l'épicéa. In the case of the sample taken at the surface, a characteristic peak at 1745 cm -1 typical of the C = O bond of an ester was observed The presence of this peak makes it possible to conclude that the esterification has taken place on the surface of the spruce.
En revanche, le pic à 1745 cm"1 n'est pas retrouvé dans le spectre IR de l'échantillon prélevé en profondeur. L'huile de lin n'a donc pas imprégné l'épicéa en profondeur et la réaction d'estérification n'a pu y avoir lieu. On the other hand, the peak at 1745 cm -1 was not found in the IR spectrum of the sample taken at depth, so linseed oil did not impregnate the spruce at depth and the esterification reaction could have taken place.
Ces résultats permettent de mettre en évidence l'importance de l'étape selon l'invention de mise en conditions de pression efficaces à l'imprégnation de l'échantillon par l'huile pour un traitement en profondeur du bois. These results make it possible to demonstrate the importance of the step according to the invention of placing under effective pressure conditions the impregnation of the sample with the oil for a deep treatment of the wood.

Claims

REVENDICATIONS
1. Procédé d'estérifïcation de tout ou partie des fonctions hydroxyles d'un matériau de type bois et/ou de l'un de ses produits dérivés caractérisé en ce qu'il met en contact ledit matériau avec un fluide à un état supercritique véhiculant au moins une huile végétale naturelle insaturée, dans des conditions propices à la réalisation de ladite estérification, comprenant au moins les étapes consistant à : 1. Process for esterification of all or part of the hydroxyl functions of a wood-type material and / or of one of its derived products, characterized in that it brings said material into contact with a fluid in a supercritical state conveying at least one unsaturated natural vegetable oil, under conditions conducive to performing said esterification, comprising at least the steps of:
i) disposer, au sein d'une enceinte, d'un matériau de type bois, possédant de préférence une teneur en eau inférieure à 20% en poids par rapport à son poids total, et d'au moins une huile végétale naturelle insaturée véhiculée, de préférence solubilisée, dans un fluide liquide apte à évoluer sous pression à un état supercritique.  i) have, within a chamber, a wood-type material, preferably having a water content of less than 20% by weight relative to its total weight, and at least one unsaturated natural vegetable oil conveyed , preferably solubilized, in a liquid fluid capable of evolving under pressure in a supercritical state.
ii) imposer à l'ensemble des conditions de pression efficaces à l'imprégnation dudit matériau par ladite huile et  ii) impose on all the pressure conditions effective to impregnation of said material with said oil and
iii) exposer ledit matériau imprégné par ladite huile obtenu en étape ii) à des conditions de pression et températures efficaces pour faire évoluer ledit fluide à un état supercritique et réaliser ladite réaction d'estérifïcation.  iii) exposing said impregnated material with said oil obtained in step ii) under conditions of pressure and temperatures effective to make said fluid evolve to a supercritical state and carry out said esterification reaction.
2. Procédé selon la revendication 1 dans lequel l'étape ii) est réalisée à température ambiante et sous une pression comprise entre 15,0 et 25,0 MPa, de préférence d'environ 20,0 MPa, à température.  The method of claim 1 wherein step ii) is performed at room temperature and at a pressure of between 15.0 and 25.0 MPa, preferably about 20.0 MPa, at temperature.
3. Procédé selon la revendication 1 ou 2 dans lequel l'étape iii) est réalisée à une pression supérieure à celle de l'étape ii) de préférence à environ 30,0 MPa, et sous chauffage de préférence, à une température variant de 100°C à 150°C et de préférence d'environ 130°C.  The process according to claim 1 or 2 wherein step iii) is carried out at a pressure greater than that of step ii) preferably at about 30.0 MPa, and under heating preferably, at a temperature varying from 100 ° C to 150 ° C and preferably about 130 ° C.
4. Procédé selon l'une quelconque des revendications précédentes dans lequel le matériau de type bois choisi parmi les bois durs tel que le hêtre et les bois résineux tel que le cèdre rouge et ceux de la famille des pinacées tels que le sapin, le pin et l'épicéa.  4. Method according to any one of the preceding claims wherein the wood-type material selected from hardwoods such as beech and softwoods such as red cedar and those of the pine family such as fir, pine and spruce.
5. Procédé selon l'une quelconque des revendications précédentes dans lequel l'huile végétale naturelle est une huile végétale insaturée siccative avantageusement choisie parmi l'huile d'œillette, l'huile de lin, l'huile de grenade, l'huile de ricin, l'huile de noix, l'huile de graine de coton, leurs produits dérivés et notamment leurs esters et de préférence une huile de lin cuite ou crue et de préférence crue. 5. Process according to any one of the preceding claims, in which the natural vegetable oil is a drying unsaturated vegetable oil advantageously chosen from carnation oil, linseed oil, pomegranate oil, coconut oil and ricin, walnut oil, cottonseed oil, their by-products and in particular their esters and preferably a cooked or raw flaxseed oil and preferably raw.
6. Procédé selon l'une quelconque des revendications précédentes mettant en œuvre de l'huile de lin et du C02 supercritique. 6. Process according to any one of the preceding claims employing linseed oil and supercritical CO 2 .
7. Procédé selon l'une quelconque des revendications précédentes réalisé dans des conditions anhydres.  7. Process according to any one of the preceding claims, carried out under anhydrous conditions.
8. Procédé selon l'une quelconque des revendications précédentes dans lequel le bois subit au préalable à sa mise en contact avec ladite huile, une étape de séchage.  8. A method according to any one of the preceding claims wherein the wood is previously subjected to its contact with said oil, a drying step.
9. Procédé selon l'une quelconque des revendications dans lequel ladite estérification est réalisée en absence d'un catalyseur d'estérification.  The process according to any one of claims wherein said esterification is carried out in the absence of an esterification catalyst.
10. Utilisation du procédé selon l'une quelconque des revendications précédentes pour un traitement hydrophobe d'un matériau de type bois et/ou de ses produits dérivés.  10. Use of the method according to any one of the preceding claims for a hydrophobic treatment of a wood-type material and / or its derivatives.
11. Utilisation du procédé selon l'une quelconque des revendications 1 à 9 pour bloquer la reprise en eau d'un matériau de type bois et/ou de ses produits dérivés.  11. Use of the method according to any one of claims 1 to 9 for blocking the water uptake of a wood-type material and / or its by-products.
12. Utilisation du procédé selon l'une quelconque des revendications 1 à 9 pour accroître la durabilité temporelle, la stabilité chimique et/ou la stabilité dimensionnelle d'un matériau de type bois et/ou de ses produits dérivés.  12. Use of the method according to any one of claims 1 to 9 for increasing the temporal durability, chemical stability and / or dimensional stability of a wood-type material and / or its products.
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JP4686775B2 (en) 2006-02-15 2011-05-25 独立行政法人森林総合研究所 Method for modifying wood
US9308667B2 (en) 2009-12-03 2016-04-12 Superwood A/S Method for increasing the water resistance of a porous material, compositions therefor and porous materials treated according to the method
FR2973270B1 (en) * 2011-03-28 2013-03-29 A R C Nucleart OLEOTHERMAL TREATMENT FOR DIMENSIONALLY STABILIZING WOOD
US20140193587A1 (en) * 2011-11-08 2014-07-10 Empire Technology Development Llc Methods of treating wood with preservatives using supercritical noble gases
FR2992579A1 (en) 2012-06-27 2014-01-03 Commissariat Energie Atomique PROCESS FOR TREATING WOOD WITH SICCATIVE UNSATURATED VEGETABLE OIL IN COMBINATION WITH CERIUM OXIDE NANOPARTICLES
CN104985653A (en) * 2015-06-24 2015-10-21 南通亚振东方家具有限公司 Method for processing wood through supercritical fluid

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