WO2011096812A1 - Method and apparatus for modifying wood, and wood product - Google Patents

Method and apparatus for modifying wood, and wood product Download PDF

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Publication number
WO2011096812A1
WO2011096812A1 PCT/NL2011/050083 NL2011050083W WO2011096812A1 WO 2011096812 A1 WO2011096812 A1 WO 2011096812A1 NL 2011050083 W NL2011050083 W NL 2011050083W WO 2011096812 A1 WO2011096812 A1 WO 2011096812A1
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WO
WIPO (PCT)
Prior art keywords
wood
hydroxymethyl
alkyl
isocyanate
furan
Prior art date
Application number
PCT/NL2011/050083
Other languages
French (fr)
Inventor
Wilhelmus Petrus Martinus Willems
Original Assignee
Via Ingenio B.V.
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Publication date
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Publication of WO2011096812A1 publication Critical patent/WO2011096812A1/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
    • B27K1/00—Damping wood
    • 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
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • 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
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/0085—Thermal treatments, i.e. involving chemical modification of wood at temperatures well over 100°C
    • B27K5/009—Thermal treatments, i.e. involving chemical modification of wood at temperatures well over 100°C using a well-defined temperature schedule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
    • F26B21/06—Controlling, e.g. regulating, parameters of gas supply
    • F26B21/08—Humidity
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
    • F26B21/06—Controlling, e.g. regulating, parameters of gas supply
    • F26B21/10—Temperature; Pressure
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B3/00—Drying solid materials or objects by processes involving the application of heat
    • F26B3/02—Drying solid materials or objects by processes involving the application of heat by convection, i.e. heat being conveyed from a heat source to the materials or objects to be dried by a gas or vapour, e.g. air
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B5/00—Drying solid materials or objects by processes not involving the application of heat
    • F26B5/04—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
    • 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
    • B27K3/025—Controlling the process
    • 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
    • B27K3/10—Apparatus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/14—Furfuryl alcohol polymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B2210/00—Drying processes and machines for solid objects characterised by the specific requirements of the drying good
    • F26B2210/16—Wood, e.g. lumber, timber

Definitions

  • the invention relates to a method for modifying wood, in particular to preserve wood and/or to improve the dimensional stability.
  • the invention also relates to a wood product.
  • the invention further relates to an apparatus for performing the method according to the invention.
  • hemicellulose and lignin become reactive.
  • the wood is cooled and cured by drying, wherein the reactive hemicellulose and lignin form cross-links.
  • the final product is wood which has acquired a greater durability and fungal resistance than the untreated wood. Since all that is required for the reaction is water in the form of steam, hydrothermo lysis is particularly advantageous compared to preserving methods in which the wood is upgraded with impregnating agents usually having an
  • the invention provides for this purpose a method for modifying wood, comprising the processing steps of: A) impregnating wood to be modified with a reactive composition, in particular a polymerisable composition, and B) allowing the impregnated wood to react in an overheated steam filled treatment space by heating the treatment space to a dry bulb temperature of at least 70 degrees Celsius, after which the dry bulb temperature in the treatment space is raised gradually with a dry bulb temperature gradient of a maximum of 40 degrees Celsius per hour, preferably between 20-40 degrees Celsius per hour, to a maximum dry bulb temperature in the treatment space of between 120 and 206 degrees Celsius; wherein at said maximum dry bulb temperature: i) the relative humidity is between 50% and 90%, ii) the wet bulb temperature in the treatment space is between 105 and 176 degrees Celsius, and iii) the wood is heated during a reaction time of at least 10 minutes.
  • step B) the composition impregnated in the wood will react chemically in a controlled and selective humid atmosphere, as a result of which the wood will be chemically modified and hence be preserved long- lastingly while the favourable properties of the wood, such as its mechanical strength and dimensional stability, will be improved as much as possible.
  • the maximum dry bulb temperature would exceed 140 degrees Celsius, and would be situated between 140 and 206 degrees Celsius, the wood is modified both thermally and chemically simultaneously during the same step of the (single) treatment process.
  • the maximum dry bulb temperature would be situated between 120 and 140 degrees Celsius, commonly merely a chemical modification of the wood will be realized.
  • Allowing the wood to react under the influence of heat and in a controlled humid environment, will lead to a controlled modification process of the wood.
  • the presence of steam is important to counteract drying out of the wood during the treatment according to the invention as much as possible, which is in favor of the efficacy and the yield of the treatment to obtain modified wood with the desired properties. It is noted that in case no steam would be used during step B) wood would be obtained commonly having poor properties and hence often insufficient quality for further use.
  • the selective combination of the dry bulb temperature and the wet bulb temperature, together determining the relative humidity, is important to come to a controlled and relatively fast treatment of the wood without affecting the quality of the wood.
  • the wet bulb temperature is directly related to the pressure, the wet bulb temperature would be about 100 degrees Celsius in this situation. Increasing the dry bulb temperature will lead to an increase of the treatment rate of the wood and is therefore often desired. However, simply increasing the dry bulb temperature within the treatment space will lead to an undesired drop of the relative humidity to a level less than 50%. It has been found that the dry bulb temperature could be increased to speeden up the treatment process, without leaving the desired relative humidity range of 50-90%), by increasing the wet bulb temperature in the treatment space to a temperature between 105 and 176 degrees Celsius. This increase of the wet bulb temperature can be established by increasing the (partial) steam pressure within the steam vessel to a pressure between 1 ,25 bar
  • the treatment space is preferably substantially sealed to realize a pressure chamber.
  • Higher wet bulb temperatures and hence higher pressure would be conceivable in theory, though will require very robust steam vessels which are commonly subjected to strict legal regulations. Moreover, these higher wet bulb temperatures and hence higher pressure will often have a negative impact of the treated wood. For example, a wet bulb temperature above 200 degrees Celsius would imply a pressure of about 17 bar which will simply destroy the wood structure.
  • the dry bulb temperature to a desired level can be increased by also increasing the wet bulb temperature, the latter to be established by increasing the (partial) steam pressure in the treatment space.
  • this superatmo spheric pressure is completely determined by the steam pressure as such.
  • Application of additional (inert) gases are commonly not preferred, since it has been found that this could easily deregulate the wood treatment process.
  • Wood impregnated and reacted (cured) with a reactive composition, in particular a polymerisable composition, in a controlled humid environment according to the invention shows improved properties such as improved durability, dimensional stability and surface hardness.
  • the obtained wood shows enhanced resistance against degradation by biological organisms, e.g. fungi, without exerting biocidal effects towards such organisms.
  • wood modified according to the present invention exhibits e.g. enhanced UV stability, cracking resistance, rot resistance and decay resistance.
  • the present wood shows an increased lifetime, is of a consistent quality. It is further noted that the present wood is environmentally friendly, since wood that has been impregnated and reacted in accordance with the present invention has qualities which are comparable with tropical hard wood, and is therefore an ideal substitute thereof.
  • the present wood does not have toxicity to organisms in the environment, including humans. Even at the end-of-life, toxic compounds are not released from the woods obtained by applying the method according to the invention. Waste of wood components due to damage by for instance splitting is also exceptionally low.
  • the reactive compositions, in particular polymerisable compositions, applied are able to penetrate into the cell structure of wood (step A) and are subsequently polymerized or reacted in another manner in situ (step B).
  • the composition becomes an integral part of the wood cell- wall structure, modifies the wood cell wall and stable impregnated wood is obtained.
  • the reactive composition remains stable at increased dry bulb temperature according to step B) and will not be decomposed due to heating.
  • DMDHEU dimethyloldihydroxyethyleneurea
  • furfurylalcohol furfurylation
  • alkoxysilane silicone/silane
  • linseed oil natural resin
  • parafin oil/wax/parafms
  • step B) the relative humidity within the treatment space is held at a substantially constant level, preferably between 60% and 85%, more preferably between 65% and 80%>, most preferably at (about) 75%.
  • a substantially constant level preferably between 60% and 85%, more preferably between 65% and 80%>, most preferably at (about) 75%.
  • a water supply container is positioned within the treatment space, wherein during step B) water is evaporated from the water supply container to humidify the treatment space.
  • the quantity of water to be evaporated from the water supply container will commonly be controlled by the combination of the dry bulb temperature within the treatment space and the temperature of the water supply container, wherein the dry bulb temperature can commonly be regulated by independent heating means adapted to heat the treatment space commonly enclosed by (a thermal oil jacket of) an autoclave and the water supply container.
  • independent heating means adapted to heat the treatment space commonly enclosed by (a thermal oil jacket of) an autoclave and the water supply container.
  • the manner to impregnate the wood to be modified with a composition is to place the wood in a treatment vessel wherein a vacuum is applied, after which the wood is exposed to the composition while substantially maintaining said vacuum, and wherein a predetermined air pressure of between 6 and 14 bar is applied to the wood for a period of time sufficient to partially impregnate the wood with the composition. Subsequently, the pressure within the treatment vessel is reduced and the surplus of composition is removed from the treatment vessel. Since during step B) the wood may be progressively thermally modified by applying increasing temperatures above 140°C, it is thinkable to merely partially impregnate by the reactive composition, in particular the polymerisable composition, during step A). In this case, an outer shell of the wood may be
  • impregnating the wood with the reactive composition, in particular the polymerisable composition will commonly be cheaper than fully impregnating the wood with the reactive composition, in particular the polymerisable composition, due to material savings.
  • the initial dry bulb temperature of the wood is normally the ambient dry bulb temperature, usually between 15 and 25 degrees Celsius.
  • the wood In the starting situation, prior to step A), the wood generally has a moisture content of between 3-18% by weight (of the dry wood mass). Since the reactive composition often comprises a liquid compound, in particular a liquid carrier, the moisture content of the wood will be increased during step A).
  • the wood is humidified during step A)
  • step D) comprising removing at least a substantial fraction of air, in particular oxygen, from the treatment space prior to execution of step B).
  • the removal of air, in particular oxygen, from the treatment space during step D) can for instance take place by displacement of air by an inert gas such as nitrogen or argon, or by steam. If air is not removed, oxygen from the presence air may lead to unwanted reactions during the modification process. The best results are achieved if the oxygen is removed by creating a vacuum in the treatment space. If a vacuum has been created in the treatment space during step D), the steam can be used to supplement the vacuum.
  • the degree of pressure decrease can be determined using a simple pressure gauge and is a reliable measure of the quantity of air, and thereby oxygen, removed.
  • the reduced pressure is lower than 13 kPa (absolute pressure). This results in a proper removal of oxygen from the treatment space.
  • the wall dry bulb temperature of the treatment space can optionally be increased to 50-70 degrees Celsius for an even better removal of oxygen. The time required for the process is moreover shortened since a start is already made with pre-heating for the subsequent processing step B).
  • step B) The chemical reaction according to step B) can be stopped by reducing the dry bulb temperature to below 120 degrees Celsius, and then further to room temperature.
  • the cooling process and conditions are dependent on the reactive composition used.
  • the heated wood may be compressed in the treatment space to obtain a wood product with a greater density.
  • the steam has a maximum degree of saturation of 95% during step C).
  • the degree of saturation is the percentage relative to 100% saturated steam at the same pressure and dry bulb temperature. This produces a better wood product, and in particular less splitting, than a comparable process in which saturated steam is used. A significant factor here is probably that condensation of water is largely prevented.
  • the reactive substance is formed by a polymerisable substance comprising a chemical compound of formula I and/or formula II
  • n is an integer between 0 and 20, preferably between 0 and 10, and more preferably between 0 and 5 wherein t and s each independently are an integer between 1 and 20, preferably between 1 and 10, and more preferably between 1 and 5, wherein w and z each independently are 0 or 1 , wherein X and Y each independently are O, S or N-R 21 and wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 18 , R 19 , R 21 are each independently hydrogen or selected from the group comprising C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C5-C12 heteroaryl, carboxaldehyde, hydroxyl, hydroxyalkyl, carboxyl, amino, nitro,
  • alkyl by itself or as part of another substituent, refers to a straight or branched saturated hydrocarbon group joined by single carbon-carbon bonds having 1 to 20 carbon atoms, for example 1 to 10 carbon atoms, for example 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1, 2, 3 or 4 carbon atoms.
  • the subscript refers to the number of carbon atoms that the named group may contain.
  • C1-C4 alkyl means an alkyl of one to four carbon atoms.
  • alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, pentyl iso-amyl and its isomers, hexyl and its isomers, heptyl and its isomers and octyl and its isomer.
  • alkyl is used as a suffix following another term, as in "hydroxyalkyl,” this is intended to refer to an alkyl group, as defined above, being substituted with one or two (preferably one) substituent(s) selected from the other, specifically-named group, also as defined herein.
  • C1-C20 alkyl refers to an alkyl of 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
  • alkenyl by itself or as part of another substituent, refers to a straight or branched alkyl chain containing at least one unsaturation in the form of a single carbon to carbon double bond and having 2 to 20 carbon atoms, for example 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2, 3 or 4 carbon atoms.
  • alkenyl groups are ethenyl (vinyl), 2-propenyl, 2-butenyl, 3-butenyl, 2- pentenyl and its isomers, 2-hexenyl and its isomers, 2-heptenyl and its isomers, 2- octenyl and its isomers, 2,4-pentadienyl and the like.
  • C2-C20 alkenyl refers to an alkenyl of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
  • alkynyl by itself or as part of another substituent, refers to a straight or branched alkyl chain containing at least one unsaturation in the form of a single carbon to carbon triple bond and having 2 to 20 carbon atoms, for example 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and for instance 2, 3, 4, 5 or 6 carbon atoms.
  • alkynyl groups are ethynyl, 2- propynyl, 2-butynyl, 3- butynyl, 2-pentynyl and its isomers, 2-hexynyl and its isomers, 2-heptynyl and its isomers, 2-octynyl and its isomers and the like.
  • C 2 -C 20 alkynyl refers to an alkynyl of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
  • alkyl groups as defined are divalent, i.e., with two single bonds for attachment to two other groups, they are termed "alkylene" groups.
  • alkylene groups includes methylene, ethylene, methylmethylene, trimethylene, propylene, tetramethylene, ethylethylene, 1 ,2-dimethylethylene, pentamethylene and
  • alkenyl groups as defined above and alkynyl groups as defined above, respectively are divalent radicals having single bonds for attachment to two other groups, they are termed “alkenylene” and “alkynylene” respectively.
  • aryl as used herein by itself or as part of another group refers but is not limited to 5 to 24 carbon-atom homocyclic (i.e., hydrocarbon) monocyclic, bicyclic or tricyclic aromatic rings or ring systems containing 1 to 4 rings which are fused together or linked covalently, typically containing 5 to 8 atoms; at least one of which is aromatic.
  • the aromatic ring may optionally include one to three additional rings (either cycloalkyl, heterocyclyl or heteroaryl) fused thereto.
  • aryl comprise phenyl, biphenylyl, biphenylenyl, 5- or 6-tetralinyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azulenyl, 1- or 2- naphthyl, 1-, 2- or 3-indenyl, 1-, 2- or 9-anthryl, 1- 2-, 3-, 4- or 5- acenaphtylenyl, 3-, 4- or 5-acenaphtenyl, 1-, 2-, 3-, 4- or 10-phenanthryl, 1- or 2- pentalenyl, 1 , 2-, 3- or 4-fluorenyl, 4- or 5-indanyl, 5-, 6-, 7- or 8-tetrahydronaphthyl, 1 ,2,3,4-tetrahydronaphthyl, 1 ,4- dihydr
  • heteroaryl as used herein by itself or as part of another group refers but is not limited to 5 to 12 carbon-atom aromatic rings or ring systems containing 1 to 3 rings which are fused together or linked covalently, typically containing 5 to 8 atoms; at least one of which is aromatic in which one or more carbon atoms in one or more of these rings can be replaced by oxygen, nitrogen or sulfur atoms where the nitrogen and sulfur heteroatoms may optionally be oxidized and the nitrogen heteroatoms may optionally bequaternized.
  • Such rings may be fused to an aryl, cycloalkyl, heteroaryl or
  • hydroxyalkyl refers to a -R b -OH group wherein R b is alkylene as defined herein.
  • amino refers to the group -NH 2 .
  • alkylamino refers to the group -N(R e )(R f ) wherein R e and R f are each independently selected from hydrogen and alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C 5 - C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, alkylfuryl, furylalkyl,
  • aminoalkyl refers to the group -R b -NH2 wherein R b is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
  • alkylaminoalkyl refers to the group -R b -NR e R f wherein R b is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C 2 - C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, alkylfuryl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, R e is hydrogen or alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, alkylfuryl, furylalkyl, hydroxyal
  • carboxy is equivalent to "hydroxycarbonyl” and refers to the group - C0 2 H.
  • alkylcarboxy is equivalent to "alkyloxycarbonyl” and refers to the group - C0 2 -R a , wherein R a is alkyl which is optionally substituted with one or more substituents selected from Ci-C 2 o alkyl, C 2 -C 2 o alkenyl, C 2 -C 2 o alkynyl, C 5 -C 2 4 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
  • alkenylcarboxy is equivalent to "alkenyloxycarbonyl" and refers to the group -C0 2 -R c , wherein R c is alkenyl which is optionally substituted with one or more substituents selected from Ci-C 2 o alkyl, C 2 -C 2 o alkenyl, C 2 -C 2 o alkynyl, C 5 -C 2 4 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
  • furylalkyl refers to the group -R b -furyl, wherein furyl is as defined above and R b is alkylene which is optionally substituted with one or more substituents selected from Ci-C 2 o alkyl, C 2 -C 2 o alkenyl, C 2 -C 2 o alkynyl, C 5 -C 2 4 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
  • hydroxyalkylfurylalkyl refers to the group -R b -furyl-R b -OH, wherein
  • alkylfuryl refers to the group -furyl-R b , wherein furyl is as defined above and R b is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl,
  • alkoxy refers to the group -0-R a wherein R a is alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino,
  • alkoxyalkyl refers to the group -R b -0-R a wherein R a is alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio and R b alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl,
  • alkenyloxy refers to the group -0-R b wherein R b is alkenyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
  • An example is vinyl ether.
  • Said alkylcarbonyl can be exemplified by acetyl, propionyl, butyryl, valeryl and pivaloyl.
  • An example hereof is vinyl ketone.
  • R c is alkenyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl,
  • hydroxyalkylfurylalkyl isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
  • isocyanate-alkyl refers to the group -R a -isocyanate, wherein R a is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C 5 - C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl,
  • hydroxyalkylfurylalkyl isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
  • nitro refers to the group -NO 2 .
  • cyano refers to the group -CN.
  • thiol or ""sulfhydryl” refers to the group -SH.
  • alkylthio refers to the group -SR a group wherein R a is alkyl which is optionally substituted with one or more substituents selected from C 1 -C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C 5 -C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
  • alkylthio groups include methylthio (SCH 3 ), ethylthio (SCH 2 CH 3 ), n- propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n- hexylthio, and the like.
  • thioalkyl refers to the group -R b -SH wherein R b is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
  • Non- limiting examples of thioalkyl groups include thio methyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl, thioheptyl, thiooctyl, thiooctadecyl, and the like.
  • alkylthioalkyl refers to the group -R b -S-R a wherein R b is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C 2 - C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio and R a is alkyl which is optionally substituted with one or more substituents selected from d- C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfury
  • halo or "halogen” as a group or part of a group is generic for fluoro, chloro, bromo or iodo.
  • haloalkyl refers to an alkyl radical having the meaning as defined above wherein one or more hydrogen atoms are replaced with a halogen as defined above.
  • Non-limiting examples of such haloalkyl radicals include chloromethyl, 1-bromoethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 ,1 -trifluoroethyl and the like.
  • haloalkenyl refers to an alkenyl radical having the meaning as defined above wherein one or more hydrogen atoms are replaced with a halogen as defined above.
  • haloaryl refers to an aryl radical having the meaning as defined above wherein one or more hydrogen atoms are replaced with a halogen as defined above.
  • substituted it is meant to indicate that one or more hydrogen atoms on the atom indicated in the expression using
  • substituted is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a chemically stable compound, i.e. a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture.
  • composition comprising substituted furan compounds as defined herein.
  • the invention relates to the use of a composition as defined above, comprising furan compounds of formula I and/or formula II wherein n is an integer between 0 and 5, and preferably is 0, 1 , 2, 3, 4, or 5 wherein t and s each independently are an integer between 1 and 5, and preferably each are 1 or 2, wherein w and z each independently are 0 or 1 , wherein X and Y each independently are O, S or N-R 21 and wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 ' R 16 , R 18 , R 19 , R 21 are each independently hydrogen or selected from the group comprising C1-C20 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, amino, nitro, alkylamino, aminoalkyl, alkoxyalkyl, al
  • carboxaldehyde hydroxyalkyl, carboxyl, alkylamino, aminoalkyl, alkylaminoalkyl, alkyloxy, alkoxyalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkenyloxy,
  • alkylcarbonylalkenyl alkenylcarbonyl, alkylcarbonyloxyalkyl
  • alkenylcarbonyloxyalkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyl, and any mixtures thereof and even more preferred from the group comprising C1-C10 alkyl, carboxaldehyde, hydroxyalkyl, alkylamino, aminoalkyl, alkylaminoalkyl, carboxyl, alkyloxy, alkoxyalkyl, furylalkyl, hydroxyalkylfurylalkyl alkenyloxy, alkylcarboxy, alkenylcarboxy, alkylcarbonyl, alkenylcarbonyl, and any mixtures thereof, and still more preferred from the group comprising C1-C10 alkyl, carboxaldehyde, hydroxyalkyl, aminoalkyl, carboxyl, and any mixtures thereof, whereby each group is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 al
  • the invention relates to the use of a composition
  • a composition comprising a compound of formula I and/or formula II, wherein n is 0, 1 , 2, 3, 4 or 5 wherein t and s each independently are 1 or 2, wherein w and z each independently are 0 or 1 , wherein X and Y each independently are O, S or N-R 21 and wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 18 , R 19 , R 21 are each independently hydrogen or selected from the group comprising C1-C2 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, aminoalkyl, alkylaminoalkyl hydroxyalkylfurylalkyl, alkyloxy, alkoxyalkyl, alkylcarbonylalkenyl, alkylcarbonyloxyal
  • alkylcarbonyloxyalkyl alkyloxycarbonylalkenyl, alkenylcarbonyloxyalkyl, oxiranyl, isocyanate, isocyanate-alkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyl,
  • the invention relates to the use of a composition
  • a composition comprising a compound of formula I and/or formula II wherein n is an integer between 0 and 5 wherein t and s each independently are 1 or 2, wherein w and z each independently are 0 or 1 , wherein X and Y are each independently O, S or N-R 21 and wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 18 , R 19 , R 21 are each independently hydrogen or selected from the group comprising C 1 -C 2 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, aminoalkyl, alkylaminoalkyl
  • R 1 , R 8 , R 17 and R 20 are each independently selected from the group comprising Ci-C 2 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, aminoalkyl, alkylaminoalkyl,
  • the a composition comprising a compound of formula I and/or formula II, wherein n is 0, 1 , 2, 3, 4, or 5, wherein t is 1 or 2, wherein s is 1 or 2, wherein w is 0 or 1 , wherein z is 0 or 1 , wherein X is O, S or N-R 21 , and wherein Y is O, S or N-R 21 ; wherein R 1 is hydrogen or selected from the group comprising Ci-Cs alkyl, C 2 -Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -
  • R 7 is hydrogen or selected from the group comprising Ci-Cs alkyl, C 2 -Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
  • R 16 is hydrogen or selected from the group comprising Ci-Cs alkyl, C 2 -C 8 alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
  • R 21 is hydrogen or selected from the group comprising Ci-Cs alkyl, C 2 -C8 alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
  • non-limiting examples of furan compounds comprised in a composition used in the method according to the invention include but are not limited to 2,5- bis(hydroxymethyl)furan; 2,3,5-tris(hydroxymethyl)furan; 5- methyl-2-furfuryl alcohol, 3- hydroxymethyl-5-methyl-2-furfurylalcohol; 2,2'- (hydroxymethyl)difurylmethane; 2, 2', 3,3'- (hydroxymethyl)difurylmethane; 2,2',4,4'- (hydroxymethyl)difurylmethane; 5- hydroxymethyl- [alpha] -(methyl)furfuryl alcohol; 5- hydroxymethyl-2-furancarboxaldehyde; 3,5- hydroxymethyl-2-furancarboxaldehyde; 4,5-hydroxymethyl-2-furancarboxaldehyde; 5- methyl-2-furancarboxaldehyde; 3- hydroxymethyl-5-methyl-2-furancarboxaldehyde; 5-nitro furfuraldehyde;
  • the impregnating composition used in the method according to the invention comprises 2,5-bis(hydroxymethyl)furan (BHMF). In another embodiment the impregnating composition used in the method according to the invention comprises 2,3,5-tris(hydroxymethyl)furan (THMF). In yet another embodiment the impregnating composition used in the method according to the invention comprises 2,2'- hydroxymethyldifurylmethane (HMDM). In still another embodiment the impregnating composition used in the method according to the invention comprises 5-hydroxymethyl- 2- furfurylamine. In still another embodiment the impregnating composition used in the method according to the invention comprises 5-hydroxymethyl-2-furancarboxaldehyde.
  • BHMF 2,5-bis(hydroxymethyl)furan
  • THMF 2,3,5-tris(hydroxymethyl)furan
  • HMDM 2,2'- hydroxymethyldifurylmethane
  • the impregnating composition used in the method according to the invention comprises 5-hydroxymethyl- 2- furfurylamine.
  • the impregnating composition used in the method according to the invention comprises 5-methyl-2-furfuryl alcohol. In still another embodiment the impregnating composition used in the method according to the invention comprises 5- hydroxymethyl- [alpha] -(methyl)furfuryl alcohol. In yet another embodiment the impregnating composition used in the method according to the invention comprises 2, 2', 3,3'- (hydroxymethyldifurylmethane. In another embodiment the impregnating composition used in the method according to the invention comprises 2,2',4,4'- (hydroxymethyl)difurylmethane.
  • the invention relates to the use of a composition comprising 2,5-bis(hydroxymethyl)furan (BHMF), 2,3,5- tris(hydroxymethyl)furan (THMF), and 2,2'-hydroxymethyldifurylmethane (HMDM).
  • BHMF 2,5-bis(hydroxymethyl)furan
  • THMF 2,3,5- tris(hydroxymethyl)furan
  • HMDM 2,2'-hydroxymethyldifurylmethane
  • the invention relates to the use of a composition comprising 2,5-bis(hydroxymethyl)furan (BHMF); 2,3,5-tris(hydroxymethyl)furan (THMF); and 2,2'-(hydroxymethyl)difurylmethane (HMDM); and optionally
  • BHMF 2,5-bis(hydroxymethyl)furan
  • THMF 2,3,5-tris(hydroxymethyl)furan
  • HMDM 2,2'-(hydroxymethyl)difurylmethane
  • condensation products of BHMF, THMF and/or HMDM condensation products of BHMF, THMF and/or HMDM, and/or mixtures thereof.
  • n is preferably between 0 and 5, and more preferably 1 , 2, 3 or 4; wherein t is 1 or 2; wherein s is 1 or 2; wherein w is 0 or 1 ; wherein z is 0 or 1 , wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are each independently hydrogen, methyl, a hydroxyalkyl or a
  • R 1 , R 8 are each independently selected from the group comprising methyl, hydroxyalkyl, and hydroxyalkylfurylalkyl.
  • the invention relates to a polymerisable composition for impregnating and modifying wood comprising a compound of formula I and/or formula II wherein n, t, s, w, z, X, Y, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 R 18 , R 19 , R 20 R 21 are as defined above, and wherein the dotted line represents a double bond, provided that R 17 and R 20 are not a C1-C20 alkyl, and preferably not methyl, and/or provided that the compound is not 2,5 dimethylfuran, 2,4 dimethylfuran, 2-acetyl-5- methylfuran, 2,5 dimethyl-3-acetylfuran, 2,3,5- trimethylfuran, 2-vinyl-3 -methylfuran, 2-methyl benzofuran, dimethylbenzo
  • Furan compounds can be applied in varying amounts in the present composition depending on the wood density and the solid content of the composition comprising substituted furan compounds. It can be adapted according to the desired properties of wood one wants to obtain such as increased density, increased hardness, increased durability, increased fire resistance (FRE or Fire Retardant Efficiency), increased dimensional stability, a desired modulus of elasticity (MOE), improved Anti swelling efficiency (ASE), reduced equilibrium moisture content (EMC), etc...
  • the amount of substituted furan compounds in the present composition varies between 3 and 100 % by weight and preferably between 10 and 60% by weight.
  • the amount of substituted furan compounds being impregnated in the wood varies between 3 and 100 % by weight on wood and preferably between 10 and 60% by weight on wood.
  • Substituted furan compounds in a composition used in the method according to the invention are used in an amount such that the weight percentage gain (WPG) of the wood after impregnation and reaction with the wood is at least 3% and for instance can vary from 3% to 150%, more preferably from 5% to 100% and even more preferable between 10%> and 60%>, and more preferably between 20 and 40%> by weight.
  • WPG weight percentage gain
  • the invention relates to a composition
  • a composition comprising more than 60 % by weight, and preferably more than 70% by weight of a compound of formula I and/or formula II, wherein n is smaller than or equal to 5, and - 0 to 40% by weight, preferably 0 to 30% by weight of condensation products thereof.
  • the invention relates to a composition
  • a composition comprising more than 70% by weight, preferably more than 80 % by weight, and more preferred more than 90% by weight of a compound of formula II, - 0 to 30%> by weight, preferably 0 to 20%> by weight, more preferred 0 to 10% by weight of a compound of formula I, wherein n is smaller than or equal to 5, and preferably smaller than or equal to 2, and more preferably 0 or 1 , and optionally 0 to 40%> by weight, preferably 0 to 30%> by weight of condensation products thereof.
  • the invention provides a composition comprising a mixture of: up to 70 %> by weight, preferably up to 55 %>, more preferably up to 25%> by weight of 2,5-bis(hydroxymethyl)furan (BHMF), up to 20 %> by weight, preferably up to 15 %>, more preferably up to 5%> by weight of 2,3,5-tris(hydroxymethyl)furan (THMF), and up to 10 %> by weight, preferably up to 5 %>, more preferably up to 1 %> by weight of 2,2'- hydroxymethyldifurylmethane (HMDM).
  • BHMF 2,5-bis(hydroxymethyl)furan
  • THMF 2,3,5-tris(hydroxymethyl)furan
  • HMDM 2,2'- hydroxymethyldifurylmethane
  • the composition may further comprise up to 40 % by weight, preferably up to 30 ) by weight of condensation products of BHMF, THMF and/or HMDM.
  • the invention relates to a composition comprising: up to 60 % by weight, and preferably up to 30% by weight of a compound of formula I and/or formula II, wherein n is smaller than or equal to 5, and up to 40%> by weight, preferably up to 60%) by weight of condensation products thereof.
  • the polymerisable impregnation composition preferably comprises disubstituted, trisubstitured or polysubstituted furan compounds or a mixture thereof and may contain a solvent, catalyst (initiator), coupling agent, filler, fire retardant, oil(wax) and/or surfactant.
  • the impregnation composition does not set nor react even over extended periods of time, such that it has a long shelf-life.
  • substituted furan compounds as defined herein, or substituted furan compounds diluted in a solvent are stable in the presence of a catalyst at room temperature.
  • the compounds of the present composition are diluted in a solvent.
  • concentration of the furan compounds in such dilution is between 5 and 95 wt%, and more preferably between 10 and 80 wt%
  • suitable solvents which may be used in a composition used in the method according to the invention comprise but are not limited to water, alcohols such as ethanol or methanol, dioxane, N,N dimethylformamide, acetone, ethyleneglycol, or glycerol.
  • the solvent is water.
  • the furan compounds according to the invention are preferably water soluble.
  • the furan compounds according to the invention are water-soluble in presence of a catalyst.
  • water soluble refers to the amount that is soluble, after standing at least 48 hours in water at room temperature, when 5.0 grams of furan compounds is added to 95.0 grams deionized water.
  • the present furan compounds can react with wood in the presence or the absence of a catalyst.
  • the composition used in the method according to the invention may thus further comprise a catalyst.
  • the catalysts may be a metallic salt, an ammonium salt, an organic acid, an anhydride, an inorganic acid or any mixtures thereof.
  • the catalysts are metallic salts such as metalhalogenides, metalsulfates, metalnitrates, metalphosphates or their mixtures. Examples are magnesium chloride, magnesium sulfate, magnesium nitrate, zinc chloride, zinc nitrate, aluminum chloride, aluminum nitrate, aluminum sulfate or their mixtures.
  • the catalyst is an ammonium salt. Examples are ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium carbonate, ammonium
  • catalysts may be organic acids or inorganic acids. Suitable examples hereof are formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, oxalic acid, maleic acid, maleic anhydride, adipic acid, citric acid, furoic acid, benzoic acid, phtalic anhydride, paratoluene sulphonic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, silicic acid, benzoylperoxide or their mixtures.
  • the composition may comprise up to 20 % (or more), generally in the range of 1-15 %, preferably 8-10 %, more preferably 5-8 %, yet more preferably 5 % by weight on catalyst on the amount of substituted furan compounds in the composition.
  • Catalyst amount is hereby calculated on the amount of "dry" furan compounds.
  • BHMF 2,5- bis(hydroxymethyl)furan
  • THMF 2,3,5- tris(hydroxymethyl)furan
  • HMDM 2,2'- (hydroxymethyl)difurylmethane
  • condensation products thereof, 2,2', 3,3'- (hydroxymethyl)difurylmethane; 2, 2', 4,4'- (hydroxymethyl)difurylmethane are obtained by hydroxymethylation of furfuryl alcohol with a formaldehyde source.
  • formaldehyde source refers to formaldehyde, paraformaldehyde, trioxane, or any hemiformal.
  • the invention also provides a wood product which obtainable in accordance with the method according to any of the foregoing claims. Such a wood product has a good durability combined with a increased mechanical strength.
  • the invention further provides a system suitable for performing the method according to the invention, comprising: an impregnation device for impregnating wood with a reactive composition, in particular a polymerisable composition, and a chemical modification device provided with heating means for allowing the impregnated wood to react under the influence of heat.
  • the impregnation device is adapted for forcing the reactive composition through the wood at least partially by using pressure.
  • the impregnating device may be pressurized by using any suitable apparatus, such as, for example, a high volume transfer or pressure pump or air pressure provided by a compressor system.
  • An inlet may be provided at one end of the device with pressure being relieved from the other end which allows for a high volume flow over and through the wood in the device.
  • the wood will generally be fully submerged in the, commonly waterborne, reactive preservative, in particular polymerisable preservative. The separation of the wood and the excess waterborne preservative may be performed by removing the wood from the preservative.
  • the chemical modification device comprises a treatment space sealable in medium-tight manner, a vacuum pump connected to the treatment space, a steam source connected to the treatment space, a heating device which is in thermal contact with the treatment space, and measuring and control equipment adapted to measure at least the dry bulb temperature, the relative humidity, and the pressure (wet bulb temperature) inside the treatment space and to control the vacuum pump, the steam source and the heat source.
  • the method according to the invention can be performed in simple manner using such a device.
  • the apparatus can herein be programmed optimally for the treatment of determined types of wood.
  • the treatment space is bounded by a double wall provided with thermally conducting oil.
  • the dry bulb temperature inside the treatment space can hereby be readily controlled and kept homogeneous.
  • the thermal oil is situated between the two walls of the double wall.
  • the apparatus according to the invention is preferably programmed for performing a method according to the invention.
  • the apparatus can be provided for this purpose with a computer with which the measuring and control equipment is read and the vacuum pump, the steam source and the heat source and possible other components are controlled.
  • Figure 1 shows a schematic view of the method according to the invention
  • Figure 2 shows an impregnation device for use in a system according to the invention
  • Figure 3 shows a chemical modification device for use in a system according to the invention
  • Figure 4 shows a chart illustrating the dependency of the dry bulb temperature, the wet bulb temperature, and the relative humidity for use in a method and system according to the invention.
  • Figure 1 shows a schematic view of the method according to the invention, wherein in a first step 1 wood to be modified is impregnated with a waterborne polymerisable composition by means of a known vacuum-pressure method, after which, in a second step 2, the wood is dried in either a natural or a forced manner until the moisture content has been reduced to about 14% by weight.
  • a third step 3 at least a fraction of oxygen contained by a treatment vessel is removed from the treatment vessel, after which, in a fourth step 4, the impregnated wood is heated gradually in the treatment vessel to chemically modify the wood, wherein the composition is polymerised within the wood, and - dependent on the maximum dry bulb temperature applied in the vessel - eventually to thermally modify the wood.
  • FIG. 2 shows an impregnation device 48 for use in a system according to the invention.
  • waterborne preservative modifying agent contained in a storage tank 7 is heated to the required temperature, such as 30-98 degrees Celsius, and then agitated by means of the agitation pump 8, wherein a valve 9 is open. Heating may be achieved either by an in-tank heater or a heat pump in the agitation line.
  • a pressure cylinder 10 is loaded with wood to be modified (not shown) and the door 11 closed and sealed.
  • An initial vacuum such as, 0-98 kPa, is drawn by means of valves 12, 13, 14 and 15 closed and valve 16 open, wherein a vacuum pump 17 is switched on.
  • a vacuum control valve 18 maintains the required level of vacuum (underpressure). The vacuum is reached and held for a predetermined time.
  • the pressure cylinder 10 is then flooded with the hot preservative and valves 15 and 16 are opened. The level of vacuum is maintained by vacuum control valve 1. Once the cylinder 10 is flooded, valves 12 and 15 are closed. The vacuum pump 17 is then turned off.
  • Pressures up to 1400 kPa are applied using a high volume pressure pump 19 with valve 15 open.
  • the pressure control valve 13 maintains the required pressure.
  • the presence of the high volume pump 19 means that there is constantly fresh hot solution passing though the pressure cylinder 10 treating and heating the wood. Pressure is released via the vacuum control valve 18 to ramp down the pressure to 0 kPa.
  • the advantage of using alternative (b) is that the pressure cylinder 10 can be emptied at the same pressure as the wood was treated or at a higher pressure meaning that any kickback is alleviated until the preservative has been removed from the cylinder and the pressure achieved, and can then be segregated. The kickback can then be collected after final vacuum and cleaned up prior to returning clean preservative to the storage tank 7.
  • all the valves are closed apart from valve 12 and a vacuum such as -80 to -98 kPa is drawn on the pressure cylinder 10. After a predetermined time, the vacuum is vented through valve 18 and any residual liquid is then cleaned and/or recycled.
  • the door 11 is then opened and the treated fixed timber removed for storage under cover until it is dispatched.
  • FIG. 3 shows a chemical modification device 20 for use in a system according to the invention, comprising a treatment space 21 adapted to receive impregnated wood, which wood may for example be impregnated with a polymerisable composition by using the device 48 as shown in figure 2.
  • the treatment space 21 is confined by a thermally isolated outer reactor wall 22, and a thermally conducting inner reactor wall 23 which is filled with a thermally conductive oil.
  • the treatment space 21 connects to a water container 24 containing water 25 that is heated by heating means 26 in order to generate steam, which is led to the treatment chamber 21 through a steam channel 27.
  • the water container 24 is incorporated within the treatment space 21.
  • the amount of water should be sufficient for achieving the desired steam pressure in the reactor chamber 21, taking into account the additional water consumed by hydrolysis reactions and the amount of water adsorbed by the wood.
  • the container 24 is sufficiently large to store the initial amount of water plus the amount released by condensation reactions, dehydration reactions and drying.
  • the treatment space 21 is provided with a mechanical stirrer 28 used to homogenize the generated steam and volatile reaction products, leading to a homogenous exposure of the treated wood parts 29.
  • the wood parts 29 are preferably spaced apart, preferably having mutual distances of 8-15 mm, allowing for an even more homogenous treatment.
  • the treatment space 21 and the water container 24 form a closed system, in order to optimize the use of water.
  • the system is provided with a safety pressure valve.
  • the water container can be used as a cold spot, wherein the water container 24 has a dry bulb temperature lower than the treatment space 21, in order to ensure that water condenses in the water container and not in the treatment space 21 where it could possibly condense on the wood 29.
  • the treatment space 21 is provided with at least one standard safety pressure release valve, set at a pressure below the maximum pressure the reactor walls 22,23 can withstand.
  • the pressure typically ranges from vacuum to a maximum of approximately 12 bar, hence the safety pressure release valve could for instance be set at 14 bar.
  • the pressure inside the treatment space 21 can be monitored by a standard pressure meter 47 covering the operating range.
  • the impregnated wood will be polymerised in the steam filled treatment space 21 by heating the treatment space 21 to a dry bulb temperature of at least 70 degrees Celsius, after which the dry bulb temperature in the treatment space is raised gradually with a dry bulb temperature gradient of a maximum of 40 degrees Celsius per hour, preferably between 20-40 degrees Celsius per hour, to a maximum dry bulb temperature of between 120 and 206 degrees Celsius; wherein the wood is heated at said maximum dry bulb temperature during a reaction time of at least 10 minutes.
  • the maximum dry bulb temperature exceeds 140 degrees Celsius during operation, the wood will be modified both chemically and thermally.
  • the treatment space 21 also connects to a first pressurized cylinder 30 comprising carbon dioxide (C0 2 ), which is connected through an first automated dispensing valve 31. Carbon dioxide may be used to lower the pH in the reactor as carbon dioxide acidifies steam.
  • the device 20 also comprises a second pressurized cylinder 32 of ammonia (NH 3 ) also connected to a second automated dispensing valve 33. Having the possibility to add predetermined amounts of acid or base may be used to maintain the pH at a predetermined value during the treatment according to the invention.
  • the pH is monitored by taking samples of the steam in the reactor space 21 by temporarily opening a sample valve 34, condensing the sampled steam in a condenser 35, and collecting the condensed steam 36 for pH measurement using regular electrochemical pH measurement equipment 37.
  • the treatment space 21 is also provided with a vacuum pump system 38 for evacuating the treatment space 21, in particular for removing oxygen gas.
  • the vacuum system 38 optionally includes a pressure meter for monitoring pressure within the treatment space 21. Instead of the optional pressure meter, it is also possible to rely on dry bulb temperature and pH measurements only.
  • the device 20 is provided with heating means 45 for heating the reactor chamber 21, and a dry bulb temperature measurement units (40, 41, 42) for the inner reactor wall 23 (unit 40), the wood 29 (unit 41) and the water 25 of the steam generator 24 (unit 42).
  • a central control unit 43 monitors the dry bulb temperature of the wood 41, the dry bulb temperature of the inner reactor wall 23, the dry bulb temperature of the steam water 25, the pressure within the treatment space 21, and the pH within the treatment space.
  • the control unit 43 will then, following the preset program or manual control, adjust these parameters. For instance, pressure can be increased by turning up the heater 26 of the steam generator, leading to increased steam evaporation, or lowered by lowering the dry bulb temperature, water evaporation and/or opening the vacuum valve 44 of the vacuum system 38.
  • the vacuum valve 44 is a three- way valve, that can also be used to depressurize the reaction vessel 21, or to let air or an inert gas such as nitrogen into the treatment space 21 in order to remove vacuum.
  • the dry bulb temperature in the treatment space 21 can be adjusted by the wall heater unit 45. pH can be lowered by adding carbon dioxide 30, or increased by adding ammonia 32.
  • impregnation device 48 as shown in figure 2 and the modification device 20 as shown in figure 3 are physically connected to each other and/or are mutually integrated at least partially.
  • Figure 4 shows a chart 49 illustrating the dependency of the dry bulb temperature (in °C), the wet bulb temperature (in °C), and the relative humidity (in %) for use in a method and system according to the invention.
  • wbT wet bulb temperatures
  • the three different wet bulb temperatures are referred to as process A, process B, and process C.
  • process A the wet bulb temperature is 100°C corresponding to a substantially atmospheric pressure of 1,05 bar.
  • process B the wet bulb temperature is 125°C corresponding to a (superatmospheric) pressure of 2,45 bar.
  • process C the wet bulb temperature is 160°C corresponding to a (superatmospheric) pressure of 6,75 bar.
  • Constant wet-bulb temperatures are physically equivalent with constant partial pressures of water vapor.
  • the system according to the invention is able to accurately control the wet-bulb temperature (water reservoir temperature) in a steam vessel (pressure chamber) of the system, or alternatively by application of an external pressure regulated steam generator coupled to said steam vessel.
  • steam can be generated internally in the vessel and/or externally at a distance from the vessel.
  • the steam vessel may be provided with a pressure relief valve to limit the maximum superatmospheric pressure.
  • the Wet-bulb temperatures in excess of 100°C are to be contained in a pressure vessel (autoclave).
  • the system according to the invention is also able to accurately control the dry-bulb temperature (wall temperature of the autoclave).
  • Dry-bulb temperature and wet-bulb temperature determine together the relative humidity.
  • the marked region in the chart 49 indicates the desired range of relative humidity of between 50% and 90%, more preferably between 60%> and 80%>, providing a desired mild climate for wood modification.
  • Relative humidities under 50%, and in particular under 35% can be destructive for wood, as there is a high risk for checks and distortion, especially in thick (in excess of 40 mm) wood specimens.
  • Chemical modifications are commonly performed in a superheated steam kiln under atmospheric conditions. Under such atmospheric conditions the wet-bulb temperature cannot exceed 100°C (process A). When the dry-bulb temperature reaches 125°C, the relative humidity is dropped within the region of harsh wood conditions, potentially leading to poor product quality.
  • process B with a wet-bulb temperature of 125°C, in a pressure autoclave with pure steam operating at 2,45 bar (absolute pressure), the dry bulb temperature can be increased to 140°C to obtain a relative humidity of 60%, still within the preferred mild region.
  • process A would be operated at 60%> relative humidity the dry-bulb should not exceed 115°C, a temperature where the curing rate is relatively low.
  • process C with a wet-bulb temperature of 160°C, in a pressure autoclave with pure steam operating at 6,75 bar (absolute pressure), the dry-bulb temperature may even be increased to 180°C to obtain a relative humidity of 60%, to achieve a very fast curing process.
  • process B and C are substantially advantageous with respect to process A and there preferred over process A.
  • untreated wood is effectively thermally modified.
  • Thermally modified wood shows a number of similar properties as chemically modified wood (notably reduced moisture swelling and increased resistance against wood-degrading fungi) but shows a major difference with respect to mechanical strength.
  • Chemical modification strengthens the wood opposed to thermal modification where strength is weakened.
  • Chemical modification is also generally more effective against fungi and other wood-deteriorating organisms.
  • High wet-bulb temperatures enable a new type of hybrid modifiation process on surface impregnated wood, to achieve a solid wood product with a thermally modified core and a surface-enhanced chemically modified layer, upgrading the overall performance of the wood product with a minimum of additives used.
  • the data used in the chart 49 are list in the table below.
  • sapwood of pine pine impregnated with a furane oligomer would be subjected to process B with a environmental dry bulb temperature of 140°C in a pure steam atmosphere of 2,45 bar (corresponding to a wet bulb temperature of 125°C), the sapwood will become chemically modified without cracking, splitting or deformation of the wood.
  • the sapwood will become merely thermally modified, wherein the shrinkage of the wood has been reduced to about 50% and the sensitivity to Basidiomycetes has been reduced substantially.
  • the bending strength has been reduced with 15%).
  • the outer surface layer of the same sapwood is impregnated with a with a furane oligomer after which the impregnated sapwood is subjected to process C with a environmental dry bulb temperature of 180°C in a pure steam atmosphere of 6,75 bar (corresponding to a wet bulb temperature of 160°C)
  • the core of the sapwood will become thermally modified and the outer surface layer (shell) of the sapwood will become both thermally and chemically modified without cracking, splitting or deformation of the wood.
  • the bending strength has been improved with 15%).
  • the outer surface layer (shell) has obtained an increased durability, which allows the modified wood to be applied in moist environments, such as in the soil.

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Abstract

The invention relates to a method for modifying wood. The invention also relates to a wood product. The invention further relates to an apparatus for performing the method according to the invention. The modification process according to the invention has a relatively short process time, wherein a good modification is realized while the wood is not distorted by stresses and checks.

Description

Method and apparatus for modifying wood, and wood product
The invention relates to a method for modifying wood, in particular to preserve wood and/or to improve the dimensional stability. The invention also relates to a wood product. The invention further relates to an apparatus for performing the method according to the invention.
Upgrading of wood by hydrothermo lysis is known. In a hydrothermo lysis wood is treated with steam at a dry bulb temperature between 160-190°C, wherein a
hemicellulose and lignin become reactive. In a subsequent step the wood is cooled and cured by drying, wherein the reactive hemicellulose and lignin form cross-links. The final product is wood which has acquired a greater durability and fungal resistance than the untreated wood. Since all that is required for the reaction is water in the form of steam, hydrothermo lysis is particularly advantageous compared to preserving methods in which the wood is upgraded with impregnating agents usually having an
environmental impact. However, drawbacks of known hydrothermo lysis methods are that they are particularly time-consuming and, moreover, leads to affection of the structural properties of the wood, whereas wood will easily split during this process, which is undesired. More specifically, the wood is treated in multiple individual steps with interim cooling and heating of the wood. Time is lost here and the wood is placed under great internal stresses as a result of contraction and expansion, which result in splitting and deformation. This results in high costs due to longer production times on the one hand and to a decrease in the economic value of the wood on the other. More rapid methods of thermal preservation are known, wherein dried wood is heated at substantially atmospheric pressure to very high dry bulb temperatures above 220 degrees Celsius. However, the drawback of this rapid method is again that the mechanical strength of the product decreases very greatly when compared to the starting products. Rapid thermal treatment methods with less high dry bulb temperatures result in products with a reduced durability when compared to the products at higher dry bulb temperatures. The known, relatively rapid methods also produce a high percentage of products of low-grade quality due to splitting and deformation. It is an object of the invention to enable a rapid modification of wood with relatively little loss in structural properties, in particular regarding distortions and checks.
The invention provides for this purpose a method for modifying wood, comprising the processing steps of: A) impregnating wood to be modified with a reactive composition, in particular a polymerisable composition, and B) allowing the impregnated wood to react in an overheated steam filled treatment space by heating the treatment space to a dry bulb temperature of at least 70 degrees Celsius, after which the dry bulb temperature in the treatment space is raised gradually with a dry bulb temperature gradient of a maximum of 40 degrees Celsius per hour, preferably between 20-40 degrees Celsius per hour, to a maximum dry bulb temperature in the treatment space of between 120 and 206 degrees Celsius; wherein at said maximum dry bulb temperature: i) the relative humidity is between 50% and 90%, ii) the wet bulb temperature in the treatment space is between 105 and 176 degrees Celsius, and iii) the wood is heated during a reaction time of at least 10 minutes. During step B) the composition impregnated in the wood will react chemically in a controlled and selective humid atmosphere, as a result of which the wood will be chemically modified and hence be preserved long- lastingly while the favourable properties of the wood, such as its mechanical strength and dimensional stability, will be improved as much as possible. In case the maximum dry bulb temperature would exceed 140 degrees Celsius, and would be situated between 140 and 206 degrees Celsius, the wood is modified both thermally and chemically simultaneously during the same step of the (single) treatment process. In case the maximum dry bulb temperature would be situated between 120 and 140 degrees Celsius, commonly merely a chemical modification of the wood will be realized.
Allowing the wood to react under the influence of heat and in a controlled humid environment, will lead to a controlled modification process of the wood. To this end, the presence of steam, preferably with a controlled humidity, is important to counteract drying out of the wood during the treatment according to the invention as much as possible, which is in favor of the efficacy and the yield of the treatment to obtain modified wood with the desired properties. It is noted that in case no steam would be used during step B) wood would be obtained commonly having poor properties and hence often insufficient quality for further use. The selective combination of the dry bulb temperature and the wet bulb temperature, together determining the relative humidity, is important to come to a controlled and relatively fast treatment of the wood without affecting the quality of the wood. It has been found that wood can be treated best at a relative humidity (RH) of between 50% en 90%. At a relative humidity below 50% wood will easily split and/or deform which will affect the quality of the wood. At a relative humidity above 90% no sufficient and satisfying curing can be established whereas e.g. solvents used in the reactive composition will hardly evaporate at this high degree of relative humidity. By applying a purposively selected relative humidity range of 50-90% a very good climate is created for chemical and thermal wood treatment. Within this advantageous relative humidity range the dry bulb temperature could vary from about 100 degrees Celsius (at a RH of 90%>) to about 120 degrees Celsius (at a RH of 50%)) in case an open (or closed) treatment space would be applied in which a substantially atmospheric pressure would be present. Since the wet bulb temperature is directly related to the pressure, the wet bulb temperature would be about 100 degrees Celsius in this situation. Increasing the dry bulb temperature will lead to an increase of the treatment rate of the wood and is therefore often desired. However, simply increasing the dry bulb temperature within the treatment space will lead to an undesired drop of the relative humidity to a level less than 50%. It has been found that the dry bulb temperature could be increased to speeden up the treatment process, without leaving the desired relative humidity range of 50-90%), by increasing the wet bulb temperature in the treatment space to a temperature between 105 and 176 degrees Celsius. This increase of the wet bulb temperature can be established by increasing the (partial) steam pressure within the steam vessel to a pressure between 1 ,25 bar
(corresponding to a wet bulb temperature of 105 degrees Celsius) and 10 bar
(corresponding to a wet bulb temperature of 176 degrees Celsius). To this end, the treatment space is preferably substantially sealed to realize a pressure chamber. Higher wet bulb temperatures and hence higher pressure would be conceivable in theory, though will require very robust steam vessels which are commonly subjected to strict legal regulations. Moreover, these higher wet bulb temperatures and hence higher pressure will often have a negative impact of the treated wood. For example, a wet bulb temperature above 200 degrees Celsius would imply a pressure of about 17 bar which will simply destroy the wood structure. Hence, by taking a desired relative humidity as a starting point, the dry bulb temperature to a desired level can be increased by also increasing the wet bulb temperature, the latter to be established by increasing the (partial) steam pressure in the treatment space. Preferably, this superatmo spheric pressure is completely determined by the steam pressure as such. Application of additional (inert) gases are commonly not preferred, since it has been found that this could easily deregulate the wood treatment process.
Wood impregnated and reacted (cured) with a reactive composition, in particular a polymerisable composition, in a controlled humid environment according to the invention shows improved properties such as improved durability, dimensional stability and surface hardness. In addition, the obtained wood shows enhanced resistance against degradation by biological organisms, e.g. fungi, without exerting biocidal effects towards such organisms. Furthermore wood modified according to the present invention exhibits e.g. enhanced UV stability, cracking resistance, rot resistance and decay resistance. In addition, the present wood shows an increased lifetime, is of a consistent quality. It is further noted that the present wood is environmentally friendly, since wood that has been impregnated and reacted in accordance with the present invention has qualities which are comparable with tropical hard wood, and is therefore an ideal substitute thereof. Also, the present wood does not have toxicity to organisms in the environment, including humans. Even at the end-of-life, toxic compounds are not released from the woods obtained by applying the method according to the invention. Waste of wood components due to damage by for instance splitting is also exceptionally low. The reactive compositions, in particular polymerisable compositions, applied are able to penetrate into the cell structure of wood (step A) and are subsequently polymerized or reacted in another manner in situ (step B). The composition becomes an integral part of the wood cell- wall structure, modifies the wood cell wall and stable impregnated wood is obtained. Preferably, the reactive composition remains stable at increased dry bulb temperature according to step B) and will not be decomposed due to heating. Different reactive compositions may be used for impregnation during step A), wherein the chemical reaction during the heat treatment according to step B) is dependent on the nature of the reactive composition used. As an example, the following non- limitative reactive compositions may be used in the method according to the invention, wherein the chemical reaction type is indicated in parenthesis: acetic anhydride (acetylation); melamine (melamine resin); (methylated-)
dimethyloldihydroxyethyleneurea (DMDHEU); furfurylalcohol (furfurylation);
alkoxysilane (silicone/silane); and linseed oil, natural resin, parafin (oil/wax/parafms).
In an embodiment of the method according to the invention, during step B) the relative humidity within the treatment space is held at a substantially constant level, preferably between 60% and 85%, more preferably between 65% and 80%>, most preferably at (about) 75%. By maintaining the relative humidity within the treatment space at a substantially constant level, the moisture content of the wood can be controlled in a satisfying manner, which is in favor of the final quality of the modified wood obtained.
In another embodiment of the method according to the invention a water supply container is positioned within the treatment space, wherein during step B) water is evaporated from the water supply container to humidify the treatment space. The quantity of water to be evaporated from the water supply container will commonly be controlled by the combination of the dry bulb temperature within the treatment space and the temperature of the water supply container, wherein the dry bulb temperature can commonly be regulated by independent heating means adapted to heat the treatment space commonly enclosed by (a thermal oil jacket of) an autoclave and the water supply container. By applying e.g. a dry bulb temperature sensor and/or a humidity and/or a pressure sensor (to determine the wet bulb temperature), connected via a control unit to said heating means, a self-regulating humid microclimate within the treatment space can be established relatively easily.
The manner to impregnate the wood to be modified with a composition is to place the wood in a treatment vessel wherein a vacuum is applied, after which the wood is exposed to the composition while substantially maintaining said vacuum, and wherein a predetermined air pressure of between 6 and 14 bar is applied to the wood for a period of time sufficient to partially impregnate the wood with the composition. Subsequently, the pressure within the treatment vessel is reduced and the surplus of composition is removed from the treatment vessel. Since during step B) the wood may be progressively thermally modified by applying increasing temperatures above 140°C, it is thinkable to merely partially impregnate by the reactive composition, in particular the polymerisable composition, during step A). In this case, an outer shell of the wood may be
impregnated, while a core of the wood will remain unimpregnated. Partially
impregnating the wood with the reactive composition, in particular the polymerisable composition, will commonly be cheaper than fully impregnating the wood with the reactive composition, in particular the polymerisable composition, due to material savings. However as said, in this case it is preferred to subject the wood, and in particular the unimpregnated part of the wood, commonly the core of the wood, to a thermal modification treatment at a dry bulb temperature of between 140 and 206 degrees Celsius, preferably about 190 degrees Celsius. Unwanted chemical and/or mechanical reactions can take place in the wood at dry bulb temperatures above 206 degrees.
In case the wood is impregnated substantially completely with the polymerisable composition, merely a chemical modification at a maximum dry bulb temperature of between 120 and 140 degrees Celsius is commonly required to obtain modified wood with desired properties. Hence, an additional thermal treatment (realized at dry bulb temperatures above 140 degrees Celsius) is not required.
During step A) the initial dry bulb temperature of the wood is normally the ambient dry bulb temperature, usually between 15 and 25 degrees Celsius. In the starting situation, prior to step A), the wood generally has a moisture content of between 3-18% by weight (of the dry wood mass). Since the reactive composition often comprises a liquid compound, in particular a liquid carrier, the moisture content of the wood will be increased during step A). In case the wood is humidified during step A), it is commonly preferred to reduce the moisture content of the wood to lower values of between 6 and 20% by weight by drying the wetted wood during step C) prior to execution of step B) to enable the existence of a hygroscopic equilibrium between the wood and the environment surrounding the wood, both during and after step B), which will commonly be in favor of a consistent quality of the modified wood obtained.
It is commonly advantageous in case the method further comprises step D) comprising removing at least a substantial fraction of air, in particular oxygen, from the treatment space prior to execution of step B). The removal of air, in particular oxygen, from the treatment space during step D) can for instance take place by displacement of air by an inert gas such as nitrogen or argon, or by steam. If air is not removed, oxygen from the presence air may lead to unwanted reactions during the modification process. The best results are achieved if the oxygen is removed by creating a vacuum in the treatment space. If a vacuum has been created in the treatment space during step D), the steam can be used to supplement the vacuum. Placing the treatment space under reduced pressure (creating a vacuum) is found to be a more rapid and effective method of removing oxygen than other methods, such as displacing air by means of nitrogen or steam. Creating a vacuum moreover simplifies control of the process: the degree of pressure decrease can be determined using a simple pressure gauge and is a reliable measure of the quantity of air, and thereby oxygen, removed. In an embodiment the reduced pressure is lower than 13 kPa (absolute pressure). This results in a proper removal of oxygen from the treatment space. During the reduced pressure the wall dry bulb temperature of the treatment space can optionally be increased to 50-70 degrees Celsius for an even better removal of oxygen. The time required for the process is moreover shortened since a start is already made with pre-heating for the subsequent processing step B).
The chemical reaction according to step B) can be stopped by reducing the dry bulb temperature to below 120 degrees Celsius, and then further to room temperature. The cooling process and conditions are dependent on the reactive composition used. During step B) the heated wood may be compressed in the treatment space to obtain a wood product with a greater density.
It is advantageous if the steam has a maximum degree of saturation of 95% during step C). The degree of saturation is the percentage relative to 100% saturated steam at the same pressure and dry bulb temperature. This produces a better wood product, and in particular less splitting, than a comparable process in which saturated steam is used. A significant factor here is probably that condensation of water is largely prevented.
In an embodiment of the method according to the invention, the reactive substance is formed by a polymerisable substance comprising a chemical compound of formula I and/or formula II
Figure imgf000009_0001
Formula I
Figure imgf000010_0001
Formula II wherein n is an integer between 0 and 20, preferably between 0 and 10, and more preferably between 0 and 5 wherein t and s each independently are an integer between 1 and 20, preferably between 1 and 10, and more preferably between 1 and 5, wherein w and z each independently are 0 or 1 , wherein X and Y each independently are O, S or N-R21 and wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R18, R19, R21 are each independently hydrogen or selected from the group comprising C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C5-C12 heteroaryl, carboxaldehyde, hydroxyl, hydroxyalkyl, carboxyl, amino, nitro, formyl, alkylamino, aminoalkyl, alkylaminoalkyl, furyl, furylalkyl, hydroxyalkylfurylalkyl, alkyloxy, alkoxyalkyl, alkenyloxy, alkylcarbonylalkenyl, oxiranyl, alkylcarbonyloxyalkyl, alkyloxycarbonylalkenyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyl, alkenylcarbonyl, halocarbonyl, haloalkyl, haloaryl, haloalkenyl, imino, thiol, alkylthio, thioalkyl, alky It hio alkyl, cyano, alkylsulfonyl, sulfonic acid, and any mixtures thereof, whereby each group is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, wherein R17 and R20 are each independently selected from the group comprising C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C5-C12 heteroaryl, carboxaldehyde, hydroxyl, hydroxyalkyl, carboxyl, amino, nitro, formyl, alkylamino, aminoalkyl, alkylaminoalkyl, furyl, furylalkyl, hydroxyalkylfurylalkyl, alkyloxy, alkoxyalkyl, alkenyloxy, alkylcarbonylalkenyl, oxiranyl, alkylcarbonyloxyalkyl, alkyloxycarbonylalkenyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyl, alkenylcarbonyl, halocarbonyl, haloalkyl, haloaryl, haloalkenyl, imino, thiol, alkylthio, thioalkyl, alkylthio alkyl, cyano, alkylsulfonyl, sulfonic acid, and any mixtures thereof, whereby each group is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, and wherein the dotted line represents an optional double bond. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art. When describing the compounds used in the method according to the invention, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.
The term "alkyl" by itself or as part of another substituent, refers to a straight or branched saturated hydrocarbon group joined by single carbon-carbon bonds having 1 to 20 carbon atoms, for example 1 to 10 carbon atoms, for example 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1, 2, 3 or 4 carbon atoms. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. Thus, for example, C1-C4 alkyl means an alkyl of one to four carbon atoms. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, pentyl iso-amyl and its isomers, hexyl and its isomers, heptyl and its isomers and octyl and its isomer. When the term "alkyl" is used as a suffix following another term, as in "hydroxyalkyl," this is intended to refer to an alkyl group, as defined above, being substituted with one or two (preferably one) substituent(s) selected from the other, specifically-named group, also as defined herein. As used herein, the term C1-C20 alkyl refers to an alkyl of 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
The term "alkenyl" by itself or as part of another substituent, refers to a straight or branched alkyl chain containing at least one unsaturation in the form of a single carbon to carbon double bond and having 2 to 20 carbon atoms, for example 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2, 3 or 4 carbon atoms.
Examples of alkenyl groups are ethenyl (vinyl), 2-propenyl, 2-butenyl, 3-butenyl, 2- pentenyl and its isomers, 2-hexenyl and its isomers, 2-heptenyl and its isomers, 2- octenyl and its isomers, 2,4-pentadienyl and the like. As used herein, the term C2-C20 alkenyl refers to an alkenyl of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. The term "alkynyl" by itself or as part of another substituent, refers to a straight or branched alkyl chain containing at least one unsaturation in the form of a single carbon to carbon triple bond and having 2 to 20 carbon atoms, for example 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and for instance 2, 3, 4, 5 or 6 carbon atoms. Examples of alkynyl groups are ethynyl, 2- propynyl, 2-butynyl, 3- butynyl, 2-pentynyl and its isomers, 2-hexynyl and its isomers, 2-heptynyl and its isomers, 2-octynyl and its isomers and the like. As used herein, the term C2-C20 alkynyl refers to an alkynyl of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
Where alkyl groups as defined are divalent, i.e., with two single bonds for attachment to two other groups, they are termed "alkylene" groups. Non-limiting examples of alkylene groups includes methylene, ethylene, methylmethylene, trimethylene, propylene, tetramethylene, ethylethylene, 1 ,2-dimethylethylene, pentamethylene and
hexamethylene. Similarly, where alkenyl groups as defined above and alkynyl groups as defined above, respectively, are divalent radicals having single bonds for attachment to two other groups, they are termed "alkenylene" and "alkynylene" respectively. The term "aryl" as used herein by itself or as part of another group refers but is not limited to 5 to 24 carbon-atom homocyclic (i.e., hydrocarbon) monocyclic, bicyclic or tricyclic aromatic rings or ring systems containing 1 to 4 rings which are fused together or linked covalently, typically containing 5 to 8 atoms; at least one of which is aromatic. The aromatic ring may optionally include one to three additional rings (either cycloalkyl, heterocyclyl or heteroaryl) fused thereto. Non-limiting examples of aryl comprise phenyl, biphenylyl, biphenylenyl, 5- or 6-tetralinyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azulenyl, 1- or 2- naphthyl, 1-, 2- or 3-indenyl, 1-, 2- or 9-anthryl, 1- 2-, 3-, 4- or 5- acenaphtylenyl, 3-, 4- or 5-acenaphtenyl, 1-, 2-, 3-, 4- or 10-phenanthryl, 1- or 2- pentalenyl, 1 , 2-, 3- or 4-fluorenyl, 4- or 5-indanyl, 5-, 6-, 7- or 8-tetrahydronaphthyl, 1 ,2,3,4-tetrahydronaphthyl, 1 ,4- dihydronaphthyl, dibenzo[a,d]cylcoheptenyl, 1-, 2-, 3-, 4- or 5-pyrenyl. As used herein, the term C5-C24 aryl refers to an aryl of 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, or 24 carbon atoms. The term
"heteroaryl" as used herein by itself or as part of another group refers but is not limited to 5 to 12 carbon-atom aromatic rings or ring systems containing 1 to 3 rings which are fused together or linked covalently, typically containing 5 to 8 atoms; at least one of which is aromatic in which one or more carbon atoms in one or more of these rings can be replaced by oxygen, nitrogen or sulfur atoms where the nitrogen and sulfur heteroatoms may optionally be oxidized and the nitrogen heteroatoms may optionally bequaternized. Such rings may be fused to an aryl, cycloalkyl, heteroaryl or
heterocyclyl ring.
The term "hydroxyalkyl" refers to a -Rb-OH group wherein Rb is alkylene as defined herein.
The term "amino" refers to the group -NH2.
The term "alkylamino" refers to the group -N(Re)(Rf) wherein Re and Rf are each independently selected from hydrogen and alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5- C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, alkylfuryl, furylalkyl,
hydro xyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "aminoalkyl" refers to the group -Rb-NH2 wherein Rb is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "alkylaminoalkyl" refers to the group -Rb-NReRf wherein Rb is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2- C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, alkylfuryl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, Re is hydrogen or alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, alkylfuryl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, and R is hydrogen or alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2- C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "carboxy" is equivalent to "hydroxycarbonyl" and refers to the group - C02H. The term "alkylcarboxy" is equivalent to "alkyloxycarbonyl" and refers to the group - C02-Ra, wherein Ra is alkyl which is optionally substituted with one or more substituents selected from Ci-C2o alkyl, C2-C2o alkenyl, C2-C2o alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. The term "alkenylcarboxy" is equivalent to "alkenyloxycarbonyl" and refers to the group -C02-Rc, wherein Rc is alkenyl which is optionally substituted with one or more substituents selected from Ci-C2o alkyl, C2-C2o alkenyl, C2-C2o alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. The term carboxaldehyde or formyl refers to the group C(=0)H.
The term "furyl" refers to the group represented by formula III:
Figure imgf000014_0001
formula III
Asterisks (*) are used herein to indicate the point at which a mono-, bi- or trivalent radical depicted is connected to the structure to which it relates and of which the radical forms part. The term "furylalkyl" refers to the group -Rb-furyl, wherein furyl is as defined above and Rb is alkylene which is optionally substituted with one or more substituents selected from Ci-C2o alkyl, C2-C2o alkenyl, C2-C2o alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. The term "hydroxyalkylfurylalkyl" refers to the group -Rb-furyl-Rb-OH, wherein furyl is as defined above and Rb is alkylene as defined above.
The term "alkylfuryl" refers to the group -furyl-Rb, wherein furyl is as defined above and Rb is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl,
halocarbonyl, thiol, and alkylthio. The term "alkoxy" or "alkyloxy" refers to the group -0-Ra wherein Ra is alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino,
hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. The term "alkoxyalkyl" or "alkyloxyalkyl" refers to the group -Rb-0-Ra wherein Ra is alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio and Rb alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. The term "alkenyloxy" refers to the group -0-Rb wherein Rb is alkenyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. An example is vinyl ether.
The term alkyloxy carbonylalkenyl refers to the group -Rd-C(=0)-0-Ra, wherein Rd is alkenylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, and Ra is alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "oxiranyl" refers to the epoxy group -C2H3O. The term "alkylcarbonyl" refers to the group-C(=0)Ra, wherein Ra is alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. Said alkylcarbonyl can be exemplified by acetyl, propionyl, butyryl, valeryl and pivaloyl.
The term "alkenylcarbonyl" refers to the group -C(=0)Rc wherein Rc is alkenyl as which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. An example hereof is vinyl ketone.
The term "alkylcarbonyloxyalkyl" refers to the group -Rb-0-C(=0)Ra wherein Rb is alkylene which is optionally substituted with one or more substituents selected from d- C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, and Ra is alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "alkenylcarbonyloxyalkyl" refers to the group -Rb-0-C(=0)Rc wherein Rb is alkylene which is optionally substituted with one or more substituents selected from Ci- C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. above and Rc is alkenyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl,
hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "alkylcarbonylalkenyl" refers to the -Rd-C(=0)-Ra group wherein Rd is alkenylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, and Ra is alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "isocyanate" refers to the group -N=C=0. The term isocyanate-alkyl refers to the group -Ra-isocyanate, wherein Ra is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5- C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl,
hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "nitro" refers to the group -NO2. The term "cyano" refers to the group -CN.
The term "imino" refers to the group -C(=NH)Rg wherein Rg is alkyl, alkenyl or aryl which are each optionally substituted with one or more substituents selected from Ci- C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "thiol" or ""sulfhydryl" refers to the group -SH. The term "alkylthio" refers to the group -SRa group wherein Ra is alkyl which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. This term refers to a group consisting of a sulfur atom attached to an alkyl group. Non- limiting examples of alkylthio groups include methylthio (SCH3), ethylthio (SCH2CH3), n- propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n- hexylthio, and the like. The term "thioalkyl" refers to the group -Rb-SH wherein Rb is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio. Non- limiting examples of thioalkyl groups include thio methyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl, thioheptyl, thiooctyl, thiooctadecyl, and the like. The term alkylthioalkyl" refers to the group -Rb-S-Ra wherein Rb is alkylene which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2- C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio and Ra is alkyl which is optionally substituted with one or more substituents selected from d- C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "sulfonic acid" refers to the group -S(=0)20H.
The term "alkylsulfonyl" refers to the group -S(=0)2Ra wherein Ra is alkyl as which is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio.
The term "halo" or "halogen" as a group or part of a group is generic for fluoro, chloro, bromo or iodo. The term "haloalkyl" refers to an alkyl radical having the meaning as defined above wherein one or more hydrogen atoms are replaced with a halogen as defined above. Non-limiting examples of such haloalkyl radicals include chloromethyl, 1-bromoethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1 ,1 ,1 -trifluoroethyl and the like.
The term "haloalkenyl" refers to an alkenyl radical having the meaning as defined above wherein one or more hydrogen atoms are replaced with a halogen as defined above. The term "halocarbonyl" refers to the group -C(=0)-Hal wherein Hal refers to a halogen as defined above. Non-limiting examples of such halocarbonyl radicals include chlorocarbonyl (-C(=0)C1), bromocarbonyl (-C(=0)Br) or fluorocarbon (-C(=0)F). The term "haloaryl" refers to an aryl radical having the meaning as defined above wherein one or more hydrogen atoms are replaced with a halogen as defined above.
Whenever the term "substituted" is used in the present invention, it is meant to indicate that one or more hydrogen atoms on the atom indicated in the expression using
"substituted" is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a chemically stable compound, i.e. a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture.
Whenever used in the present invention the term "compounds of the invention" or a similar term is meant to include the compounds of formula I, formula II, formula ΙΓ, and formula IV and V (see below) as defined herein.
The terms "composition", "impregnation composition", "impregnating solution" and "furan resin" are used herein as synonyms, and all refer to a composition comprising substituted furan compounds as defined herein.
In another preferred embodiment, the invention relates to the use of a composition as defined above, comprising furan compounds of formula I and/or formula II wherein n is an integer between 0 and 5, and preferably is 0, 1 , 2, 3, 4, or 5 wherein t and s each independently are an integer between 1 and 5, and preferably each are 1 or 2, wherein w and z each independently are 0 or 1 , wherein X and Y each independently are O, S or N-R21 and wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15' R16, R18, R19, R21 are each independently hydrogen or selected from the group comprising C1-C20 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, amino, nitro, alkylamino, aminoalkyl, alkoxyalkyl, alkylaminoalkyl, alkylcarboxy, alkenylcarboxy, furyl, furylalkyl, hydroxyalkylfurylalkyl, alkyloxy, alkenyloxy, alkylcarbonylalkenyl, oxiranyl, alkenylcarbonyl, alkylcarbonyloxyalkyl, alkyloxycarbonylalkenyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, alkylcarbonyl, halocarbonyl, haloalkyl, haloaryl, haloalkenyl, imino, thioalkyl, alkylthioalkyl, cyano and any mixtures thereof, and preferably from the group comprising, C1-C20 alkyl,
carboxaldehyde, hydroxyalkyl, carboxyl, alkylamino, aminoalkyl, alkylaminoalkyl, alkyloxy, alkoxyalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkenyloxy,
alkylcarbonylalkenyl, alkenylcarbonyl, alkylcarbonyloxyalkyl,
alkyloxycarbonylalkenyl, alkenylcarbonyloxyalkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyl, and any mixtures thereof, and even more preferred from the group comprising C1-C10 alkyl, carboxaldehyde, hydroxyalkyl, alkylamino, aminoalkyl, alkylaminoalkyl, alkyloxy, alkoxyalkyl, furylalkyl, hydroxyalkylfurylalkyl, carboxyl, alkenyloxy, alkylcarboxy, alkenylcarboxy, alkylcarbonyl, alkenylcarbonyl, and any mixtures thereof, and still more preferred from the group comprising C1-C10 alkyl, carboxaldehyde, hydroxyalkyl, aminoalkyl, alkylaminoalkyl, alkoxyalkyl, furylalkyl, hydroxyalkylfurylalkyl, carboxyl, and any mixtures thereof, whereby each group is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, and wherein R17 and R20 are each independently selected from the group comprising C1-C20 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, amino, nitro, alkylamino, aminoalkyl, alkoxyalkyl, alkylaminoalkyl, alkylcarboxy, alkenylcarboxy, furyl, furylalkyl, hydroxyalkylfurylalkyl, alkyloxy, alkenyloxy, alkylcarbonylalkenyl, oxiranyl, alkenylcarbonyl, alkylcarbonyloxyalkyl, alkyloxycarbonylalkenyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, alkylcarbonyl, and any mixtures thereof, and preferably from the group comprising C1-C20 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, alkylamino, aminoalkyl, alkylaminoalkyl, alkyloxy, alkoxyalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkenyloxy, alkylcarbonylalkenyl, alkenylcarbonyl, alkylcarbonyloxyalkyl, alkyloxycarbonylalkenyl,
alkenylcarbonyloxyalkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyl, and any mixtures thereof, and even more preferred from the group comprising C1-C10 alkyl, carboxaldehyde, hydroxyalkyl, alkylamino, aminoalkyl, alkylaminoalkyl, carboxyl, alkyloxy, alkoxyalkyl, furylalkyl, hydroxyalkylfurylalkyl alkenyloxy, alkylcarboxy, alkenylcarboxy, alkylcarbonyl, alkenylcarbonyl, and any mixtures thereof, and still more preferred from the group comprising C1-C10 alkyl, carboxaldehyde, hydroxyalkyl, aminoalkyl, carboxyl, and any mixtures thereof, whereby each group is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, and wherein the dotted line represents a double bond.
In another preferred embodiment the invention relates to the use of a composition comprising a compound of formula I and/or formula II, wherein n is 0, 1 , 2, 3, 4 or 5 wherein t and s each independently are 1 or 2, wherein w and z each independently are 0 or 1 , wherein X and Y each independently are O, S or N-R21 and wherein R2, R3, R4, R5, R6, R7, R9, R10, R11, R12, R13, R14, R15, R16, R18, R19, R21 are each independently hydrogen or selected from the group comprising C1-C2 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, aminoalkyl, alkylaminoalkyl hydroxyalkylfurylalkyl, alkyloxy, alkoxyalkyl, alkylcarbonylalkenyl, alkylcarbonyloxyalkyl, alkyloxycarbonylalkenyl, alkenylcarbonyloxyalkyl, oxiranyl, isocyanate, isocyanate-alkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyl, alkenylcarbonyl, halocarbonyl, haloalkyl, haloaryl, haloalkenyl, imino, thioalkyl, alkylthioalkyl, cyano and any mixtures thereof, whereby each group is optionally substituted with one or more substituents selected from C1-C2 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, hydroxyl, carboxyl, nitro, amino, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, and thiol, wherein R1, R8, R17 and R20 are each independently selected from the group comprising C1-C2 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, aminoalkyl, alkylaminoalkyl,
hydroxyalkylfurylalkyl, alkyloxy, alkoxyalkyl, alkylcarbonylalkenyl,
alkylcarbonyloxyalkyl, alkyloxycarbonylalkenyl, alkenylcarbonyloxyalkyl, oxiranyl, isocyanate, isocyanate-alkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyl,
alkenylcarbonyl, halocarbonyl, haloalkyl, haloaryl, haloalkenyl, imino, thioalkyl, alkylthioalkyl, cyano and any mixtures thereof, whereby each group is optionally substituted with one or more substituents selected from C1-C2 alkyl, C2-C4 alkenyl, C2- C4 alkynyl, hydroxyl, carboxyl, nitro, amino, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, and thiol, and wherein the dotted line represents a double bond.
In another preferred embodiment the invention relates to the use of a composition comprising a compound of formula I and/or formula II wherein n is an integer between 0 and 5 wherein t and s each independently are 1 or 2, wherein w and z each independently are 0 or 1 , wherein X and Y are each independently O, S or N-R21 and wherein R2, R3, R4, R5, R6, R7, R9, R10, R11, R12, R13, R14, R15, R16, R18, R19, R21 are each independently hydrogen or selected from the group comprising C1-C2 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, aminoalkyl, alkylaminoalkyl
hydroxyalkylfurylalkyl, alkoxyalkyl, oxiranyl and isocyanate, wherein R1, R8, R17 and R20 are each independently selected from the group comprising Ci-C2 alkyl, carboxaldehyde, hydroxyalkyl, carboxyl, aminoalkyl, alkylaminoalkyl,
hydroxyalkylfurylalkyl, alkoxyalkyl, oxiranyl and isocyanate, and wherein the dotted line represents a double bond.
In another preferred embodiment of the invention the a composition is used comprising a compound of formula I and/or formula II, wherein n is 0, 1 , 2, 3, 4, or 5, wherein t is 1 or 2, wherein s is 1 or 2, wherein w is 0 or 1 , wherein z is 0 or 1 , wherein X is O, S or N-R21 , and wherein Y is O, S or N-R21; wherein R1 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, - CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3- N=C=0, -0-CH=CH2, -C(=0)OCH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0- C(=0)-CH=CH2, wherein R2 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-C8 alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R3 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-C8 alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, -C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, - C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R4 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R5 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R6 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, -
C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R7 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R8 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=0)OCH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R9 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanatealkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2 -fury I- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R10 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R11 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R12 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R13 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H3O, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-fliryl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R14 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-C8 alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R15 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-C8 alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, -
C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R16 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-C8 alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R17 is selected from the group comprising Ci-Cs alkyl, C2-C8 alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl,
hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is - CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -N02, - C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, -C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R18 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-C8 alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, - CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -N02, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, -C(=0)OCH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or - CH2-0-C(=0)-CH=CH2, wherein R19 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, - CH2OH, -CH2NH2, -COOH, -C(=0)H, -N02, -C2H30, - CH2NH2, -N=C=0, -CH3- N=C=0, -0-CH=CH2, -C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0- C(=0)-CH=CH2, wherein R20 is selected from the group comprising Ci-Cs alkyl, C2-Cs alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, -
C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, wherein R21 is hydrogen or selected from the group comprising Ci-Cs alkyl, C2-C8 alkenyl, carboxaldehyde, hydroxyalkyl, carboxyl, formyl, aminoalkyl, alkylaminoalkyl, furylalkyl, hydroxyalkylfurylalkyl, alkylcarboxy, alkenylcarboxy,
alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, and even more preferred is -CH3, - C2H5, -C3H7, -C4H9, -CH2=CH, -CH2OH, -CH2NH2, -COOH, -C(=0)H, -NO2, -C2H30, - CH2NH2, -N=C=0, -CH3-N=C=0, -0-CH=CH2, - C(=O)0CH3, -C(=0)OC2H5, -CH2-furyl- CH2OH or -CH2-0-C(=0)-CH=CH2, whereby each R group is optionally substituted with one or more substituents selected from Ci- C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, and preferably by one or more substituents selected from C1-C2 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, hydroxyl, carboxyl, nitro, amino, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, and thiol, and wherein the dotted line represents a double bond.
In another preferred embodiment, non-limiting examples of furan compounds comprised in a composition used in the method according to the invention include but are not limited to 2,5- bis(hydroxymethyl)furan; 2,3,5-tris(hydroxymethyl)furan; 5- methyl-2-furfuryl alcohol, 3- hydroxymethyl-5-methyl-2-furfurylalcohol; 2,2'- (hydroxymethyl)difurylmethane; 2, 2', 3,3'- (hydroxymethyl)difurylmethane; 2,2',4,4'- (hydroxymethyl)difurylmethane; 5- hydroxymethyl- [alpha] -(methyl)furfuryl alcohol; 5- hydroxymethyl-2-furancarboxaldehyde; 3,5- hydroxymethyl-2-furancarboxaldehyde; 4,5-hydroxymethyl-2-furancarboxaldehyde; 5- methyl-2-furancarboxaldehyde; 3- hydroxymethyl-5-methyl-2-furancarboxaldehyde; 5-nitro furfuraldehyde; 2,5- bis(carboxaldehyde)furan; 3-hydroxymethyl-2,5- bis(carboxaldehyde)furan; 4- hydroxymethyl-2,5-bis(carboxaldehyde)furan; 5- hydroxymethyl-2-furoic acid; 5- methyl-2-furoic acid; 5-carboxaldehyde-2-furoic acid; 2,5- furandicarboxylic acid; 2,5- furan diacid dichloride; 2,5-furan dicarboxylic acid dimethyl ester; 5-hydroxymethyl-2- furfurylamine; 5-methyl-2-furfurylamine; 5-carboxaldehyde-2- furfurylamine; 5- carboxy-2-furfurylamine; 2,5-bis(aminomethyl)furan; 5-methyl-2- vinylfuroate; 5- tertbutyl-2-vinyl furoate; 5-methyl-2-vinyl furan; 5-methyl-2-furfurylidene acetone; 5- methyl-2-furyloxirane; 5 -methyl- fur furyl vinyl ether; 5-hydroxymethyl-2-ethyl furanacrylate; bis-(2,5-isocyanatemethyl) furan; and bis(2,5-isocyanate) furan; or any mixtures thereof.
In an embodiment, the impregnating composition used in the method according to the invention comprises 2,5-bis(hydroxymethyl)furan (BHMF). In another embodiment the impregnating composition used in the method according to the invention comprises 2,3,5-tris(hydroxymethyl)furan (THMF). In yet another embodiment the impregnating composition used in the method according to the invention comprises 2,2'- hydroxymethyldifurylmethane (HMDM). In still another embodiment the impregnating composition used in the method according to the invention comprises 5-hydroxymethyl- 2- furfurylamine. In still another embodiment the impregnating composition used in the method according to the invention comprises 5-hydroxymethyl-2-furancarboxaldehyde. In still another embodiment the impregnating composition used in the method according to the invention comprises 5-methyl-2-furfuryl alcohol. In still another embodiment the impregnating composition used in the method according to the invention comprises 5- hydroxymethyl- [alpha] -(methyl)furfuryl alcohol. In yet another embodiment the impregnating composition used in the method according to the invention comprises 2, 2', 3,3'- (hydroxymethyldifurylmethane. In another embodiment the impregnating composition used in the method according to the invention comprises 2,2',4,4'- (hydroxymethyl)difurylmethane. In a further embodiment, the invention relates to the use of a composition comprising 2,5-bis(hydroxymethyl)furan (BHMF), 2,3,5- tris(hydroxymethyl)furan (THMF), and 2,2'-hydroxymethyldifurylmethane (HMDM).
In another further embodiment, the invention relates to the use of a composition comprising 2,5-bis(hydroxymethyl)furan (BHMF); 2,3,5-tris(hydroxymethyl)furan (THMF); and 2,2'-(hydroxymethyl)difurylmethane (HMDM); and optionally
condensation products of BHMF, THMF and/or HMDM, and/or mixtures thereof.
The term "condensation product" as used herein refers to a compound with structural formula IV
Figure imgf000028_0001
formula IV wherein n is preferably between 0 and 5, and more preferably 1 , 2, 3 or 4; wherein t is 1 or 2; wherein s is 1 or 2; wherein w is 0 or 1 ; wherein z is 0 or 1 , wherein R2, R3, R4, R5, R6, R7 are each independently hydrogen, methyl, a hydroxyalkyl or a
hydroxyalkylfurylalkyl, wherein R1, R8 are each independently selected from the group comprising methyl, hydroxyalkyl, and hydroxyalkylfurylalkyl. In a more preferred embodiment R2, R3, R4, R5, R6, and R7 are each independently -H, -CH3, -CH2OH or - CH2-furyl-CH2OH (=hydroxymethylfurylmethyl), and R1 and R8 are each independently -CH3, -CH2OH or - CH2-furyl-CH2OH.
In another preferred embodiment the invention relates to a polymerisable composition for impregnating and modifying wood comprising a compound of formula I and/or formula II wherein n, t, s, w, z, X, Y, R2, R3, R4, R5, R6, R7, R9, R10, R11, R12, R13, R14, R15, R16, R17 R18, R19, R20 R21 are as defined above, and wherein the dotted line represents a double bond, provided that R17 and R20 are not a C1-C20 alkyl, and preferably not methyl, and/or provided that the compound is not 2,5 dimethylfuran, 2,4 dimethylfuran, 2-acetyl-5- methylfuran, 2,5 dimethyl-3-acetylfuran, 2,3,5- trimethylfuran, 2-vinyl-3 -methylfuran, 2-methyl benzofuran, dimethylbenzo furan, dibenzofuran, 2,3-dimethyl-5-ethylfuran, 3,4- dimethyl-5-ethylfuran, 2-ethyl-2,3- dihydro-5-methylfuran, 2,5-tetrahydrodimethylfuran, 2- methyltetrahydrofuran-3-one, 2,5-dimethyltetrahydrofuran-3-one, 2-acetyltetrahydrofuran- 3-one, 4-methyl-2-furoic acid, 2-(5-methylfuryl)-methyl ketone, 4-methyl furfural, 5 -methyl furfural, 2-methyl-3- furfural, 3-methyl-2-furfural, 5-hydroxymethyl-2-furfural, bis furfuryl-2- furan, or 2,5- difurfuryledine- 1 -cyclopentanone.
Furan compounds can be applied in varying amounts in the present composition depending on the wood density and the solid content of the composition comprising substituted furan compounds. It can be adapted according to the desired properties of wood one wants to obtain such as increased density, increased hardness, increased durability, increased fire resistance (FRE or Fire Retardant Efficiency), increased dimensional stability, a desired modulus of elasticity (MOE), improved Anti swelling efficiency (ASE), reduced equilibrium moisture content (EMC), etc... In a preferred embodiment, the amount of substituted furan compounds in the present composition varies between 3 and 100 % by weight and preferably between 10 and 60% by weight.
In another preferred embodiment, the amount of substituted furan compounds being impregnated in the wood varies between 3 and 100 % by weight on wood and preferably between 10 and 60% by weight on wood.
Substituted furan compounds in a composition used in the method according to the invention are used in an amount such that the weight percentage gain (WPG) of the wood after impregnation and reaction with the wood is at least 3% and for instance can vary from 3% to 150%, more preferably from 5% to 100% and even more preferable between 10%> and 60%>, and more preferably between 20 and 40%> by weight.
In another embodiment, the invention relates to a composition comprising more than 60 % by weight, and preferably more than 70% by weight of a compound of formula I and/or formula II, wherein n is smaller than or equal to 5, and - 0 to 40% by weight, preferably 0 to 30% by weight of condensation products thereof. Preferably, the invention relates to a composition comprising more than 70% by weight, preferably more than 80 % by weight, and more preferred more than 90% by weight of a compound of formula II, - 0 to 30%> by weight, preferably 0 to 20%> by weight, more preferred 0 to 10% by weight of a compound of formula I, wherein n is smaller than or equal to 5, and preferably smaller than or equal to 2, and more preferably 0 or 1 , and optionally 0 to 40%> by weight, preferably 0 to 30%> by weight of condensation products thereof. In a preferred embodiment, the invention provides a composition comprising a mixture of: up to 70 %> by weight, preferably up to 55 %>, more preferably up to 25%> by weight of 2,5-bis(hydroxymethyl)furan (BHMF), up to 20 %> by weight, preferably up to 15 %>, more preferably up to 5%> by weight of 2,3,5-tris(hydroxymethyl)furan (THMF), and up to 10 %> by weight, preferably up to 5 %>, more preferably up to 1 %> by weight of 2,2'- hydroxymethyldifurylmethane (HMDM).
Optionally the composition may further comprise up to 40 % by weight, preferably up to 30 ) by weight of condensation products of BHMF, THMF and/or HMDM. In another embodiment, the invention relates to a composition comprising: up to 60 % by weight, and preferably up to 30% by weight of a compound of formula I and/or formula II, wherein n is smaller than or equal to 5, and up to 40%> by weight, preferably up to 60%) by weight of condensation products thereof.
In the present invention the polymerisable impregnation composition preferably comprises disubstituted, trisubstitured or polysubstituted furan compounds or a mixture thereof and may contain a solvent, catalyst (initiator), coupling agent, filler, fire retardant, oil(wax) and/or surfactant. In accordance with the present invention the impregnation composition does not set nor react even over extended periods of time, such that it has a long shelf-life. In addition, substituted furan compounds as defined herein, or substituted furan compounds diluted in a solvent are stable in the presence of a catalyst at room temperature.
In a preferred embodiment of the present invention the compounds of the present composition are diluted in a solvent. Preferably the concentration of the furan compounds in such dilution is between 5 and 95 wt%, and more preferably between 10 and 80 wt% Examples of suitable solvents which may be used in a composition used in the method according to the invention comprise but are not limited to water, alcohols such as ethanol or methanol, dioxane, N,N dimethylformamide, acetone, ethyleneglycol, or glycerol. In a more preferred embodiment the solvent is water. The furan compounds according to the invention are preferably water soluble. In a more preferred embodiment the furan compounds according to the invention are water-soluble in presence of a catalyst. As used herein the term "water soluble" refers to the amount that is soluble, after standing at least 48 hours in water at room temperature, when 5.0 grams of furan compounds is added to 95.0 grams deionized water. The percentage of water solubility can be calculated by the formula: % Water solubility = 100 x (5.0 grams furan compounds - weight of water insoluble residue) / (5.0 grams furan compounds).
In the present invention, the present furan compounds can react with wood in the presence or the absence of a catalyst. The composition used in the method according to the invention may thus further comprise a catalyst. The catalysts may be a metallic salt, an ammonium salt, an organic acid, an anhydride, an inorganic acid or any mixtures thereof. In an embodiment the catalysts are metallic salts such as metalhalogenides, metalsulfates, metalnitrates, metalphosphates or their mixtures. Examples are magnesium chloride, magnesium sulfate, magnesium nitrate, zinc chloride, zinc nitrate, aluminum chloride, aluminum nitrate, aluminum sulfate or their mixtures. In another embodiment the catalyst is an ammonium salt. Examples are ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium carbonate, ammonium
bicarbonate, ammonium oxalate, ammonium citrate, ammonium nitrate, ammonium fumarate, ammonium levulinate or their mixtures. Other catalysts may be organic acids or inorganic acids. Suitable examples hereof are formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, oxalic acid, maleic acid, maleic anhydride, adipic acid, citric acid, furoic acid, benzoic acid, phtalic anhydride, paratoluene sulphonic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, silicic acid, benzoylperoxide or their mixtures. Depending on the type of catalyst and of the curing temperature and desired wood properties, the composition may comprise up to 20 % (or more), generally in the range of 1-15 %, preferably 8-10 %, more preferably 5-8 %, yet more preferably 5 % by weight on catalyst on the amount of substituted furan compounds in the composition. Catalyst amount is hereby calculated on the amount of "dry" furan compounds. In another preferred embodiment, several compounds according to the present invention, including but not limited to 2,5- bis(hydroxymethyl)furan (BHMF); 2,3,5- tris(hydroxymethyl)furan (THMF); 2,2'- (hydroxymethyl)difurylmethane; (HMDM); condensation products thereof, 2,2', 3,3'- (hydroxymethyl)difurylmethane; 2, 2', 4,4'- (hydroxymethyl)difurylmethane, are obtained by hydroxymethylation of furfuryl alcohol with a formaldehyde source. The term "formaldehyde source" as used herein refers to formaldehyde, paraformaldehyde, trioxane, or any hemiformal. The invention also provides a wood product which obtainable in accordance with the method according to any of the foregoing claims. Such a wood product has a good durability combined with a increased mechanical strength.
The invention further provides a system suitable for performing the method according to the invention, comprising: an impregnation device for impregnating wood with a reactive composition, in particular a polymerisable composition, and a chemical modification device provided with heating means for allowing the impregnated wood to react under the influence of heat. In an embodiment of the system according to the invention the impregnation device is adapted for forcing the reactive composition through the wood at least partially by using pressure. The impregnating device may be pressurized by using any suitable apparatus, such as, for example, a high volume transfer or pressure pump or air pressure provided by a compressor system. An inlet may be provided at one end of the device with pressure being relieved from the other end which allows for a high volume flow over and through the wood in the device. The wood will generally be fully submerged in the, commonly waterborne, reactive preservative, in particular polymerisable preservative. The separation of the wood and the excess waterborne preservative may be performed by removing the wood from the preservative.
In an embodiment the chemical modification device comprises a treatment space sealable in medium-tight manner, a vacuum pump connected to the treatment space, a steam source connected to the treatment space, a heating device which is in thermal contact with the treatment space, and measuring and control equipment adapted to measure at least the dry bulb temperature, the relative humidity, and the pressure (wet bulb temperature) inside the treatment space and to control the vacuum pump, the steam source and the heat source. The method according to the invention can be performed in simple manner using such a device. The apparatus can herein be programmed optimally for the treatment of determined types of wood. In a particular embodiment the treatment space is bounded by a double wall provided with thermally conducting oil. The dry bulb temperature inside the treatment space can hereby be readily controlled and kept homogeneous. The thermal oil is situated between the two walls of the double wall. The apparatus according to the invention is preferably programmed for performing a method according to the invention. The apparatus can be provided for this purpose with a computer with which the measuring and control equipment is read and the vacuum pump, the steam source and the heat source and possible other components are controlled.
The invention will now be elucidated on the basis of the following non- limitative embodiment, wherein:
Figure 1 shows a schematic view of the method according to the invention,
Figure 2 shows an impregnation device for use in a system according to the invention, Figure 3 shows a chemical modification device for use in a system according to the invention, and
Figure 4 shows a chart illustrating the dependency of the dry bulb temperature, the wet bulb temperature, and the relative humidity for use in a method and system according to the invention.
Figure 1 shows a schematic view of the method according to the invention, wherein in a first step 1 wood to be modified is impregnated with a waterborne polymerisable composition by means of a known vacuum-pressure method, after which, in a second step 2, the wood is dried in either a natural or a forced manner until the moisture content has been reduced to about 14% by weight. In a third step 3 at least a fraction of oxygen contained by a treatment vessel is removed from the treatment vessel, after which, in a fourth step 4, the impregnated wood is heated gradually in the treatment vessel to chemically modify the wood, wherein the composition is polymerised within the wood, and - dependent on the maximum dry bulb temperature applied in the vessel - eventually to thermally modify the wood. In a subsequent fifth step 5 the wood is cooled down in a controlled manner, dependent on the wood and the polymerised composition used. In a final step 6 the modified wood is removed from the treatment vessel and can be used e.g. as a constructive element. Figure 2 shows an impregnation device 48 for use in a system according to the invention. Referring to this figure, waterborne preservative (modifying agent) contained in a storage tank 7 is heated to the required temperature, such as 30-98 degrees Celsius, and then agitated by means of the agitation pump 8, wherein a valve 9 is open. Heating may be achieved either by an in-tank heater or a heat pump in the agitation line.
Agitation of the storage tank 7 is continuous. A pressure cylinder 10 is loaded with wood to be modified (not shown) and the door 11 closed and sealed. An initial vacuum, such as, 0-98 kPa, is drawn by means of valves 12, 13, 14 and 15 closed and valve 16 open, wherein a vacuum pump 17 is switched on. A vacuum control valve 18 maintains the required level of vacuum (underpressure). The vacuum is reached and held for a predetermined time. The pressure cylinder 10 is then flooded with the hot preservative and valves 15 and 16 are opened. The level of vacuum is maintained by vacuum control valve 1. Once the cylinder 10 is flooded, valves 12 and 15 are closed. The vacuum pump 17 is then turned off. Pressures up to 1400 kPa are applied using a high volume pressure pump 19 with valve 15 open. The pressure control valve 13 maintains the required pressure. The presence of the high volume pump 19 means that there is constantly fresh hot solution passing though the pressure cylinder 10 treating and heating the wood. Pressure is released via the vacuum control valve 18 to ramp down the pressure to 0 kPa. Once the modification treatment has been completed, there are two alternatives for draining the pressure cylinder 10 as follows:
(a) closing valve 15, opening vales 13, 14 and 16 and using the high volume pressure pump 17 pump the cylinder dry; or
(b) using the vacuum pump 17 as an air compressor so that the liquid can be blown out of the pressure cylinder 10 via line using valve 16 and by-passing the pump.
The advantage of using alternative (b) is that the pressure cylinder 10 can be emptied at the same pressure as the wood was treated or at a higher pressure meaning that any kickback is alleviated until the preservative has been removed from the cylinder and the pressure achieved, and can then be segregated. The kickback can then be collected after final vacuum and cleaned up prior to returning clean preservative to the storage tank 7. After draining the cylinder, all the valves are closed apart from valve 12 and a vacuum such as -80 to -98 kPa is drawn on the pressure cylinder 10. After a predetermined time, the vacuum is vented through valve 18 and any residual liquid is then cleaned and/or recycled. The door 11 is then opened and the treated fixed timber removed for storage under cover until it is dispatched. A short holding period may be required before the wood leaves the treatment containment area. This impregnation process as such is also known as the Bethall process. Prior heating of the polymerisable preservative may be omitted. Suitable compositions of the preservative used in the impregnation device 48 are given in the preceding description. Figure 3 shows a chemical modification device 20 for use in a system according to the invention, comprising a treatment space 21 adapted to receive impregnated wood, which wood may for example be impregnated with a polymerisable composition by using the device 48 as shown in figure 2. The treatment space 21 is confined by a thermally isolated outer reactor wall 22, and a thermally conducting inner reactor wall 23 which is filled with a thermally conductive oil. The treatment space 21 connects to a water container 24 containing water 25 that is heated by heating means 26 in order to generate steam, which is led to the treatment chamber 21 through a steam channel 27.
Alternatively, the water container 24 is incorporated within the treatment space 21. The amount of water should be sufficient for achieving the desired steam pressure in the reactor chamber 21, taking into account the additional water consumed by hydrolysis reactions and the amount of water adsorbed by the wood. The container 24 is sufficiently large to store the initial amount of water plus the amount released by condensation reactions, dehydration reactions and drying. The treatment space 21 is provided with a mechanical stirrer 28 used to homogenize the generated steam and volatile reaction products, leading to a homogenous exposure of the treated wood parts 29. The wood parts 29 are preferably spaced apart, preferably having mutual distances of 8-15 mm, allowing for an even more homogenous treatment. If wood parts 29 are packed closely together, inner parts in a pile of wood parts 29 are less exposed than outer parts, leading to different treatment of the parts. Preferably, the treatment space 21 and the water container 24 form a closed system, in order to optimize the use of water. Preferably, the system is provided with a safety pressure valve. During the processing of the impregnated wood, the water container can be used as a cold spot, wherein the water container 24 has a dry bulb temperature lower than the treatment space 21, in order to ensure that water condenses in the water container and not in the treatment space 21 where it could possibly condense on the wood 29. For safety reasons, the treatment space 21 is provided with at least one standard safety pressure release valve, set at a pressure below the maximum pressure the reactor walls 22,23 can withstand. Under operating conditions according to the invention, the pressure typically ranges from vacuum to a maximum of approximately 12 bar, hence the safety pressure release valve could for instance be set at 14 bar. The pressure inside the treatment space 21 can be monitored by a standard pressure meter 47 covering the operating range. During operation the impregnated wood will be polymerised in the steam filled treatment space 21 by heating the treatment space 21 to a dry bulb temperature of at least 70 degrees Celsius, after which the dry bulb temperature in the treatment space is raised gradually with a dry bulb temperature gradient of a maximum of 40 degrees Celsius per hour, preferably between 20-40 degrees Celsius per hour, to a maximum dry bulb temperature of between 120 and 206 degrees Celsius; wherein the wood is heated at said maximum dry bulb temperature during a reaction time of at least 10 minutes. In case the maximum dry bulb temperature exceeds 140 degrees Celsius during operation, the wood will be modified both chemically and thermally.
The treatment space 21 also connects to a first pressurized cylinder 30 comprising carbon dioxide (C02), which is connected through an first automated dispensing valve 31. Carbon dioxide may be used to lower the pH in the reactor as carbon dioxide acidifies steam. The device 20 also comprises a second pressurized cylinder 32 of ammonia (NH3) also connected to a second automated dispensing valve 33. Having the possibility to add predetermined amounts of acid or base may be used to maintain the pH at a predetermined value during the treatment according to the invention. The pH is monitored by taking samples of the steam in the reactor space 21 by temporarily opening a sample valve 34, condensing the sampled steam in a condenser 35, and collecting the condensed steam 36 for pH measurement using regular electrochemical pH measurement equipment 37. The treatment space 21 is also provided with a vacuum pump system 38 for evacuating the treatment space 21, in particular for removing oxygen gas. The vacuum system 38 optionally includes a pressure meter for monitoring pressure within the treatment space 21. Instead of the optional pressure meter, it is also possible to rely on dry bulb temperature and pH measurements only. The device 20 is provided with heating means 45 for heating the reactor chamber 21, and a dry bulb temperature measurement units (40, 41, 42) for the inner reactor wall 23 (unit 40), the wood 29 (unit 41) and the water 25 of the steam generator 24 (unit 42). A central control unit 43 monitors the dry bulb temperature of the wood 41, the dry bulb temperature of the inner reactor wall 23, the dry bulb temperature of the steam water 25, the pressure within the treatment space 21, and the pH within the treatment space. The control unit 43 will then, following the preset program or manual control, adjust these parameters. For instance, pressure can be increased by turning up the heater 26 of the steam generator, leading to increased steam evaporation, or lowered by lowering the dry bulb temperature, water evaporation and/or opening the vacuum valve 44 of the vacuum system 38. The vacuum valve 44 is a three- way valve, that can also be used to depressurize the reaction vessel 21, or to let air or an inert gas such as nitrogen into the treatment space 21 in order to remove vacuum. The dry bulb temperature in the treatment space 21 can be adjusted by the wall heater unit 45. pH can be lowered by adding carbon dioxide 30, or increased by adding ammonia 32.
In figure 3 the characters A-H represent the following parameters:
A: pH set
B: pH read
C: Twaii set
D: Twaii read
E: Twood read
F. Twater Set
G: Twater read
H: TWater Control
It is conceivable that the impregnation device 48 as shown in figure 2 and the modification device 20 as shown in figure 3 are physically connected to each other and/or are mutually integrated at least partially.
Figure 4 shows a chart 49 illustrating the dependency of the dry bulb temperature (in °C), the wet bulb temperature (in °C), and the relative humidity (in %) for use in a method and system according to the invention. At three different wet bulb temperatures (wbT) the relation is shown between the relative humidity and the dry bulb temperature. The three different wet bulb temperatures are referred to as process A, process B, and process C. In process A the wet bulb temperature is 100°C corresponding to a substantially atmospheric pressure of 1,05 bar. In process B the wet bulb temperature is 125°C corresponding to a (superatmospheric) pressure of 2,45 bar. In process C the wet bulb temperature is 160°C corresponding to a (superatmospheric) pressure of 6,75 bar. Constant wet-bulb temperatures are physically equivalent with constant partial pressures of water vapor. The system according to the invention is able to accurately control the wet-bulb temperature (water reservoir temperature) in a steam vessel (pressure chamber) of the system, or alternatively by application of an external pressure regulated steam generator coupled to said steam vessel. Hence, steam can be generated internally in the vessel and/or externally at a distance from the vessel. The steam vessel may be provided with a pressure relief valve to limit the maximum superatmospheric pressure. The Wet-bulb temperatures in excess of 100°C are to be contained in a pressure vessel (autoclave). The system according to the invention is also able to accurately control the dry-bulb temperature (wall temperature of the autoclave). Dry-bulb temperature and wet-bulb temperature determine together the relative humidity. The marked region in the chart 49 indicates the desired range of relative humidity of between 50% and 90%, more preferably between 60%> and 80%>, providing a desired mild climate for wood modification. Relative humidities under 50%, and in particular under 35% can be destructive for wood, as there is a high risk for checks and distortion, especially in thick (in excess of 40 mm) wood specimens. Chemical modifications are commonly performed in a superheated steam kiln under atmospheric conditions. Under such atmospheric conditions the wet-bulb temperature cannot exceed 100°C (process A). When the dry-bulb temperature reaches 125°C, the relative humidity is dropped within the region of harsh wood conditions, potentially leading to poor product quality. In process B, with a wet-bulb temperature of 125°C, in a pressure autoclave with pure steam operating at 2,45 bar (absolute pressure), the dry bulb temperature can be increased to 140°C to obtain a relative humidity of 60%, still within the preferred mild region. When process A would be operated at 60%> relative humidity the dry-bulb should not exceed 115°C, a temperature where the curing rate is relatively low. In process C, with a wet-bulb temperature of 160°C, in a pressure autoclave with pure steam operating at 6,75 bar (absolute pressure), the dry-bulb temperature may even be increased to 180°C to obtain a relative humidity of 60%, to achieve a very fast curing process. Hence, process B and C are substantially advantageous with respect to process A and there preferred over process A. Under these conditions, however, untreated wood is effectively thermally modified. Thermally modified wood shows a number of similar properties as chemically modified wood (notably reduced moisture swelling and increased resistance against wood-degrading fungi) but shows a major difference with respect to mechanical strength. Chemical modification strengthens the wood opposed to thermal modification where strength is weakened. Chemical modification is also generally more effective against fungi and other wood-deteriorating organisms. High wet-bulb temperatures enable a new type of hybrid modifiation process on surface impregnated wood, to achieve a solid wood product with a thermally modified core and a surface-enhanced chemically modified layer, upgrading the overall performance of the wood product with a minimum of additives used. The data used in the chart 49 are list in the table below.
Figure imgf000039_0001
In case sapwood of pine (Pinus sylvestris) impregnated with a furane oligomer would be subjected to process B with a environmental dry bulb temperature of 140°C in a pure steam atmosphere of 2,45 bar (corresponding to a wet bulb temperature of 125°C), the sapwood will become chemically modified without cracking, splitting or deformation of the wood.
In case sapwood of pine {Pinus sylvestris), not being impregnated with any reactive composition, would be subjected to process C with a environmental dry bulb
temperature of 180°C in a pure steam atmosphere of 6,75 bar (corresponding to a wet bulb temperature of 160°C), the sapwood will become merely thermally modified, wherein the shrinkage of the wood has been reduced to about 50% and the sensitivity to Basidiomycetes has been reduced substantially. The bending strength has been reduced with 15%). However, in case the outer surface layer of the same sapwood is impregnated with a with a furane oligomer after which the impregnated sapwood is subjected to process C with a environmental dry bulb temperature of 180°C in a pure steam atmosphere of 6,75 bar (corresponding to a wet bulb temperature of 160°C), the the core of the sapwood will become thermally modified and the outer surface layer (shell) of the sapwood will become both thermally and chemically modified without cracking, splitting or deformation of the wood. The bending strength has been improved with 15%). Moreover, the outer surface layer (shell) has obtained an increased durability, which allows the modified wood to be applied in moist environments, such as in the soil. It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. Use of the verb "comprise" and its conjugations does not exclude the presence of elements or steps other than those stated in a claim. The article "a" or "an" preceding an element does not exclude the presence of a plurality of such elements. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.

Claims

Claims
1. Method for modifying wood, in particular for preserving wood, comprising the processing steps of:
A) impregnating wood to be modified with a reactive composition, in particular a polymerisable composition, and
B) allowing the impregnated wood to react in an overheated steam filled treatment space by heating the treatment space to a dry bulb temperature of at least 70 degrees Celsius, after which the dry bulb temperature in the treatment space is raised gradually with a dry bulb temperature gradient of a maximum of 40 degrees Celsius per hour, preferably between 20 and 40 degrees Celsius per hour; to a maximum dry bulb temperature of between 120 and 206 degrees Celsius; wherein at said maximum dry bulb temperature:
o the relative humidity lies between 50% and 90%;
o the wet bulb temperature lies between 105 and 176 degrees Celsius; and o the wood is heated during a reaction time of at least 10 minutes.
2. Method as claimed in claim 1, wherein during step B) the relative humidity within the treatment space is held at a substantially constant level.
3. Method as claimed in claim 1 or 2, wherein during step B) the relative humidity lies between 60%> and 85%, in particular between 65% and 80%.
4. Method as claimed in any of the foregoing claims, wherein a water supply container is positioned within the treatment space, wherein during step B) water is evaporated from the water supply container.
5. Method as claimed in any of the foregoing claims, wherein the wood is fully impregnated with a reactive composition, in particular a polymerisable composition.
6. Method as claimed in any of the claims 1-5, wherein the wood is partially impregnated with the polymerisable composition.
7. Method as claimed in any of the foregoing claims, wherein during step B) the partial steam pressure in the treatment space at the maximum dry bulb temperature is at least 1,25 bar.
8. Method as claimed in any of the claims 1-6, wherein during step B) the maximum dry bulb temperature amounts to 190 degrees Celsius.
9. Method as claimed in any of the foregoing claims, wherein the method further comprises step C), comprising of at least partially drying the impregnated wood prior to execution of step B).
10. Method as claimed in any of the foregoing claims, wherein the method further comprises step D), comprising of removing at least a substantial fraction of air, in particular oxygen, from the treatment space prior to execution of step B).
11. Method as claimed in any of the foregoing claims, wherein during step B) the moisture content of the wood lies between 6 en 20% by weight of the dry wood mass.
12. Method as claimed in any of the foregoing claims, wherein the steam has a maximum degree of saturation of 95% during step C).
13. Method as claimed in any of the foregoing claims, wherein during step B) the treatment space is substantially closed, preferably sealed.
Figure imgf000042_0001
Formula I
Figure imgf000043_0001
Formula II wherein n is an integer between 0 and 20, preferably between 0 and 10, and more preferably between 0 and 5, wherein t and s each independently are an integer between 1 and 20, preferably between 1 and 10, and more preferably between 1 and 5, wherein w and z each independently are 0 or 1 , wherein X and Y each independently are O, S or N-R21 and wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R18, R19, R21 are each independently hydrogen or selected from the group comprising C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C5-C12 heteroaryl, carboxaldehyde, hydroxyl, hydroxyalkyl, carboxyl, amino, nitro, formyl, alkylamino, aminoalkyl, alkylaminoalkyl, furyl, furylalkyl, hydroxyalkylfurylalkyl, alkyloxy, alkoxyalkyl, alkenyloxy, alkylcarbonylalkenyl, oxiranyl, alkylcarbonyloxyalkyl, alkyloxycarbonylalkenyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyl, alkenylcarbonyl, halocarbonyl, haloalkyl, haloaryl, haloalkenyl, imino, thiol, alkylthio, thioalkyl, alky It hio alkyl, cyano, alkylsulfonyl, sulfonic acid, and any mixtures thereof,
whereby each group is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, wherein R17 and R20 are each independently selected from the group comprising C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C5-C12 heteroaryl, carboxaldehyde, hydroxyl, hydroxyalkyl, carboxyl, amino, nitro, formyl, alkylamino, aminoalkyl, alkylaminoalkyl, furyl, furylalkyl,
hydroxyalkylfurylalkyl, alkyloxy, alkoxyalkyl, alkenyloxy, alkylcarbonylalkenyl, oxiranyl, alkylcarbonyloxyalkyl, alkyloxycarbonylalkenyl, alkenylcarbonyloxyalkyl, isocyanate, isocyanate-alkyl, alkylcarboxy, alkenylcarboxy, alkylcarbonyl,
alkenylcarbonyl, halocarbonyl, haloalkyl, haloaryl, haloalkenyl, imino, thiol, alkylthio, thioalkyl, alkylthio alkyl, cyano, alkylsulfonyl, sulfonic acid, and any mixtures thereof, whereby each group is optionally substituted with one or more substituents selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, hydroxyl, carboxyl, nitro, amino, furyl, furylalkyl, alkylfuryl, hydroxyalkylfurylalkyl, isocyanate, formyl, halocarbonyl, thiol, and alkylthio, and wherein the dotted line represents an optional double bond. 15. Method as claimed in any of the foregoing claims, wherein during step A) the wood is impregnated with a polymerisable composition selected from the group comprising 2,5- bis(hydroxymethyl)furan; 2,3,5-tris(hydroxymethyl)furan; 5-methyl-2- furfuryl alcohol, 3- hydroxymethyl-5-methyl-2-furfurylalcohol; 2,2'- (hydroxymethyl)difurylmethane; 2, 2', 3,3'- (hydroxymethyl)difurylmethane; 2,2',4,4'- (hydroxymethyl)difurylmethane; 5- hydroxymethyl- [alpha] -(methyl)furfuryl alcohol; 5- hydroxymethyl-2-furancarboxaldehyde; 3,5- hydroxymethyl-2-furancarboxaldehyde; 4,5-hydroxymethyl-2-furancarboxaldehyde; 5- methyl-2-furancarboxaldehyde; 3- hydroxymethyl-5-methyl-2-furancarboxaldehyde; 5-nitro furfuraldehyde; 2,5- bis(carboxaldehyde)furan; 3-hydroxymethyl-2,5-bis(carboxaldehyde)furan; 4- hydroxymethyl-2,5-bis(carboxaldehyde)furan; 5- hydroxymethyl-2-furoic acid; 5- methyl-2-furoic acid; 5-carboxaldehyde-2-furoic acid; 2,5- furandicarboxylic acid; 2,5- furan diacid dichloride; 2,5-furan dicarboxylic acid dimethyl ester; 5-hydroxymethyl-2- furfurylamine; 5-methyl-2-furfurylamine; 5-carboxaldehyde-2- furfurylamine; 5- carboxy-2-furfurylamine; 2,5-bis(aminomethyl)furan; 5-methyl-2- vinylfuroate; 5- tertbutyl-2-vinyl furoate; 5-methyl-2-vinyl furan; 5-methyl-2-furfurylidene acetone; 5- methyl-2-furyloxirane; 5 -methyl- fur furyl vinyl ether; 5-hydroxymethyl-2-ethyl furanacrylate; bis-(2,5-isocyanatemethyl) furan; and bis(2,5-isocyanate) furan; or any mixtures thereof. 16. Method as claimed in any of the foregoing claims, wherein during step A) the wood is impregnated with a polymerisable composition comprising a chemical compound selected from the group comprising 2,5-bis(hydroxymethyl)furan (BHMF); 2,3,5-tris(hydroxymethyl)furan (THMF); 2,2'-(hydroxymethyl)difurylmethane;
(HMDM); 2,2*,3,3*(hydroxymethyl)difurylmethane; 2,2*,4,4*- (hydroxymethyl)difurylmethane or any mixtures thereof.
17. Method as claimed in any of the foregoing claims, wherein during step A) the wood is impregnated with a polymerisable composition comprising a chemical compound selected from the group comprising 2,5-bis(hydroxymethyl)furan (BHMF); 2,3,5-tris(hydroxymethyl)furan (THMF); and 2,2'-(hydroxymethyl)difurylmethane (HMDM); and optionally condensation products thereof, or mixtures thereof.
18. Method as claimed in claim 16 or 17, wherein the chemical compound is obtained by hydroxymethylation of at least one furfuryl alcohol compound with a formaldehyde source.
19. Method as claimed in any of the foregoing claims, wherein the concentration of the chemical compound of formula I and/or formula II in the polymerisable composition is between 3 and 100% by weight.
20. Method as claimed in any of the foregoing claims, wherein the chemical compounds are diluted in a solvent, in particular water. 21. Method as claimed in any of the foregoing claims, wherein the reactive composition, in particular the polymerisable composition, also comprises a catalyst.
22. Modified wood product obtainable in accordance with the method as claimed in any of the foregoing claims.
23. System suitable for performing the method as claimed in any of the claims 1-21, comprising:
- an impregnation device for impregnating wood with a reactive composition, in particular a polymerisable composition, and
- a chemical modification device provided with heating means for allowing the impregnated wood to react under the influence of heat.
24. System as claimed in claim 23, wherein the chemical modification device comprises:
- a treatment space sealable in substantially medium-tight manner,
- a vacuum pump connected to the treatment space,
- a steam source connected to the treatment space,
- a heating device which is in thermal contact with the treatment space, and - measuring and control equipment adapted to measure at least the dry bulb temperature
and pressure inside the treatment space and to control the vacuum pump, the steam source and the heat source.
25. System as claimed in claim 24, wherein the the treatment space is bounded by a double wall provided with thermally conducting oil.
26. System as claimed in any of the claims 23-25, wherein the impregnating device is adapted for pressing under pressure the reactive composition, in particular the polymerisable composition, through the wood to be modified.
27. System as claimed in any of the claims 24-26, wherein the measuring and control equipment is adapted to the measure the relative humidity in the treatment space.
28. System as claimed in any of the claims 23-27, programmed for performing a method as claimed in any of the claims 1-21.
PCT/NL2011/050083 2010-02-04 2011-02-04 Method and apparatus for modifying wood, and wood product WO2011096812A1 (en)

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CN116209553A (en) * 2020-07-29 2023-06-02 株式会社富然木材 Method for producing modified wooden material, furan derivative resinification solution, and modified wooden material
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