WO2011144608A1 - Procédé pour l'imprégnation de polymère dans du bois - Google Patents

Procédé pour l'imprégnation de polymère dans du bois Download PDF

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Publication number
WO2011144608A1
WO2011144608A1 PCT/EP2011/057962 EP2011057962W WO2011144608A1 WO 2011144608 A1 WO2011144608 A1 WO 2011144608A1 EP 2011057962 W EP2011057962 W EP 2011057962W WO 2011144608 A1 WO2011144608 A1 WO 2011144608A1
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WO
WIPO (PCT)
Prior art keywords
wood
wooden article
temperature
wooden
pressure
Prior art date
Application number
PCT/EP2011/057962
Other languages
English (en)
Inventor
Rune Bendiksten
Morten Eilertsen
Per Brynildsen
Original Assignee
Kebony Asa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kebony Asa filed Critical Kebony Asa
Publication of WO2011144608A1 publication Critical patent/WO2011144608A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • B27K3/156—Combined with grafting onto wood fibres
    • 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
    • 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

Definitions

  • This invention relates to a process for forming a composite composed of wood or wooden articles and a polymeric material particularly but not exclusively for formation of composites or composite articles comprising wooden or wooden articles impregnated or filled with a polymerisable composition particularly but not exclusively furfuryl alcohol, derivatives of furfuryl alcohol or oligomers of these compounds and subsequently polymerised.
  • Various processes have been used for polymer treatment of wood.
  • EP- A- 1341648 and EP-A- 1368167 discloses furan impregnated wood compositions.
  • WO-A-2004/011216 discloses a process wherein wood is impregnated with an aqueous solution of furfuryl alcohol, an initiator such as an organic acid or anhydride, and a stabiliser. Impregnated wood is cured at a temperature from 25 to 140°C preferably 70 to 100°C to polymerise the furfuryl alcohol.
  • WO-A-2007/147804 discloses impregnation of wood with a di, tri and/or poly substituted furan compounds including bis hydroxymethyl furan, tris hydroxymethyl furan and hydroxymethyl difurylmethane using a catalyst at a temperature of between 70 and 200°C.
  • Oscillating pressure methods have been used for woods e.g. spruce which are difficult to penetrate.
  • the concentration of furfuryl alcohol in the aqueous solution may be from about 0.5% to approaching saturation, usually about 10-50%.
  • a co-solvent for example ethanol or methanol may be used, for example, in an amount of 30-75%. Drying of wood after polymerisation causes strain on a modified wood composite, leading to cracking and deformation. Such a strain during drying is generally undesirable for all woods. Drying of shaped wooden articles having a large thickness or other dimension is also prone to cause warping or cracking during drying as planks.
  • PCT/GB2010/000729 discloses a process for controlling treatment of wood or wooden articles, the disclosure of which is incorporated herein by reference for all purposes.
  • a process for impregnating wood or a wooden article comprises a process for forming a composite comprising wood or a wooden article and a polymeric material comprising the steps of:
  • wood compatible polymerisable monomers selected from the group consisting of furfuryl alcohol (FA), bishydroxymethyl furan (BHMF), trihydroxymethyl furan (THMF), oligomers of FA, BHMF and THMF condensation products of these compounds and mixtures thereof;
  • a solvent selected from the group consisting of: water, CrC 4 alcohols and mixtures thereof, wherein the one or more wood compatible polymerises or monomers or oligomers has a boiling point not less than 50° C higher than the boiling point of the solvent and atmospheric pressure; and iv. optionally one or more stabilisers or other ingredients;
  • the impregnated wood or wooden article to a water removal process comprising maintaining the wood or wooden article in an atmosphere having a pressure of about 0.1 to about 0.5 bar, a temperature of about 50 to about 90°C, for a duration sufficient to cause removal of water from the wood or wooden article; and maintaining the wood or wooden article at a higher temperature to cause polymerisation of the composition to form the polymeric material to produce polymer treated wood or wooden article.
  • the preferred solvent is water, although methanol, ethanol, acetone or other volatile solvents may be employed.
  • a vacuum is preferably applied to the wood before drying or solvent removal and curing to remove air. This serves to reduce the risk of an explosion.
  • Preferred monomers are derived from biomass or are derived from renewable and sustainable resources and are capable of impregnating a wood or a wooden article.
  • a single monomer may be most convenient for simplicity and ease of uniform impregnation.
  • Use of furfuryl alcohol or bishydroxymethyl furan is preferred.
  • Suitable monomers or oligomers may include 2,5-furan dicarboxylic acid (FBCA) and succinic acid (SA).
  • FBCA 2,5-furan dicarboxylic acid
  • SA succinic acid
  • the invention is particularly applicable to impregnation of woods which are sensitive to cracking or deformation during drying and curing at elevated temperatures.
  • the invention is particularly suitable for treatment of hardwoods, especially beech, ash and maple.
  • the invention is also applicable to impregnation of large dimension pieces of pine or other softwoods, for example, having a thickness greater than 30cm.
  • the process may be applied to a wide variety of wood species that can be impregnated, both softwoods and hardwoods, for example, Scots pine, southern yellow pine, beech, maple, birch, oak, aspen, poplar and alder.
  • the catalyst may be selected from the group consisting of: acids, for example, maleic anhydride, phthalic anhydride, maleic acid, malic acid, phthalic acid, benzoic acid, citric acid, zinc chloride, aluminium chloride, other cyclic organic anhydrides or latent catalysts such as ammonium salts organic anhydrides and mixtures thereof.
  • the stabilisers which preferably act as buffers may be selected from the group consisting of: sodium carbonate, sodium bicarbonate, sodium citrate, phosphates and calcium or ammonium salts of lignosulphonic acids.
  • Optional further compounds may include borates, for example borax, disodium tetraborate, and boric acid.
  • the relative humidity is maintained at about 80 to about 100%, more preferably at about 90%, for a period of 1 to 200 hours, usually 120 hours, followed by curing at a temperature preferably about 50 to about 180°C, more preferably about 90 to about 140°C, most preferably about 100 to about 130°C, especially about 120°C.
  • a heat exchanger or heat battery may be provided to allow direct heating of the atmosphere within the vessel.
  • Further heating may be preferably provided by injecting superheated steam into the vessel.
  • Superheated steam is preferred in order to cause drying of the wood.
  • the relative humidity may be determined by the difference between the actual pressure at a given temperature as a percentage of the saturation pressure of steam at that temperature.
  • Relative humidity within the chamber generally decreases during the drying process as water is removed from the chamber.
  • the relative humidity is maintained above a minimum level during the heating up phase and at the end of the drying process in order to minimise deformation and cracking of the wood.
  • the relative humidity by range from about 30% to about 100%.
  • a preferred minimum relative humidity is about 35% more preferably about 40% dependent on the wood species and the dimension of the wooden pieces or articles being processed.
  • the relative humidity within the container may be controlled by regulation of pressure and temperature. Following the drying step the wood or wooden articles are heated to a higher temperature to cure the polymer. It is beneficial to remove water from the wood or wooden articles before curing. This allows more rapid curing since thermal energy is not lost by evaporation. A lower temperature may be used in comparison to a conventional process. Also heating of the wood to the curing temperature may be achieved in less time and with less energy due to the reduction of evaporative losses.
  • drying and curing steps may be carried out in the same container, that is without a need for unloading from a drying oven and reloading into a separate curing oven.
  • the pressure within the container may be maintained at about 1 bar and a relative humidity of about 40 to about 100%, preferably about 50 to about 90%.
  • a pressure greater than 1 bar may be used, for example, about 1 to about 4 bar.
  • apparatus for polymer impregnation of wood or a wooden article comprises a container adapted to receive a quantity of wood or one or more wooden articles to be treated, the container having a pump for applying reduced pressure to the container, a steam generator adapted to supply superheated steam to the chamber and sensors adapted to monitor parameters selected from pressure, temperature, humidity and concentration of volatile organic compounds within the container.
  • An inlet for superheated steam may be provided.
  • a heat exchanger within the vessel may be provided for direct heating.
  • the process in accordance with this invention may be applied to timber or shaped wooden articles, for example floor boards, decking, cladding, roofing, poles, sleepers or other partially or fully machined or worked components.
  • Stock timber for subsequent machining into constructional, engineering laminates and joinery components may be used.
  • the invention finds particular applicability to high performance wood or wooden articles with improved stability, increased hardness and prolonged durability for manufacture of products with precise dimensional and performance tolerances. In this specification percentages and other amounts are by weight unless indicated otherwise. Percentages and other proportions are selected from any ranges quoted to total 100%.
  • Figure 1 is a schematic view of a timber impregnation plant in accordance with this invention.
  • Figure 2 illustrates the drying vessel of the plant; .
  • Figure 1 is a schematic view of a timber impregnation plant.
  • a supply of wood or wooden articles, for example planks (1) is organised into a separated stack (2) on a trolley or other carrier (not shown) using spacers so that each plank is separated from adjacent planks.
  • the stack is then moved on the trolley into an impregnation autoclave (3).
  • the autoclave (3) is filled with an impregnating solution from buffer tanks (4,5) supplied from storage tanks (6,7,8) via a mixing and measuring tank (9).
  • each drying chamber is provided with a heat exchanger, or inlet for superheated steam and a condenser (14) connected to an outlet for recycling condensate collected from the condenser (14) to the storage tank (7). Gases from the condenser are routed through an air purifier (26).
  • the wood or wooden articles may be impregnated by any conventional technique including application of pressure up to 15 atmospheres, vacuum followed by pressure or by application of atmospheric or low pressure followed by higher pressure and a final vacuum step.
  • the impregnating solution may comprise one or more monomers selected from furfuryl alcohol, bis hydroxymethyl furan, tris hydroxymethyl furan or oligomers of these compounds.
  • Mixtures of monomers or of monomers and oligomers may be used, provided that they are sufficiently fluid to penetrate and impregnate the wood.
  • a general method which may be used includes the steps of securing the wood so that it will not float; closing the autoclave and applying a partial vacuum; filling the autoclave with the treating mixture while maintaining the vacuum to submerge the wood; pressurising the autoclave to a pressure in the range of 5-14 atmospheres dependent on the wood species, dimensions of the wood or wooden articles and desired rate of impregnation; reducing the pressure to 2 or 3 atmospheres and expelling the liquid using the remaining pressure within the autoclave. Finally, the pressure is released and the treated wood is removed.
  • a typical treatment solution may comprise:
  • a liquid uptake of 150% in relation to dry wood mass for pine sapwood may be achieved.
  • FIG 2 is a diagrammatic view of a drying chamber (10) shown in Figure 1.
  • the chamber (10) includes nine fans (11) and an air inlet valve (12).
  • An outlet (13) for evaporated water communicates with a condenser (14).
  • a steam inlet (15) delivers superheated steam from a boiler (not shown) to an inlet (16) to supply heating and humidity to the chamber (10).
  • Heat exchangers (17) circulate hot water from a heat exchanger (18) supplied by the steam inlet (15). In this way, dry heat is provided to the chamber as necessary.
  • a condensate tank (19) serves to collect condensate from the bottom of the tank (10). The condensate is separated in separator (27).
  • Condensate from the condenser (14) is delivered to measuring tanks (20) for measuring the amount of condensed water vapour.
  • a pump tank (21) delivers the measured condensate to a pump (22) indicated with a water outlet and condensate storage tank (23).
  • a gas water separator (24) separates gas from the condensed water.
  • the condensed water is cooled by a heat exchanger (25).
  • steam may be supplied directly to the tank (10) through inlets (16) and dry heat may be supplied by the heat exchanger (17) so that the temperature and humidity within the tank can be independently controlled.
  • a pre-vacuum is applied for a short period to remove any air from the chamber in order to prevent a risk of fire or explosion.
  • the pressure during the pre-vacuum period may be up to 0.3 bar due to evaporation of water from the impregnated wood.
  • the container is then heated to a temperature of about 70°C over a period of 3-6 hours. During this heating up period the pressure may rise from the pre-vacuum pressure of less than 0.2 bar to between about 0.2 and about 0.4 bar, preferably about 0.3 bar.
  • the relative humidity may be about 90%.
  • the conditions within the container are maintained by control of pressure, injection of superheated steam and external heating.
  • the moisture content of the wood is determined by measurement of the amount of water collected from the container.
  • the drying stage may be complete when the moisture content of the wood is about 15% or lower.
  • the pressure is allowed to rise to about 1 bar and the temperature is increased to from about 100 to about 140°C preferably about 100°C with the relative humidity increasing to about 60 to about 80% by addition of superheated steam to the container, in order to prevent cracking or deformation of the wood.
  • the curing conditions may be maintained for about 10 hours dependent on the nature of the polymer composition and the thickness of the wood or wooden articles.
  • the polymer impregnated wood or wooden articles may be removed from the container for machining, package and distribution.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Forests & Forestry (AREA)

Abstract

L'invention porte sur un procédé pour l'imprégnation de bois ou d'un article en bois comprenant un procédé pour la formation d'un composite comprenant du bois ou un article en bois et un matériau polymère comprenant les étapes consistant à : imprégner le bois ou l'article en bois avec une composition polymérisable comprenant : (i) un ou plusieurs monomères ou oligomères polymérisables compatibles avec le bois choisis dans le groupe constitué par l'alcool furfurylique (FA), le bishydroxyméthylfurane (BHMF), le trihydroxyméthylfurane (THMF), les oligomères de FA, de BHMF et de THMF, les produits de condensation de ces composés et les mélanges de ceux-ci ; (ii) un catalyseur ; (iii) un solvant choisi dans le groupe constitué par : l'eau, les alcools en C1-C4 et les mélanges de ceux-ci, ledit ou lesdits monomères ou oligomères polymérisables compatibles avec le bois ayant un point d'ébullition supérieur ou égal à 50°C de plus que le point d'ébullition du solvant à pression atmosphérique ; et (iv) éventuellement un ou plusieurs stabilisants ou autres ingrédients, pour produire du bois imprégné ou un article en bois imprégné ; soumettre le bois ou article en bois imprégné à un procédé d'élimination de l'eau consistant à maintenir le bois ou l'article en bois dans une atmosphère ayant une pression d'environ 0,1 à environ 0,5 bar, une température d'environ 50 à environ 90°C, pendant une durée suffisante pour provoquer l'élimination de l'eau du bois ou de l'article en bois ; et maintenir le bois ou l'article en bois à une température plus élevée pour provoquer la polymérisation de la composition pour former le matériau polymère pour produire du bois ou un article en bois traité par polymère.
PCT/EP2011/057962 2010-05-20 2011-05-17 Procédé pour l'imprégnation de polymère dans du bois WO2011144608A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB201008464A GB201008464D0 (en) 2010-05-20 2010-05-20 Process for polymer impregnating wood
GB1008464.8 2010-05-20

Publications (1)

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WO2011144608A1 true WO2011144608A1 (fr) 2011-11-24

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3406994A1 (fr) 2017-05-22 2018-11-28 Kebony AS Appareil et procédé de séchage et/ou de durcissement de matériaux
EP4039430A1 (fr) 2021-02-09 2022-08-10 Leko Labs SA Procédé de fabrication d'un composite bois-polymère
WO2022199774A1 (fr) * 2021-03-25 2022-09-29 Peter Klaas Procédé combiné d'hydrolyse et d'estérification de bois
NO20220354A1 (en) * 2022-03-23 2023-09-25 Kebony As Polymerizable solution for obtaining a furan polymer impregnated material
WO2024002448A1 (fr) 2022-06-29 2024-01-04 Alpha Holding Brande Aps Modification de bois hybride à pression élevée

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1341648A2 (fr) 2000-10-12 2003-09-10 Wood Polymer Technologies AS Bois impregne de polymere furannique, procede de preparation du polymere et utilisations associees
EP1368167A1 (fr) 2001-02-01 2003-12-10 Wood Polymer Technologies ASA Bois impregne de polymere furanne
WO2004011214A2 (fr) 2002-07-26 2004-02-05 Wood Polymer Technologies Asa Bois impregne de polymere furannique
WO2004011216A2 (fr) 2002-07-26 2004-02-05 Wood Polymer Technologies Asa Bois imprégné de polymère furannique
WO2007147804A1 (fr) 2006-06-21 2007-12-27 Transfurans Chemicals Procédé de modification de bois et bois ainsi obtenu
WO2010122156A1 (fr) * 2009-04-23 2010-10-28 Kebony Asa Réalisation d'un pont de bateau decking

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1341648A2 (fr) 2000-10-12 2003-09-10 Wood Polymer Technologies AS Bois impregne de polymere furannique, procede de preparation du polymere et utilisations associees
EP1368167A1 (fr) 2001-02-01 2003-12-10 Wood Polymer Technologies ASA Bois impregne de polymere furanne
WO2004011214A2 (fr) 2002-07-26 2004-02-05 Wood Polymer Technologies Asa Bois impregne de polymere furannique
WO2004011216A2 (fr) 2002-07-26 2004-02-05 Wood Polymer Technologies Asa Bois imprégné de polymère furannique
WO2007147804A1 (fr) 2006-06-21 2007-12-27 Transfurans Chemicals Procédé de modification de bois et bois ainsi obtenu
WO2010122156A1 (fr) * 2009-04-23 2010-10-28 Kebony Asa Réalisation d'un pont de bateau decking

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3406994A1 (fr) 2017-05-22 2018-11-28 Kebony AS Appareil et procédé de séchage et/ou de durcissement de matériaux
WO2018215267A1 (fr) 2017-05-22 2018-11-29 Kebony As Appareil et procédé de séchage et/ou de durcissement de matériaux
EP4039430A1 (fr) 2021-02-09 2022-08-10 Leko Labs SA Procédé de fabrication d'un composite bois-polymère
WO2022171613A1 (fr) 2021-02-09 2022-08-18 Leko Labs Sa Procédé de fabrication d'un composite bois-polymère
WO2022199774A1 (fr) * 2021-03-25 2022-09-29 Peter Klaas Procédé combiné d'hydrolyse et d'estérification de bois
NO20220354A1 (en) * 2022-03-23 2023-09-25 Kebony As Polymerizable solution for obtaining a furan polymer impregnated material
WO2023180473A1 (fr) * 2022-03-23 2023-09-28 Kebony As Solution polymérisable permettant d'obtenir un matériau imprégné de polymère de furane
WO2024002448A1 (fr) 2022-06-29 2024-01-04 Alpha Holding Brande Aps Modification de bois hybride à pression élevée

Also Published As

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