WO2020053818A1 - Produit en bois imprégné - Google Patents

Produit en bois imprégné Download PDF

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Publication number
WO2020053818A1
WO2020053818A1 PCT/IB2019/057722 IB2019057722W WO2020053818A1 WO 2020053818 A1 WO2020053818 A1 WO 2020053818A1 IB 2019057722 W IB2019057722 W IB 2019057722W WO 2020053818 A1 WO2020053818 A1 WO 2020053818A1
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WO
WIPO (PCT)
Prior art keywords
furan
monomer
wood product
initiator
polymer
Prior art date
Application number
PCT/IB2019/057722
Other languages
English (en)
Inventor
Warren James Grigsby
Original Assignee
New Zealand Forest Research Institute Limited
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Filing date
Publication date
Application filed by New Zealand Forest Research Institute Limited filed Critical New Zealand Forest Research Institute Limited
Publication of WO2020053818A1 publication Critical patent/WO2020053818A1/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
    • 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
    • B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
    • B27K3/0292—Processes; Apparatus involving an additional treatment during or after impregnation for improving fixation
    • 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
    • B27K3/50—Mixtures of different organic 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
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/001—Heating
    • 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
    • B27K5/02—Staining or dyeing wood; Bleaching 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
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/06—Softening or hardening of wood
    • B27K5/065—Hardening
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/36—Furfuryl alcohol
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/006—Processes utilising sub-atmospheric pressure; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/50—Ageing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/70—Hydrophobation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation

Definitions

  • the present invention relates to impregnated wood products, in particular, cured furan polymer impregnated wood products, methods for producing such products, and
  • Modified wood are pieces of treated timber with improved properties such as durability.
  • Furfuryl alcohol (FA) treatment and polymerization within wood termed “furfurylation” is a well-known wood modification technology to enhance the dimensional stability and hardness of wood (Lande, S., O. Hoibo, and E. Larnoy, Variation in treatability of Scots pine (Pinus sylvestris) by the chemical modification agent furfuryl alcohol dissolved in water. Wood Science and Technology, 2010. 44(1) : p. 105-118.).
  • furfurylation of wood results in a darker coloured wood. With some species, such as Radiata pine, this colour change can be significant.
  • Living wood is protected physically by bark and chemically by terpenes and other chemicals that have anti-microbial and anti-fungal properties.
  • the bark no longer offers physical protection, meaning surfaces (and in the absence of treatments the interior or the wood) are exposed to microbes and fungi that use the wood as a food source and to UV light that can contribute to the degradation of the cell wall, particularly polymers such as cellulose, lignin, hemicellulose etc.
  • terpenes, etc are no longer generated by living cells and may be degraded in the drying process thus resulting in a decrease in resistance to fungi and microbes.
  • wood extractives leaching, degrading and being washed away may remove or change components that contribute to wood colour.
  • Silvering of wood products on weathering is typically a combination of UV aging (particularly photo-oxidation of lignin), extractive changes and colonisation of the wood surface by microbes and fungi.
  • UV aging particularly photo-oxidation of lignin
  • extractive changes and colonisation of the wood surface by microbes and fungi.
  • wood treatments such as polymerised FA reduce vulnerability to degradation both by filling lumen and other spaces in the wood structure to limit physical access or microbes and fungi and possibly to an extent UV light.
  • Furfurals also provide some chemical protection but surfaces exposed to light, moisture, etc remain somewhat vulnerable so still change at least in appearance. Dark materials generally have greater perceived colour change on weathering, as they lighten and grey. Light coloured materials on weathering can darken or yellow (yellowing is mostly an oxidation of lignin effect) but the perceived change tends to be lesser/slower.
  • wood products with modified properties including for example hardness, brittleness, dimensional stability, colour, and weathering characteristics. It is an object of the present invention to go some way to meeting this need; and/or to at least provide the public with a useful choice.
  • the present invention broadly consists in a cured furan polymer
  • the cured furan polymer comprises a cured reaction product of:
  • an initiator that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction;
  • the present invention broadly consists in a method of producing a cured furan polymer impregnated wood product, the method comprising :
  • an initiator that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction; and/or a monomer, oligomer, or polymer that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction;
  • the present invention broadly consists in a cured furan polymer impregnated wood product produced by a method of the present invention.
  • the present invention broadly consists in a formulation for impregnating a wood product, the formulation comprising :
  • an initiator that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction;
  • the wood product is lumber, timber, a wood composite, or wood fibres, particles, flakes, strands, chips, or sheets.
  • the wood product is lumber.
  • the furan monomer is selected from the group consisting of furfuryl alcohol (FA), bishydroxymethyl furan (BHMF), tri hydroxymethyl furan (THMF), furfural, oligomers thereof, condensation products thereof, and combinations thereof.
  • FA furfuryl alcohol
  • BHMF bishydroxymethyl furan
  • THMF tri hydroxymethyl furan
  • furfural oligomers thereof, condensation products thereof, and combinations thereof.
  • the furan monomer is furfuryl alcohol (FA).
  • the monomer, oligomer, or polymer that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction is a prepolymer comprising a reaction product of a furan monomer and an initiator that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction.
  • the monomer modifies the helicity of the furan polymer and/or the spacing between furan units of different chains in the furan polymer.
  • the initiator is capable of Diels Alder reaction with the furan monomer and/or polymerised chains thereof.
  • the initiator is an imide, preferably a cyclic imide, preferably maleimide, N-methyl maleimide, or succinimide, preferably maleimide.
  • the initiator is a cyclic imide. In various embodiments, the initiator is selected from the group consisting of maleimide, N-methyl maleimide, or succinimide.
  • the initiator is maleimide.
  • the initiator is an oxazolidine, preferably an oxazolidine that is a methylene donor, preferably an oxazolidine formed from the condensation of formaldehyde and tris(hydroxymethyl)methylamine (Tris), an oxazolidine formed from the condensation of formaldehyde and 2-amino-2-methyl-l, 3-propanediol, or 2,3-dihydro-l,3-benzoxazole, preferably an oxazolidine formed from the condensation of formaldehyde and
  • Tris tris(hydroxymethyl)methylamine
  • Tris preferably l-aza-5-methylol-3,7- dioxabicyclo[3.3.0]octane.
  • the initiator is selected from the group consisting of an oxazolidine formed from the condensation of formaldehyde and tris(hydroxymethyl)methylamine (Tris), an oxazolidine formed from the condensation of formaldehyde and 2-amino-2-methyl-l,3- propanediol, or 2,3-dihydro-l,3-benzoxazole.
  • the initiator is an oxazolidine formed from the condensation of formaldehyde and
  • the initiator is l-aza-5- methylol-3,7-dioxabicyclo[3.3.0]octane.
  • the initiator is a methylene donor.
  • the initiator is a dialdehyde.
  • the initiator is an olefinically unsaturated aldehyde.
  • the initiator is a cyclic or acyclic diene.
  • the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1 :30, 1 :25, 1 : 20, 1 : 15, 1 : 12, 1 : 10, 1 :7, or 1 : 5, preferably at least 1 : 15, and useful ranges may be selected between any two of these values, for example from about 1 :30 to 1 : 5, 1 :25 to 1 : 5, 1 :20 to 1 : 5, 1 : 15 to 1 : 5, 1 :30 to 1 :7, 1 :25 to 1 :7, 1 :20 to 1 :7, 1 : 15 to 1 :7, 1 :30 to 1 : 10, 1 :25 to 1 : 10, 1 :20 to 1 : 10, or 1 : 15 to 1 : 10.
  • the stoichiometric ratio of initiator to furan rings provided by the furan monomer is from about 1:30 to 1:5, 1:25 to 1:5, 1:20 to 1:5, 1:15 to 1:5, 1:30 to 1:7, 1:25 to 1:7, 1:20 to 1:7, 1:15 to 1:7, 1:30 to 1:10, 1:25 to 1:10, 1:20 to 1:10, or 1:15 to 1:10.
  • the initiator is an imide and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:15, for example at least 1:12, 1:10, 1:7, or 1:5, and useful ranges may be selected between any two of these values, for example from about 1:15 to 1:5, 1:15 to 1:7, or 1:15 to 1:10.
  • the initiator is an imide and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1 : 12. In various embodiments, the initiator is an imide and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:10. In various embodiments, the initiator is an imide and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:7. In various embodiments, the initiator is an imide and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:5. In various embodiments, the initiator is an imide and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is from about 1:15 to 1:5, 1:15 to 1:7, or 1:15 to 1:10.
  • the initiator is an oxazolidine and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:27, for example at least about 1:25, 1:20, 1:15, 1:12, 1:10, 1:7, or 1:5, and useful ranges may be selected between any two of these values, for example from about 1:27 to 1:5, 1:25 to 1:5, 1:20 to 1:5, 1:15 to 1:5, 1:27 to 1:7, 1:25 to 1:7, 1:20 to 1:7, 1:15 to 1:7, 1:27 to 1:10, 1:25 to 1:10, 1:20 to 1:10, or 1:15 to 1:10.
  • initiator is an oxazolidine and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:20. In various embodiments, initiator is an oxazolidine and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:15. In various embodiments, initiator is an oxazolidine and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:12. In various embodiments, initiator is an oxazolidine and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:10.
  • initiator is an oxazolidine and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:7. In various embodiments, initiator is an oxazolidine and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1:5.
  • initiator is an oxazolidine and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is from about 1:27 to 1:5, 1:25 to 1:5, 1:20 to 1:5, 1:15 to 1:5, 1:27 to 1:7, 1:25 to 1:7, 1:20 to 1:7, 1:15 to 1:7, 1:27 to 1:10, 1:25 to 1:10, 1:20 to 1:10, or 1:15 to 1:10.
  • the initiator is an oxazolidine that is a methylene donor and the stoichiometric ratio of initiator, on a methylene donor basis, to furan rings provided by the furan monomer is at least about 1:14, for example at least 1:12, 1:10, 1:7, or 1:5, and useful ranges may be selected between any two of these values, for example from about 1 : 14 to 1 : 5, 1 : 14 to 1 : 7, or 1 : 14 to 1 : 10.
  • the initiator is an oxazolidine that is a methylene donor and the stoichiometric ratio of initiator, on a methylene donor basis, to furan rings provided by the furan monomer is at least 1:12. In various embodiments, the initiator is an oxazolidine that is a methylene donor and the stoichiometric ratio of initiator, on a methylene donor basis, to furan rings provided by the furan monomer is at least 1 : 10.
  • the initiator is an oxazolidine that is a methylene donor and the stoichiometric ratio of initiator, on a methylene donor basis, to furan rings provided by the furan monomer is at least 1:7.
  • the initiator is an oxazolidine that is a methylene donor and the stoichiometric ratio of initiator, on a methylene donor basis, to furan rings provided by the furan monomer is at least 1:5. In various embodiments, the initiator is an oxazolidine that is a methylene donor and the stoichiometric ratio of initiator, on a methylene donor basis, to furan rings provided by the furan monomer is from about 1:14 to 1:5, 1:14 to 1:7, or 1:14 to 1:10.
  • the impregnated wood product comprises at least about 15% (w/w) of the cured furan polymer for example at least 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80% (w/w), and useful ranges may be selected between any two of these values, for example 15 to 80, 20 to 80, 30 to 80, 40 to 80, 15 to 70, 20 to 70, 30 to 70, or 40 to 70%.
  • the weight uptake of the cured furan polymer in the impregnated wood product is at least about 20% (w/w) of the wood product prior to impregnation, for example at least about 22, 25, 27, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% (w/w), and useful ranges may be selected between any two of these values for example 20 to 85, 30 to 85, 40 to 85, 20 to 80, 30 to 80, 40 to 80, 20 to 70, 30 to 70, or 40 to 70%.
  • the impregnated wood product has CIE value for L* of from about 35 to 75, for example from about 35 to 70, 35 to 65, 35 to 60, 35 to 55, 40 to 75, 40 to 70, 40 to 65, 40 to 60, 40 to 55, 45 to 75, 45 to 70, 45 to 65, 45 to 60, or 45 to 55, preferably from about 45 to 55.
  • the impregnated wood product has CIE value for L* of from about 45 to 55.
  • the impregnated wood product has a CIE value for L* of at least 60% of the wood product prior to impregnation, for example at least 65, 70, 75, or 80%.
  • the impregnated wood product has a Janka hardness, as measured in accordance with ASTM D143, from about 50% to about 150% of the wood product prior to impregnation, for example from about 60 to 150, 70 to 150, 80 to 150, or 90 to 150%.
  • impregnated wood product has an anti-shrink efficiency (ASE) of at least 50%. In various embodiments, the impregnated wood product has an anti-shrink efficiency (ASE) of at least 60%.
  • the impregnated wood product further comprises one or more impregnatable colourants, pigments, or dyes.
  • the one or more impregnatable colourants, pigments, or dyes prevent or reduce the appearance of a change in colour on weathering of the impregnated wood product, for example for a period at least 3, 4, 5, or at least 6 months, preferably for a period of about 3-6 months.
  • the one or more impregnatable colourants, pigments, or dyes prevent or reduce the appearance of a change in colour on weathering of the impregnated wood product for a period of about 3-6 months.
  • the impregnated wood product further comprises and/or the cured reaction product is produced in the presence of a source of acid, for example a lactone, preferably lactide; and/or a source of base.
  • a source of acid for example a lactone, preferably lactide; and/or a source of base.
  • the impregnated wood product further comprises a source of acid, for example a lactone, preferably lactide; and/or a source of base.
  • the impregnated wood product further comprises a lactone.
  • the impregnated wood product further comprises a lactide.
  • the cured reaction product is produced in the presence of a source of acid, for example a lactone, preferably lactide; and/or a source of base.
  • a source of acid for example a lactone, preferably lactide; and/or a source of base.
  • the cured reaction product is produced in the presence of a lactone.
  • the cured reaction product is produced in the presence of a lactide.
  • the impregnated wood product further comprises and/or the cured reaction product is produced in the presence of one or more additives capable of reacting with the furan monomer, for example an amine, such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • one or more additives capable of reacting with the furan monomer for example an amine, such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • the impregnated wood product further comprises one or more additives capable of reacting with the furan monomer, for example an amine, such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • the impregnated wood product further comprises an amine.
  • the impregnated wood product further comprises an amino acid and/or amino alcohol.
  • the impregnated wood product further comprises lysine and/or Tris.
  • the cured reaction product is produced in the presence of one or more additives capable of reacting with the furan monomer, for example an amine, such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • an amine such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • the cured reaction product is produced in the presence of an amine. In various embodiments, the cured reaction product is produced in the presence of an amino acid and/or amino alcohol. In various embodiments, the cured reaction product is produced in the presence of lysine and/or Tris.
  • the method comprises impregnating the wood product with the furan monomer and the initiator.
  • the method comprises impregnating the wood product with the furan monomer and the monomer, oligomer, or polymer.
  • the monomer, oligomer, or polymer that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction is a prepolymer comprising a reaction product of a furan monomer and an initiator that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction; and the method further comprises the step of producing the prepolymer, prior to impregnation.
  • producing the prepolymer comprises reacting the furan monomer and the initiator under conditions effective for Diels Alder reaction.
  • producing the prepolymer comprises reacting the furan monomer and the initiator at an elevated temperature, for example at a temperature from about 40 to 80, 45 to 75, or 50 to 70°C, preferably 60°C, for a period of time, for example at least 1, 3, 6, or 12h, preferably about 12h; and optionally allowing the mixture to stand for a period of time, for example at least 24h, 48h, 72h, a week, two weeks, a month, or two or more months.
  • an elevated temperature for example at a temperature from about 40 to 80, 45 to 75, or 50 to 70°C, preferably 60°C, for a period of time, for example at least 1, 3, 6, or 12h, preferably about 12h; and optionally allowing the mixture to stand for a period of time, for example at least 24h, 48h, 72h, a week, two weeks, a month, or two or more months.
  • producing the prepolymer comprises reacting the furan monomer and the initiator at from about 40 to 80, 45 to 75, or 50 to 70°C, for at least 1, 3, 6, or 12h, preferably about 12h. In various embodiments, producing the prepolymer comprises reacting the furan monomer and the initiator at about 60°C, for about 12h. In various embodiments producing the prepolymer comprises allowing the mixture to stand for two or more months.
  • the method further comprises: providing a liquid formulation comprising the furan monomer and the initiator and/or the monomer, oligomer, or polymer; and
  • the impregnating comprises: subjecting the wood product to a vacuum in a vessel;
  • the reacting to produce the cured furan polymer comprises heating the wood product at a temperature from about 70 to about 140°C, preferably from preferably 90 to 120°C. In various embodiments, the reacting to produce the cured furan polymer comprises heating the wood product at a temperature from about 90 to 120°C.
  • the reacting to produce the cured furan polymer comprises heating the wood product at a first temperature from about 60 to about 90°C, preferably 90°C, for a first period of time, and heating the wood product at a second temperature from about 100 to 120°C, preferably 120°C, for a second period of time.
  • the reacting to produce the cured furan polymer comprises heating the wood product at about 90°C, for a first period of time, and heating the wood product at a second temperature about 120°C, for a second period of time.
  • the method further comprises impregnating the wood product, preferably prior to reacting to produce the cured furan polymer, with one or more impregnatable colourants, pigments, or dyes.
  • the method further comprises impregnating the wood product, prior to reacting to produce the cured furan polymer, with a source of acid, for example a lactone, preferably lactide; and/or a source of base.
  • the method further comprises impregnating the wood product, prior to reacting to produce the cured furan polymer, with a lactone.
  • the method further comprises impregnating the wood product, prior to reacting to produce the cured furan polymer, with a lactide.
  • the method further comprises impregnating the wood product, prior to reacting to produce the cured furan polymer, with one or more additives capable of reacting with the furan monomer, for example an amine, such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • the method further comprises impregnating the wood product, prior to reacting to produce the cured furan polymer, with an amine.
  • the method further comprises
  • the method further comprises impregnating the wood product, prior to reacting to produce the cured furan polymer, with lysine and/or Tris.
  • the method further comprises recovering unimpregnated liquid formulation comprising the furan monomer and the initiator and/or the monomer, oligomer, or polymer for reuse.
  • the method comprises impregnating the wood product with a liquid formulation comprising the furan monomer and the initiator and/or the monomer, oligomer, or polymer, wherein the liquid formulation is an unimpregnated liquid formulation recovered for reuse.
  • the formulation further comprises one or more impregnatable colourants, pigments, or dyes.
  • the formulation further comprises a source of acid, for example a lactone, preferably lactide; and/or a source of base.
  • a source of acid for example a lactone, preferably lactide.
  • the formulation further comprises one or more additives capable of reacting with the furan monomer, for example an amine, such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • an amine such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • the formulation further comprises an amine.
  • the formulation further comprises an amino acid and/or amino alcohol. In various embodiments, the formulation further comprises lysine and/or Tris. In various embodiments, the formulation is a liquid, optionally comprising one or more diluents and/or solvents suitable for impregnation.
  • the formulation is a liquid comprising one or more diluents and/or solvents suitable for impregnation. In various embodiments, the formulation is a liquid comprising one or more diluents suitable for impregnation. In various embodiments, the formulation is a liquid comprising one or more solvents suitable for impregnation.
  • the formulation is anhydrous.
  • the formulation is aqueous.
  • the impregnated wood product has a CIE value for L* that is at least 10% greater, for example at least 15%, 20%, 25%, 30%, 40%, or at least 50% greater, than the CIE value for L* of a corresponding impregnated wood product formed in the absence of the initiator and/or the monomer, oligomer, or polymer.
  • the invention may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, in any or all combinations of two or more of said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which the invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.
  • Figure 1 is a photograph showing a control sample and FA treated samples after cure and conditioning, as described in Example 1. Left to right are: Control (left); 3% maleimide; 5% maleimide; 10% maleimide; and 5% maleimide with dye.
  • Figure 2 is a photograph showing colours of pairs of a control sample and treated wood samples post-cure using pre-reacted FA treatment formulations, as described in Example 2 and Table 3. Untreated (left), standard FA/B130 6: 1, FA/B130-heat (pre-reacted),
  • FA/B130-re-used and FA/maleimide-heat (pre-reacted) (right).
  • FA/B130 samples were treated at pH 4, with all samples cured using the 90°C and 120°C stepped heating ramp described herein.
  • Figure 3 is a photograph showing colours of pairs of a control sample and treated wood samples post-cure using differing FA/Oxazolidine ratios or methylene content as described in Example 2 and Table 3.
  • Figure 4 is a photograph showing colours of pairs of a control sample and treated wood samples post-cure using different differing formulations including additional catalysts, alternate methylene donors post-cure as described in Example 2 and Table 3.
  • Untreated control left).
  • FA/B130 14 1, FA/Tris, FA/Hexamine, FA/B130/lysine, FAB130/5%lactide and FA/Tris/5%lactide (right). All samples treated at pH 4 and cured with the 90°C and 120°C stepped heating ramp.
  • Figure 5 are photographs taken from different angles showing colouring contributed by different FA treatments, as described in Example 4. Left to right: unmodified wood; FA/Mal; FA/NMM; FA/Succ; FA/Mal/AHPO; FA/APD; and FA/BPh.
  • Figure 6 is a graph showing CIE L* (horizontal lined bars - leftmost in each set of 3), a* (sideways hashed bars - middle in each set of 3), and b* (grey bars - rightmost in each set of 3) colour values for different FA treatments, as described in Example 4. Colour-meter measurements undertaken on freshly sanded surfaces. In the graph the sample labelled FA/Mal/Ox equates to FA/Mal/AHPO.
  • Figure 7 is a graph showing heating ramps and hold temperatures employed in FA/B130 curing regimes, as described in Example 3.
  • the timelines for curing will vary depending on the size of the wood substrate and the treatment formulation.
  • alkyl refers to a radical of a straight-chain or branched saturated hydrocarbon group. In some embodiments, alkyl groups have from 1 to 8, 1 to 6, or 1 to 4 carbon atoms. Examples of alkyl groups include but are not limited to methyl, ethyl, n- propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, n-pentyl, 3-pentanyl, amyl, neopentyl, 3-methyl-2-butanyl, tertiary amyl, n-hexyl, and the like.
  • Carbocyclic refers to a ring system in which all of the ring atoms are carbon atoms.
  • Carbocyclic ring systems include monocyclic and bicyclic ring systems.
  • the ring(s) of the carbocyclic ring system may be saturated, unsaturated (including partially unsaturated), or aromatic.
  • Carbocyclic ring systems include phenyl, cycloalkyl (e.g., cyclopentyl, cyclohexyl and the like), and cycloalkenyl (e.g., cyclopentenyl, cyclohexenyl, and the like) ring systems.
  • carbocyclic ring systems comprise from 3 to 12 ring carbon atoms, for example from 3 to 10, 3 to 8, 3 to 6, 4 to 12, 5 to 12, 5 to 10, 5 to 8, or 5 or 6 ring carbon atoms.
  • Examples of carbocyclic ring systems include but are not limited to phenyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl,
  • heterocyclic refers to a carbocyclic ring system in which one or more of the ring carbon atoms are replaced with a heteroatom.
  • Heterocyclic ring systems include monocyclic and bicyclic ring systems.
  • the ring(s) of the heterocyclic ring system may be saturated, unsaturated (including partially unsaturated), or aromatic.
  • the heterocyclic ring system may comprise 1, 2, 3, or 4 ring heteroatoms.
  • each heteroatom is independently selected from O, N, S.
  • heterocyclic ring systems comprise from 3 to 12 ring atoms, for example from 3 to 10, 3 to 8, 3 to 6, 4 to 12, 5 to 12, 5 to 10, 5 to 8, or 5 or 6 ring atoms.
  • heterocyclic ring systems include, but are not limited to, pyrrolidines, pyrroles, imidazoles, triazoles, thiophenes, oxazoles, pyridines, piperidines, pyrans, azepines, and indoles.
  • the present invention relates to a cured furan polymer impregnated wood product.
  • the cured furan polymer comprises a cured reaction product of a furan monomer and an initiator that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction; and/or a monomer, oligomer, or polymer that prevents or reduces crosslinking between chains of polymerised furan monomer by furan- furan Diels Alder reaction.
  • wood product refers to a product comprising wood.
  • wood products include, but not limited to, lumber, timber, and wood composites.
  • wood composites include, but are not limited to, particleboard, oriented strand board, waferboard, fibreboard, parallel strand lumber, laminated strand lumber, plywood, laminated veneer lumber, finger jointed lumber, and the like.
  • Wood products also include wood fibres, particles, flakes, strands, chips, or sheets, for example from which wood composites may be produced.
  • the wood may be a softwood or hardwood.
  • Specific woods useful in the invention described herein include pine, for example Pinus radiata, Scots pine, or southern yellow pine, beech, ash, maple, birch, alder, oak, aspen, poplar, and the like.
  • the wood product may be any suitable dimension.
  • the wood product is a large dimension product, for example a large piece of lumber or timber.
  • the moisture content of the wood product that is impregnated can vary and, for example, may be of up to about 30%, for example from about 5 to 30, 10 to 30, 15 to 30, 5 to 25, 10 to 25, 5 to 20, or 10 to 20% by weight of the wood product prior to impregnation.
  • the cured furan polymer comprises a cured reaction product produced by reacting the furan monomer and the initiator and/or the monomer, oligomer, or polymer to polymerise the furan monomer and cure the resultant polymer.
  • the reaction product may, thus, be referred to herein as a polymerisation reaction product.
  • the furan monomer is a monomer comprising one or more furan rings capable of polymerising to provide a furan polymer.
  • suitable furan monomers include but are not limited to furfuryl alcohol (FA), bishydroxymethyl furan (BHMF), tri hydroxymethyl furan (THMF), furfural, oligomers thereof, condensation products thereof, and combinations thereof.
  • a preferred furan monomer is furfuryl alcohol (FA).
  • furfuryl alcohol polymerises to form black crosslinked products (Gandini, A., Furans as offspring of sugars and polysaccharides and progenitors of a family of remarkable polymers: a review of recent progress, Polymer chemistry, 2010. p. 245-251.). This dark colour is primarily due to Diels-Alder reaction between furan rings of different polymer chains, which results in a crosslinked or conjugated structure.
  • the initiator and/or the monomer, oligomer, or polymer prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction, compared to reaction products formed in the absence of the initiator and/or the monomer, oligomer, or polymer.
  • This prevention or reduction in crosslinking via furan-furan Diels Alder reaction between chains of polymerised furan monomer results in the impregnated wood product having a lighter colour.
  • embodiments of the present invention can provide cured furan polymer impregnated wood products that are lighter in colour and may be less brittle, but are still dimensionally stable.
  • the initiator is a compound capable of initiating polymerisation of the furan monomer, in addition to preventing or reducing crosslinking by furan-furan Diels Alder reaction.
  • the initiator may be capable of reacting in a Diels Alder reaction with furan rings of the furan monomer and/or polymerised chains thereof.
  • the initiator is an imide.
  • an "imide” is a compound comprising two acyl groups bound to a nitrogen atom.
  • An imide may be a cyclic or acyclic. In some embodiments, the imide may comprise from 4 to 20 carbon atoms, for example 4 to 16, 4 to 12, 4 to 10, 4 to 8, or 4 to 6 carbon atoms.
  • a cyclic imide may comprise a 5-8 membered ring, preferably 5 or 6 membered ring, preferably a 5 membered ring, comprising the imide nitrogen.
  • the ring may be a saturated ring or an unsaturated, non-aromatic ring.
  • the cyclic imide is an imide of a dicarboxylic acid.
  • the nitrogen atom of the imide may unsubstituted or substituted, for example with an alkyl group of 1 to 6 carbon atoms, such as a methyl group.
  • suitable imides include but are not limited to maleimide, N-methyl maleimide, and succinimide.
  • a preferred imide is maleimide.
  • the initiator is an oxazolidine.
  • an "oxazolidine” is a compound comprising a 5-membered ring with an oxygen atom at the 1 position, a nitrogen atom at the 3 position, and carbons atoms at the remaining positions of the ring.
  • Oxazolidines include monocyclic and bicyclic oxazolidines.
  • the oxazolidine may comprise from 5 to 12 ring atoms, preferably 5 or 8 ring atoms, and/or from 3 to 20 carbon atoms, for example 3 to 16, 3 to 12, 3 to 10, 3 to 8, 5 to 20, 5 to 16, or 5 to 12 carbon atoms.
  • Bicyclic oxazolidines include but are not limited to compounds wherein the 5 membered oxazolidine ring is fused to another ring via the carbon atoms at positions 4 and 5 of the oxazolidine ring or via the nitrogen atom and the carbon atom at position 4 of the oxazolidine ring.
  • the ring fused to the oxazolidine ring may be a 5-8 membered, preferably 5 or 6 membered carbocyclic or heterocyclic ring, which may be saturated, unsaturated, or aromatic.
  • the oxazolidine is a methylene donor.
  • the carbon atom at position 2 of the oxazolidine ring is bound to two hydrogen atoms.
  • Such oxazolidines may be formed by condensation of an appropriate amino alcohol with formaldehyde by methods well known in the art.
  • Suitable oxazolidines include but are not limited to oxazolidines formed by the condensation of formaldehyde and tris(hydroxymethyl)methylamine (Tris), 2-amino-2- methyl-1, 3-propanediol, and 2-aminophenol. Condensation of one or two equivalents of formaldehyde with Tris provides the oxazolidines
  • oxazolidine l-aza-5- methyl-3,7-dioxabicyclo[3.3.0]octane.
  • Condensation of formaldehyde and 2-aminophenol provides the oxazolidine 2,3-dihydro-l,3-benzoxazole.
  • a preferred oxazolidine is the oxazolidine formed by the condensation of Tris and two equivalents of formaldehyde, i.e.
  • R 2 is hydrogen, alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 1 to 8 carbon atoms, benzyl, or phenylcarbamyl, and each of R 3 , R 4 , and R 5 is hydrogen or an alkyl of 1 to 8 carbon atoms.
  • oxazolidines there can be mentioned : 4,4-dimethyl-l,3- oxazolidine; 3-(2-hydroxyethyl)-l,3-oxazolidine; 3-(2-hydroxypropyl)-5-methyl-l,3- oxazolidine; 5-methyl-l,3-oxazolidine; 3-ethyl-l,3-oxazolidine; 3-benzyl-l,3-cyclohexyl-5- methyl-l,3-oxazolidine; 3-phenylcarbamyl-4,4-dimethyl-l,3-oxazolidine; as well as the corresponding bis(l,3-oxazolidino)methanes such as bis(4,4-dimethyl-l,3- oxazolidino)methane.
  • R is hydrogen, methyl, ethyl, n-propyl, isopropyl, methylol, beta-hydroxyethyl, acetoxymethyl or methoxymethyl.
  • oxazolidines there can be mentioned : l-aza-3,7-dioxabicyclo[3.3.0]octane; l-aza-5-methyl-3,7-dioxabicyclo[3.3.0]octane; 1-aza- 5-ethyl-3,7-dioxabicyclo[3.3.0]octane; l-aza-5-n-propyl-3,7-dioxabicyclo[3.3.0]octane; 1- aza-5-isopropyl-3,7-dioxabicyclo[3.3.0]octane; l-aza-5-methylol-3,7- dioxabicyclo[3.3.0]octane; l-aza
  • a preferred oxazolidine is l-aza-5-methylol- 3,7-dioxabicyclo[3.3.0]octane, such as that sold under the trademark ZOLDINE ZT-55 by Angus Chemical Company.
  • the initiator is a methylene donor.
  • the methylene donor may be an oxazolidine, as described herein. However, other methylene donors are also useful in the invention.
  • Suitable methylene donors include but are not limited to oxazinanes, dioxolanes, dioxanes, imidazolidines, piperizines, hexamines, and the like, preferably oxazinanes, dioxolanes, imidazolidines, and hexamines.
  • the oxazinanes, dioxolanes, dioxanes, imidazolidines, and piperizines contemplated herein include monocyclic or bicyclic compounds.
  • Bicyclic oxazinanes, dioxolanes, dioxanes, imidazolidines, piperizines include fused bicyclic compounds, including an oxazinane, dioxolane, dioxane, imidazolidine, or piperazine ring and a fused 5-8 membered, preferably 5 or 6 membered, carbocyclic or heterocyclic ring, which fused ring may be saturated, unsaturated, or aromatic.
  • the initiator is a dialdehyde.
  • the dialdehyde comprises from 4 to 10 carbon atoms, for example from 4 to 8 carbon atoms, or from 4 to 6 carbon atoms.
  • One example of a suitable dialdehyde is glutaraldehyde.
  • Other suitable aldehydes will be apparent to those skilled in the art.
  • the initiator is an olefinically unsaturated aldehyde comprising one or more one olefin (non-aromatic carbon-carbon double bond) and one or more aldehyde.
  • the olefinically unsaturated aldehyde comprises from 4 to 10 carbon atoms, from 4 to 8 carbon atoms, or from 4 to 6 carbon atoms. In some embodiments, the olefinically unsaturated aldehyde comprises an a,b-unsaturated aldehyde. In some embodiments, the olefinically unsaturated aldehyde comprises two or more olefins, which optionally may be conjugated. One example of a suitable unsaturated aldehyde is sorbaldehyde. Other suitable olefinically unsaturated aldehydes will be apparent to those skilled in the art.
  • the initiator is a cyclic or acyclic diene.
  • the diene is capable of undergoing a 2+2 addition to a furan ring.
  • the diene comprises from 4 to 16 carbon atoms, 4 to 10 carbon atoms, from 4 to 8 carbon atoms, or from 4 to 6 carbon atoms.
  • the cyclic diene may be carbocyclic or heterocyclic.
  • Carbocyclic or heterocyclic dienes may comprise from 4 to 12 ring atoms, preferably 5 to 12 ring atoms. Cyclic dienes include monocyclic and bicyclic dienes.
  • the cyclic diene may be a non-aromatic carbocyclic diene or an aromatic or non-aromatic heterocyclic diene, the heterocyclic diene preferably comprising one or more oxygen, nitrogen, or sulfur atoms in the ring(s).
  • the cyclic or acyclic diene comprises a conjugated diene.
  • suitable cyclic or acyclic dienes include thiophene and 2-(alkyl) butadienes (for example, 2-methylbutadiene), respectively.
  • Any suitable amount of the initiator may be used. The amount may depend on the initiator used and the desired properties of the impregnated wood product, for example colour, hardness, dimensional stability, and the like.
  • the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1 :30, 1 :25, 1 :20, 1 : 15, 1 : 12, 1 : 10, 1 :7, or 1 : 5, preferably at least 1 : 15.
  • the initiator is an imide and the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1 : 15.
  • the initiator is an oxazolidine and the
  • the stoichiometric ratio of initiator to furan rings provided by the furan monomer is at least about 1 :27.
  • the initiator is an oxazolidine that is a methylene donor and the stoichiometric ratio of initiator, on a methylene donor basis, to furan rings provided by the furan monomer is at least about 1 : 14. It has been found that such ratios provide wood products having relatively light colour compared to traditional furfurylation, and in some embodiments useful other properties, such as reduced hardness or brittleness.
  • Any suitable monomer, oligomer, or polymer in the present invention that prevents or reduces crosslinking by furan-furan Diels Alder reaction between chains of polymerised furan monomer may be used in the invention.
  • suitable monomers, oligomers, or polymers include but are not limited to furan monomers comprising a sterically bulky group, for example at position 3 or 4 of the furan ring, and oligomers and polymers comprising such monomers.
  • the monomer modifies the helicity of the furan polymer and/or the spacing between furan units of different chains in the furan polymer.
  • furan polymers exhibit helicity and that the reaction of a monomer that leads to a modification, for example reduction, in the helicity of the chains of the furan polymer produced (compared to the helicity of a corresponding polymer formed in the absence of the helicity modifying monomer) which prevents or reduces crosslinking, in particular furan-furan Diels Alder reactions, between chains of polymerised furan monomer.
  • reacting a monomer that modifies the spacing i.e.
  • the monomer that modifies the spacing between furan units of the polymer also modifies the helicity of the polymer. Modification of helicity and/or spacing may be due to the incorporation of such a monomer or a group derived therefrom into chains of the polymer (e.g. between two adjacent furan units of a chain) or substitution of chains of the polymer with such a monomer or group.
  • the monomer that modifies helicity and/or spacing comprises a sterically bulky group (such as the 3- or 4-substituted furan monomers described above) and/or other group that increases the distance between furan units of different chains.
  • the monomer, oligomer, or polymer is a prepolymer comprising a reaction product of a furan monomer and an initiator that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction.
  • prepolymers may be prepared as described herein.
  • the amount of cured furan polymer in the wood product can vary.
  • the impregnated wood product may comprise at least 15% (w/w) of the cured furan polymer.
  • the weight uptake of the cured furan polymer in the impregnated wood product is at least 20% (w/w) of the wood product prior to impregnation.
  • a colour may be defined by the International Commission on Illumination (French).
  • a range of colours may be defined by a Delta-E metric that provides a measure of the difference between two colours, for example, the International Commission on Illumination CIE DE2000 Delta-E value. Unless otherwise specified, in this specification and claims, Delta-E is the CIE DE2000 value.
  • the L*, a* and b* measurements referred to herein unless indicated otherwise relate to freshly prepared surfaces, for example freshly sanded surfaces for lumber, as the colour of surfaces can change over time.
  • the impregnated wood product of the invention may have a CIE value for L* of from about 35 to 75, preferably from about 45 to 55; and/or a CIE value for L* of at least 60% of the wood product prior to impregnation.
  • the prevention or reduction in crosslinking provided by the initiator and/or the monomer, oligomer, or polymer is characterised by the impregnated wood product having a lighter colour compared to a corresponding impregnated wood product formed in the absence of the initiator and/or the monomer, oligomer, or polymer, for example by traditional furfurylation in the presence of an acid catalyst, such as zinc-chloride.
  • the lighter colour may be determined visually or by other suitable methods. In some embodiments, the lighter colour is determined by an increased CIE value for L*.
  • the impregnated wood product has a CIE value for L* that is at least 10% greater, for example at least 15%, 20%, 25%, 30%, 40%, or at least 50% greater than the CIE value for L* of a corresponding impregnated wood product formed in the absence of the initiator and/or the monomer, oligomer, or polymer reacted in the present invention.
  • the impregnated wood product may have Janka hardness, as measured in accordance with ASTM D143, from about 50% to about 150% of the wood product prior to impregnation.
  • the Janka hardness will depend in part on the wood product, with some wood products being harder than others.
  • the impregnated wood product preferably has useful dimensional stability. Dimensional stability may be determined by anti-shrink efficiency (ASE).
  • ASE anti-shrink efficiency
  • the impregnated wood product may have an ASE of at least 40%, preferably 50%, preferably 60%.
  • the impregnated wood product may comprise one or more impregnatable colourants, pigments, or dyes, for example that prevent or reduce the appearance of a change in colour on weathering of the impregnated wood product, for example for a period at least 3, 4, 5, or at least 6 months, preferably for a period from about 3-6 months. Any suitable impregnatable colourant, pigment, or dye for wood products may be used.
  • the impregnated wood product may comprise and/or the cured reaction product may be produced in the presence of one or more additional agents, for example a source of acid, for example a lactone, preferably lactide; and/or a source of base; and/or one or more additives capable of reacting with the furan monomer, for example an amine, such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • a source of acid for example a lactone, preferably lactide
  • a source of base for example an amine, such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • the furan polymer impregnated wood product may comprise or be impregnated with various other compounds, agents,
  • compositions, and formulations such as resins and wood preservation formulations, for example pesticides, fire retardants, and anti-sapstains.
  • the present invention also relates to a method of producing a cured furan polymer impregnated wood product.
  • the method comprises:
  • the wood product; the furan monomer; the initiator; and/or the monomer, oligomer, or polymer; may be as described herein with respect to the cured furan polymer impregnated wood product of the invention.
  • the monomer, oligomer, or polymer that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction is a prepolymer comprising a reaction product of a furan monomer and an initiator that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction; and the method further comprises the step of producing the prepolymer prior to impregnation.
  • the conditions for producing the prepolymer depend, in part, on the initiator used. For example, where an initiator capable of reacting with furan monomer via Diels Alder reaction is used, producing the prepolymer may comprise reacting the furan monomer and the initiator under conditions effective for Diels Alder reaction.
  • Producing the prepolymer typically comprises reacting the furan monomer and the initiator at an elevated temperature for a period of time.
  • the elevated temperature may be from about 40 to 80, 45 to 75, or 50 to 70°C, preferably 60°C.
  • the period of time for which the reaction mixture is heated can vary. In some embodiments, the period of time is at least 1, 3, 6, or 12h, preferably about 12h.
  • the temperature and period of time may be selected such that the furan monomer does not polymerise to any significant extent, for example any oligomers or polymers formed remain soluble in the solution. After heating, the mixture may be allowed to stand for a period of time, for example at least 24h, or even weeks or months.
  • the furan monomer and the initiator and/or the monomer, oligomer, or polymer may be impregnated into the wood product separately or together in the form of liquid
  • the impregnation of a single liquid formulation comprising all of the ingredients to be impregnated is typically preferred.
  • the stoichiometric ratio of initiator to furan rings provided by the furan monomer in the material impregnated into the wood product and/or the impregnated wood product may be as described herein with respect to the impregnated wood product of the invention.
  • any suitable method for impregnating the wood product may be used, for example vacuum pressure soaking (VPS).
  • the impregnating comprises subjecting the wood product to a vacuum in a vessel; immersing the wood product in the liquid formulation; and pressurising the vessel.
  • impregnation may be carried out without pressure and/or vacuum.
  • the furan monomer and the initiator and/or the monomer, oligomer, or polymer are then reacted under conditions effective for polymerisation to produce the cured furan polymer.
  • This polymerisation and curing step typically comprises delivering heat to the wood product. Heat may be delivered by any suitable means, for example hot air, steam, or high frequency heating. The heat activates the initiators and starts polymerisation. Reacting to produce the cured furan polymer may comprise heating the wood product at a temperature from about 70 to about 140°C, preferably from preferably 90 to 120°C.
  • reacting to produce the cured furan polymer comprises heating at a first temperature from about 60 to about 90°C, preferably 90°C, for a first period of time, and heating at a second temperature from about 100 to 120°C, preferably 120°C, for a second period of time.
  • the period of time for which the wood product is heated for polymerisation and curing will vary, for example depending on the size of the wood product and the type of oven or kiln. Times may range from about 0.5h to about 24h, for example from 1 to 24, 1 to 18, 1 to 12, 6 to 24, 6 to 18, or 6 to 12h.
  • the method may further comprise impregnating one or more additional agents, prior to reacting to produce the cured furan polymer, for example one or more impregnatable colourants, pigments, or dyes; and/or with a source of acid, for example a lactone, preferably lactide; and/or a source of base; and/or one or more additives capable of reacting with the furan monomer, for example an amine, such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • the one or more additional agents may be in the liquid formulation for impregnating the furan monomer and the initiator and/or the monomer, oligomer, or polymer.
  • unimpregnated liquid formulation comprising the furan monomer and the initiator and/or the monomer, oligomer, or polymer may be recovered for reuse, and recycled in the method. Such recycling can provide significant cost savings.
  • the present invention also relates to a cured furan polymer impregnated wood product produced by a method of the present invention.
  • the present invention also relates to a formulation for impregnating a wood product, the formulation comprising :
  • an initiator that prevents or reduces crosslinking between chains of polymerised furan monomer by furan-furan Diels Alder reaction;
  • the wood product; the furan monomer; the initiator; and/or the monomer, oligomer, or polymer; and/or the stoichiometric ratio of initiator to furan rings provided by the furan monomer may be as described herein with respect to the cured furan polymer impregnated wood product of the invention.
  • the formulation may further comprise various additional agents for impregnation, for example one or more impregnatable colourants, pigments, or dyes, a source of acid, for example a lactone, preferably lactide; and/or a source of base; and/or one or more additives capable of reacting with the furan monomer, for example an amine, such as an amino acid and/or amino alcohol, for example lysine and/or Tris.
  • a source of acid and/or a source of base may be used to control the pH of the formulation, for example prior to and/or on impregnation.
  • the formulation may be a liquid, solid, semisolid or other suitable form.
  • a liquid formulation may be provided in the form of a concentrate that is diluted prior to impregnation or in the form of a ready to use formulation comprising a suitable diluent and/or solvent.
  • Solid or semisolid formulations are converted to liquid form for impregnation, for example by dissolving or suspending in a suitable diluent and/or solvent.
  • Diluents and/or solvents suitable for impregnation will be apparent to those skilled in the art and include but are not limited to water, alcohols, for example ethanol, and the like.
  • the formulation may be anhydrous or aqueous. In some embodiments, aqueous formulations are preferred.
  • Pinus radiata wood was obtained green and kiln-dried (KD, 90/60°C) to 12% moisture content. Samples (18 x 18 x 100 mm) were then machined and set aside prior to treatment.
  • FA furfuryl alcohol
  • H20 furfuryl alcohol 15:4: 1
  • maleimide was added at 3%, 5% and 10% (w/w) and thoroughly mixed.
  • the relative ratios of components are 71.1% FA, 5.1% maleimide, 19% water and 4.7% ethanol.
  • Kiln-dried wood samples (18x18x100 mm) were immersed in the FA treatment solution and subjected to a vacuum pressure soak treatment. A vacuum was drawn for 30 mins followed by pressure (1400 kPa) for 1 h. Samples were then heated in a steam box for 12 h followed by conditioning in a kiln (90/60°C) for 2 h. Samples were then equilibrated at 65% relative humidity (RH) and 20°C to achieve constant weight.
  • RH relative humidity
  • Relative hardness measurements used Janka hardness testing protocols (ASTM D143). A 5 mm ball bearing was pushed into the wood and the maximum force calculated to achieve the penetration depth. Treated and reference samples were first conditioned at 20°C and 65% RH then testing undertaken on both radial and tangential faces.
  • Samples (18 x 18 x 20 mm) were accurately measured and weighed. Samples were first subjected to vacuum pressure soaking in water (30 minutes vacuum and then 1 h 200 bar). Samples were then re-weighed and measured before being placed in an oven (105°C) for at least 16 h. At least 12 specimens were used per sample. Average ASE values are based on sample volume swell and were calculated by:
  • V volume change
  • WS water soaked sample
  • OD oven dried sample
  • the wood used was kiln-dried radiata pine with approximated 12% MC.
  • Parent boards (6 in total) in green state were sourced from a local saw mill (Red Stag Ltd) and then kiln-dried in-house using a standard 90/60 drying regime. Boards were then cut into 18x18x100 mm specimens and stored at EMC (20°C/65% RH) until required.
  • the oxazolidine B130 solution was prepared by mixing paraformaldehyde (18.24 g) and water (46.4 g) and thoroughly dispersing before adding tris(hydroxymethyl)methylamine (“Tris”) (35.6 g). After further mixing the solution was left to stand overnight giving a colourless B130 solution.
  • Tris tris(hydroxymethyl)methylamine
  • An aqueous 75% furfuryl alcohol solution was prepared by adding furfuryl alcohol and water (FA:water 3: 1). This aqueous FA solution (100 g) and B130 solution (7.5 g) were then mixed and allowed to stand for at least 7 days before use. Each formulation was prepared in sufficient volume (>600 mL) to undertake treatment of 8 (18x18x100 mm) KD specimens by vacuum pressure soaking.
  • Kiln-dried wood samples (18x18x100 mm) were immersed in the FA treatment solution and subjected to a vacuum pressure soak treatment. A vacuum was drawn for 30 mins followed by an over pressure (1400 kPa) for 1 h. Samples were then heated in a metal box for >14 h using the stated curing regime. Samples were then equilibrated at 65% RH and 20°C to achieve constant weight. Specimens were accurately weighed and measured before and after treatment and when equilibrated.
  • Wood specimens (treated or retained as untreated, reference samples) were cut from 6 individual radiata pine parent boards. While attempts were made to obtain identical, matched boards for comparative purposes, subsequent conditioning and testing of samples revealed variations in wood density and properties which manifest in (un)treated sample data sets.
  • FA-treated products are typically associated with increased wood brittleness.
  • FA/B130 does not appear to deliver a rigid crosslinked FA polymer, it may be anticipated there is no significant change in wood brittleness. This appears to also be the case for the pre-reacted FA/Mal treatment which was revealed to have lower hardness than found with FA/Mal work in earlier Examples.
  • the greater densification achieved with FA deposition in the wood may also manifest in other wood properties beyond brittleness.
  • Treatment solutions were generally prepared using an aqueous 75% furfuryl alcohol solution (furfuryl alcohol:water:ethanol, 15:4: 1 or 5 parts water only). This FA solution had 5%
  • the 75% FA solution had maleimide added at 3%, 5% and 10% (w/w).
  • cured FA weight uptake was greater with higher maleimide content, but the three initiator loadings gave visually similar treated wood colour.
  • Higher maleimide gave greater wood hardness and anti-shrink efficiency (dimensional stability).
  • Treatment with 5% maleimide/FA provided a useful a balance of uptake and property enhancement while providing reduced colour compared to typical FA treatment.
  • Calculation of the mole ratio of FA to maleimide for the 3%, 5% and 10% (w/w) treatment solutions are 25: 1, 15: 1 and 7.5: 1 (FA: Mal), respectively.
  • At 5% maleimide incorporation just 1 maleimide unit is added per 15 furan units.
  • FA/B130 treatment solutions at pH 4, 7 and 9 were adjusted with lactic acid (or acetic acid) or sodium hydroxide at least 24 hours (typically >72 h) prior to treatment.
  • Curing at 110- 120°C (ramp/hold) delivered a relatively colour-neutral modification with pH 7 and pH 9 whereas the pH 4 treatment gave a light brown colour and moderately greater hardness and ASE.
  • the heating regime used was dependent on sample dimensions and kiln size/packing.
  • B130 can react with the methylol (-CH2OH) giving amino functionality, or grafting to C2 and C3 via alkylation.
  • -CH2OH methylol
  • the steric hindrance or modified FA polymer helicity is sufficient to reduce/inhibit furan ring cycloaddition and conjugation (dark colour).
  • the minimum, effective mole ratio of FA to B130 was 14: 1, which is relatively similar to that for FA/Mal (15: 1).
  • Lactide-catalysed curing of FA within wood Lactide a cyclic lactone (the di-ester of lactic acid), has been used to substitute the organic acid or anhydride in furfurylation treatments.
  • the FA/lactide formulation has been scaled, with treatments undertaken on 50x100x1200mm samples.
  • FA/B130 treatments were combined with lactide, lysine and Tris to compare amine and carboxylic functionalities in FA/B130 treatments solutions.
  • FA/B130 with lactide led to 48% FA uptake, similar to FA/B130/Lysine (50%).
  • Samples have a range of brown colours darker than FA/B130 ( Figure 4) as well as differing hardness (2.2 to >4 kN).
  • ASE values were all ca. 45%, similar to FA/lactide.
  • the lactide-modified FA/B130 formulations give uptakes and dimensional stability typical of wood furfurylation, but provide other colour options, including neutral to light brown colour options, and variants to formulate FA treatments.
  • amino-methylpropanediol (APD) oxazolidine solution was prepared.
  • a 75% aqueous FA solution 1000 g was prepared by combining furfuryl alcohol (750 g) and water (250 g).
  • the APD oxazolidine solution 68 g was then added, mixed and allowed to stand for at least 7 days before use. 24 Hours prior to wood treatment this FA/APD solution was adjusted to pH 4.7 with lactic acid and then left overnight.
  • Benzoxazolidine (BPh) was first formed by mixing 2-aminophenol (51.9 g) and water (190 g) and thoroughly dispersing. Next paraformaldehyde (14.5 g) was carefully added with stirring of this solution. The solution was then allowed to stand overnight to yield a BPh benzoxazolidine suspension.
  • furfuryl alcohol 750 g
  • water 120 g
  • the BPh benzoxazolidine suspension was then added to the aqueous FA solution, mixed and then allowed to stand for at least 7 days prior to use. This dark solution was then adjusted to pH 4.7 with lactic acid 24 hours prior to FA/APD treatment.
  • the FA/Succ treatment solution was formed by adding succinimide (Succ) (52 g) to a 75% aqueous FA solution (1000 g). After mixing and then standing for at least 24 h the solution was heated at 60°C for 12 hours. This FA/Succ solution was then allowed to stand before wood treatment. Preparation of FA/NMM treatment solution
  • the FA/NMM treatment solution was formed by adding N-methyl maleimide (NMM) (58 g) to a 75% aqueous FA solution (1000 g) then mixed and allowed to stand for at least 24 h. This solution was then heated at 60°C for 12 hours prior to FA/NMM treatment.
  • NMM N-methyl maleimide
  • a 2-amino-2-methyl-l,3-propanediol oxazolidine (AHPO) solution was prepared first.
  • the FA/Mal/AHPO treatment solution was prepared by combining a 75% aqueous FA solution (1000 g) with maleimide (50 g) and mixing. Next, AHPO solution (75 g) was added and the solution thoroughly mixed. After standing for 24 h, this treatment solution was pre- reacted at 60°C for 12 h. Prior to treatment, the solution was adjusted to pH 4.7 with lactic acid 24 h prior to wood treatment.
  • Kiln-dried wood samples (18x18x100 mm, total of 8) were placed in 2 L Parr vessel and weighted to be below the anticipated treatment solution level. A vacuum was drawn for 30 mins followed by adding the FA treatment solution and flooding the treatment vessel. A pressure (1400 kPa) was then applied for 1 h. The treatment vessel was then de- pressurised. Treated samples were then removed and weighed.
  • ASE specimens (18x18x20 mm) were cut from the ends of each treated 18x18x100 mm specimen. The remaining centre section was used for hardness testing. Test specimens are also similarly cut from untreated controls.
  • Conditioned samples (18 x 18 x 20 mm) are accurately measured and weighed. Samples were first subjected to vacuum pressure soaking in water (30 minutes vacuum and then 1 h 1400 kPa). Samples were then re-weighed and measured before being placed in an oven (105°C) for at least 16 h. At least 12 test specimens were used per sample. At least 12 specimens were used per sample. Average ASE values are based on sample volume swell and were calculated by the equation in Example 1.
  • each was prepared, applied and then cured in situ within the treated wood using the same processing protocols described for the FA/Mal and FA/Oxazolidine formulations in the Example 3 above.
  • Table 5 Shown in Table 5 are equilibrated FA (%weight) uptakes for the various treatments.
  • the table includes 3 series of data - an "Original" trial with the maleimide style treatment; a “Repeated” trial with the maleimide-style treatments, due to differences in kiln schedules (Table 5). Results show a high degree of variability in specimen weight uptakes, which range from ⁇ 15% to greater than 70% weight uptake. While the differences in the maleimide-style treatments can be attributed to the two differing kiln schedules, the range of uptakes in the oxazolidine-style treatments was equally variable and may be attributable to chemical and reactivity differences and FA curing across treatment formulations. Table 5. Summary of furfuryl alcohol treated sample weight uptakes (as FA) on equilibration at 20°C and 65% RH.
  • the kiln schedule for the curing temperature profiles for three treated sample sets was set up to follow a 90°C and 120°C heat and hold procedure.
  • the set points for this standard schedule were a ramp to 90°C (2 h), 90°C hold (5 h) then ramp to 120°C (1 h) before the final hold at 120°C (>7 h).
  • the wood temperature reached only 85°C before proceeding to the final 120°C curing step. This resulted in calculated weight gains ⁇ 40%, attributable to FA loss from these samples (Table 5).
  • the curing schedule was then adapted to first achieve 90°C during the cure before holding.
  • the FA/Maleimide weight uptake was comparable to that in preceding Examples as was the treated sample colour and performance. This treatment involved the kiln schedule achieving 90°C to induce FA curing and associated performance. The 60°C pre-reaction of
  • FA/maleimide also provided a lighter coloured treatment solution compared to oxazolidine addition.
  • N-Methyl maleimide was similar to maleimide in producing low colour, but had a lower degree of cure, which may be due to insufficient cure time (the Kiln regime being too short) and/or the N-methyl impacting on FA cure and cross-linking in the treated sample.

Abstract

L'invention concerne des produits en bois imprégnés d'un polymère furanique durci. Le polymère furanique durci contient : un produit de réaction durci d'un monomère furanique et d'un initiateur qui empêche ou réduit une réticulation entre des chaînes d'un monomère furanique polymérisé par une réaction de Diels-Alder du furane-furane ; et/ou un monomère, un oligomère ou un polymère qui empêche ou réduit une réticulation entre des chaînes d'un monomère furanique polymérisé par une réaction de Diels-Alder du furane-furane. L'invention concerne également des procédés de production de tels produits et des formulations d'imprégnation de produits en bois.
PCT/IB2019/057722 2018-09-14 2019-09-13 Produit en bois imprégné WO2020053818A1 (fr)

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WO2023180473A1 (fr) * 2022-03-23 2023-09-28 Kebony As Solution polymérisable permettant d'obtenir un matériau imprégné de polymère de furane

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WO2005108454A1 (fr) * 2004-04-23 2005-11-17 Angus Chemical Company Resine phenolique
WO2007147804A1 (fr) * 2006-06-21 2007-12-27 Transfurans Chemicals Procédé de modification de bois et bois ainsi obtenu
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US20090004395A1 (en) * 2007-06-29 2009-01-01 Marc Henry Schneider Waterborne furfural-urea modification of wood
WO2015088341A1 (fr) * 2013-12-12 2015-06-18 Furanix Technologies B.V. Composition comprenant de l'alcool furfurylique
WO2015154635A1 (fr) * 2014-04-11 2015-10-15 Branko Hermescec Produits dérivés du bois et non dérivés du bois chimiquement modifiés et leurs procédés de production
CN106363732A (zh) * 2016-10-11 2017-02-01 阜阳市伟叶家具有限公司 一种添加糠醇复配酚醛树脂的速生木材改性剂

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US3297611A (en) * 1964-06-05 1967-01-10 Borden Co Curing furfuryl-alchol-modified urea formaldehyde condensates
WO2005016606A1 (fr) * 2003-08-15 2005-02-24 Wood Polymer Technologies Asa Formulation de traitement du bois
WO2005108454A1 (fr) * 2004-04-23 2005-11-17 Angus Chemical Company Resine phenolique
WO2007147804A1 (fr) * 2006-06-21 2007-12-27 Transfurans Chemicals Procédé de modification de bois et bois ainsi obtenu
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US20090004395A1 (en) * 2007-06-29 2009-01-01 Marc Henry Schneider Waterborne furfural-urea modification of wood
WO2015088341A1 (fr) * 2013-12-12 2015-06-18 Furanix Technologies B.V. Composition comprenant de l'alcool furfurylique
WO2015154635A1 (fr) * 2014-04-11 2015-10-15 Branko Hermescec Produits dérivés du bois et non dérivés du bois chimiquement modifiés et leurs procédés de production
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WO2023180473A1 (fr) * 2022-03-23 2023-09-28 Kebony As Solution polymérisable permettant d'obtenir un matériau imprégné de polymère de furane

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