WO2011095824A1 - Process for the acetylation of wood elements - Google Patents
Process for the acetylation of wood elements Download PDFInfo
- Publication number
- WO2011095824A1 WO2011095824A1 PCT/GB2011/050202 GB2011050202W WO2011095824A1 WO 2011095824 A1 WO2011095824 A1 WO 2011095824A1 GB 2011050202 W GB2011050202 W GB 2011050202W WO 2011095824 A1 WO2011095824 A1 WO 2011095824A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- elements
- wood
- wood elements
- product containing
- composite
- Prior art date
Links
- 239000002023 wood Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000021736 acetylation Effects 0.000 title claims abstract description 13
- 238000006640 acetylation reaction Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 230000008961 swelling Effects 0.000 claims abstract description 10
- 238000005452 bending Methods 0.000 claims abstract description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 241000218657 Picea Species 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000012512 characterization method Methods 0.000 abstract 1
- 206010042674 Swelling Diseases 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920002522 Wood fibre Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000576 coating method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 208000032912 Local swelling Diseases 0.000 description 1
- 235000005018 Pinus echinata Nutrition 0.000 description 1
- 241001236219 Pinus echinata Species 0.000 description 1
- 235000011334 Pinus elliottii Nutrition 0.000 description 1
- 235000017339 Pinus palustris Nutrition 0.000 description 1
- 235000008566 Pinus taeda Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0466—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a non-reacting gas
- B05D3/0473—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a non-reacting gas for heating, e.g. vapour 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27M—WORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
- B27M1/00—Working of wood not provided for in subclasses B27B - B27L, e.g. by stretching
- B27M1/08—Working of wood not provided for in subclasses B27B - B27L, e.g. by stretching by multi-step processes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
- C09J165/02—Polyphenylenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31975—Of cellulosic next to another carbohydrate
- Y10T428/31978—Cellulosic next to another cellulosic
- Y10T428/31986—Regenerated or modified
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31989—Of wood
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/4935—Impregnated naturally solid product [e.g., leather, stone, etc.]
- Y10T428/662—Wood timber product [e.g., piling, post, veneer, etc.]
Definitions
- the invention relates to plain or decorative sheets and/or mouldings, in particular for indoor or outdoor applications in buildings being pressed single- or multi lap core layers made from wood strands, wood particles, wood fibres and/or from cellulose fibres, where the wood elements have been acetylated, impregnated with a synthetic resin as binder, heat- hardened and pressed.
- these sheets/mouldings will be referred to as "composites”, and typically include engineered wood products such as medium density fibreboard, oriented strand board and particle board, derived primarily from soft wood starting materials such as spruce or pine.
- An article comprising such a composite can be used for external facade cladding of buildings, exterior siding applications, structural application in screening and bracing, walls, roofs and floors, cladding for a balcony, or of a parapet panel or apron panel, or else for the internal lining of walls or furniture, or of wet-rooms or laboratory equipment.
- the surface of the composite can be plain or finished with a decorative layer consisting of a coating or laminating veneer.
- the prior art discloses sheets made from woodchips and from wood fibres with a matrix of synthetic resins or cement.
- the sheets are generally of uniform density and are not usually suitable for external applications or internal applications in damp conditions. Neither are these type of sheets maintenance-free, and generally require post-treatment on all sides due to severe water absorption through the edges or surface. Water absorption can cause severe swelling, with an increase in sheet dimensions, and a substantial loss in the mechanical strength of the material.
- Another object of the invention is to provide a wood based composite that has a long life span and is durable, ie that will not rot, decay or disintegrate under the influence of weather or biological attack.
- Still another object of the invention is to provide a wood based composite that after being immersed in water at ambient temperature and in equilibrium therewith, for a significant period of time, will show substantially less reduction in mechanical strength properties such as a modulus of rupture and modulus of elasticity, when compared with existing composites.
- By 'significant period of time' is meant for several weeks or months.
- Another object of the invention is to provide a wood based composite which possesses a surface that remains smooth after wetting or priming with substantially no fibres or wood elements coming loose or standing up from the surface. This enables coatings and paints to be more efficiently, and thereby cost effectively, applied. In addition this property in combination with improved dimensional stability results in a substantially longer service life for the coating and thereby lower maintenance costs.
- fibres or wood elements may stand up from the surface of the composite by 1 to 2 mm, giving the surface a 'hairy feel'.
- a further object of the invention is the provision of a process for producing acetylated wood elements as basic raw material for producing the wood based composites according to the invention.
- wood elements suitable for acetylation according to the present invention are described in the table I below:- Table I
- acetylated wood elements may be prepared either by acetylating large geometry elements, eg wafers which are then further size reduced to the desired final geometry, or by first converting green wood directly to the desired final geometry before acetylation.
- the present invention comprises a composite wood product containing acetylated wood elements characterised by an average value in thickness swelling not exceeding 5% after subjection to 25 wet-dry/freeze-thaw test cycles as described in Table II.
- the composite containing acetylated wood elements may be characterised by retaining an average value of at least 90% of its modulus of elasticity after subjection to 25 wet-dry/freeze-thaw test cycles as described in Table II.
- the composite containing acetylated wood elements may be characterised by retaining an average value of at least 90% of its bending strength after subjection to 25 wet-dry/freeze-thaw test cycles as described in Table II.
- the composite containing acetylated wood elements may be characterised by retaining at least 70% of its modulus of rupture after soaking for 48 hours in water at ambient temperature.
- the composite containing acetylated wood elements may also be characterised by having two or more of the above product properties.
- the present invention also comprises a two stage process for the acetylation of wood elements in which the elements are (a) treated with acetic anhydride at a temperature of 30°C to 190°C at a pressure of atmospheric to 15 barg for up to 80 minutes and thereafter (b) heated with an inert gas which may be mixed with acetic anhydride or a mixture of acetic anhydride and acetic acid to a temperature of 150°C to 190°C at a pressure of 1 to 5 barg for a period of 5 to 300 minutes.
- the stages (a) and (b) may readily be carried out in a suitable pressure reactor.
- the wood elements prior to acetylation are dried to a moisture content of 2% to 10% by weight of water by conventional methods.
- a vacuum is applied to the elements to remove resident gases.
- the elements may conveniently be allowed to dry at atmospheric pressure or be vacuum dried or both.
- stage (a) acetic anhydride at a temperature of 60°C to 130°C is preferred, at a pressure of 8 to 12 barg for 5 to 20 minutes, while in stage (b) it is preferred to use an inert gas (e.g. nitrogen) at a temperature of 130°C to 145°C for 2 to 4 hours.
- an inert gas e.g. nitrogen
- the pressure in the reactor may rise to 1 to 3 barg, and the inert gas become fully saturated with acetic anhydride and acetic acid.
- wood chip (approx. 40mm x 40mm x 10mm) derived from spruce and having a moisture content of 4% - 10% by weight of water was placed in wire mesh walled baskets (to allow the easy passage of fluids), and placed in a pressure reactor. A vacuum of -0.95 barg was then applied to the chip for 5 minutes. Thereafter, pre-heated acetylation fluid (comprising of a mixture of acetic anhydride 95% and acetic acid 5%) at 130°C was introduced into the reactor which was pressurised to 10 barg for 10 minutes. The reactor was then drained and the chip exposed to circulating nitrogen gas heated to 145°C for 60 minutes.
- acetylation fluid comprising of a mixture of acetic anhydride 95% and acetic acid 5%
- the pressure in the reactor may rise to 1 - 2 barg.
- the acetylated chip was vacuum dried at -0.92 barg and cooled for 5 to 10 hours, typically 6 - 7 hours in total (i.e. drying and cooling).
- Acetylation levels were of the order of 20% acetyl group content (measured by high performance liquid chromatography/near-infrared
- the acetylated chip was then broken down to fibre by passing through a
- Another benefit of the present invention is its advantageous effect on the surface adhesion of composites comprising acetylated wood elements, as may be demonstrated by a simple test.
- a length of aluminium adhesive tape is applied to the surface of sample A, following 25 wet-dry stress cycles, virtually no fibres are found to adhere to the tape on its removal.
- sample B a few fibres adhere to the tape, but in contrast when the tape is removed from sample D almost 100% of the adhesive surface is covered by non- acetylated wood fibre.
- the surfaces of the acetylated samples were also found to remain smooth after wetting unlike the surfaces of non- acetylated samples.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Forests & Forestry (AREA)
- Biochemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
Description
Claims
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2012137514/05A RU2569536C2 (en) | 2010-02-04 | 2011-02-04 | Acetylation of wood parts |
CN201180009580.5A CN102822282B (en) | 2010-02-04 | 2011-02-04 | For the acetylizad method of Timber sections |
BR112012019630-8A BR112012019630B1 (en) | 2010-02-04 | 2011-02-04 | process for the manufacture of a composite wood product from wooden elements |
SG2012057915A SG183181A1 (en) | 2010-02-04 | 2011-02-04 | Process for the acetylation of wood elements |
MX2012009021A MX336534B (en) | 2010-02-04 | 2011-02-04 | Process for the acetylation of wood elements. |
NZ60167511A NZ601675A (en) | 2010-02-04 | 2011-02-04 | Process for the acetylation of wood elements |
CA2788597A CA2788597C (en) | 2010-02-04 | 2011-02-04 | Process for the acetylation of wood elements |
EP11704089A EP2531561A1 (en) | 2010-02-04 | 2011-02-04 | Process for the acetylation of wood elements |
JP2012551691A JP2013518743A (en) | 2010-02-04 | 2011-02-04 | Acetylation method for wood components |
KR1020127023011A KR101921340B1 (en) | 2010-02-04 | 2011-02-04 | Process for the acetylation of wood elements |
US13/577,157 US8865318B2 (en) | 2010-02-04 | 2011-02-04 | Process for the acetylation of wood elements |
AU2011212184A AU2011212184B2 (en) | 2010-02-04 | 2011-02-04 | Process for the acetylation of wood elements |
UAA201210423A UA118832C2 (en) | 2010-02-04 | 2011-04-02 | Process for the acetylation of wood elements |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1001750.7 | 2010-02-04 | ||
GBGB1001750.7A GB201001750D0 (en) | 2010-02-04 | 2010-02-04 | Composite and process thereof |
GB1022090.3 | 2010-12-30 | ||
GBGB1022090.3A GB201022090D0 (en) | 2010-12-30 | 2010-12-30 | Manufacturing process |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011095824A1 true WO2011095824A1 (en) | 2011-08-11 |
Family
ID=43901358
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2011/050202 WO2011095824A1 (en) | 2010-02-04 | 2011-02-04 | Process for the acetylation of wood elements |
Country Status (19)
Country | Link |
---|---|
US (1) | US8865318B2 (en) |
EP (1) | EP2531561A1 (en) |
JP (2) | JP2013518743A (en) |
KR (1) | KR101921340B1 (en) |
CN (1) | CN102822282B (en) |
AU (1) | AU2011212184B2 (en) |
BR (1) | BR112012019630B1 (en) |
CA (1) | CA2788597C (en) |
CL (1) | CL2012002179A1 (en) |
CO (1) | CO6571904A2 (en) |
CR (1) | CR20120441A (en) |
EC (1) | ECSP12012133A (en) |
MX (1) | MX336534B (en) |
NZ (1) | NZ601675A (en) |
PE (1) | PE20130617A1 (en) |
RU (1) | RU2569536C2 (en) |
SG (1) | SG183181A1 (en) |
UA (1) | UA118832C2 (en) |
WO (1) | WO2011095824A1 (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013045551A1 (en) | 2011-09-28 | 2013-04-04 | Titan Wood Limited | Panels of medium density fibreboard |
WO2014036204A1 (en) * | 2012-08-29 | 2014-03-06 | Eastman Chemical Company | Moisturized acetylated wood and methods for making the same |
GB2511120A (en) * | 2013-02-26 | 2014-08-27 | Medite Europ Ltd | Acetylated wood fibre |
GB2511121A (en) * | 2013-02-26 | 2014-08-27 | Medite Europ Ltd | Process for manufacturing products from acetylated wood fibre |
WO2014195860A1 (en) * | 2013-06-03 | 2014-12-11 | Chemconserve B.V. | Modified wood fibres for manufacture in composites |
JP2015508027A (en) * | 2012-02-07 | 2015-03-16 | タイタン ウッド リミテッド | Method for acetylating wood and acetylated wood |
US9453302B2 (en) | 2011-06-10 | 2016-09-27 | Titan Wood Limited | Wood fibre acetylation |
WO2016166180A1 (en) * | 2015-04-13 | 2016-10-20 | Tricoya Technologies Ltd | Method for continuous acetylation of wood elements |
CN106042110A (en) * | 2016-06-01 | 2016-10-26 | 江苏科技大学 | Production process for flame-retardant wood board |
JP2018134869A (en) * | 2012-05-22 | 2018-08-30 | タイタン ウッド リミテッド | Reactor system and process for modification of wood |
WO2019197041A1 (en) | 2018-04-13 | 2019-10-17 | Tricoya Technologies Ltd | Acetylated wood and method of making same |
WO2020157333A1 (en) | 2019-02-01 | 2020-08-06 | Tricoya Technologies Ltd | Boards from acetylated rubberwood |
EP3741793A1 (en) | 2019-05-22 | 2020-11-25 | Basf Se | Fibre mouldings |
WO2022023452A1 (en) | 2020-07-28 | 2022-02-03 | Titan Wood Limited | Purification of wood acetylation fluid |
US11338468B2 (en) | 2015-04-13 | 2022-05-24 | Tricoya Technologies Ltd. | Method for continuous acetylation of wood elements |
US11697221B2 (en) | 2016-06-23 | 2023-07-11 | Tricoya Technologies Ltd | Cooling acetylated wood elements |
WO2024100210A1 (en) | 2022-11-09 | 2024-05-16 | Tricoya Technologies Ltd | Purification of acetic acid by heteroazeotropic distillation with water |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2623281A1 (en) * | 2012-01-31 | 2013-08-07 | Titan Wood Limited | Acetylated wood |
US10982011B2 (en) * | 2014-05-21 | 2021-04-20 | Titan Wood Limited | Process for acetylation of wood in the presence of an acetylation catalyst |
AR104243A1 (en) * | 2015-04-13 | 2017-07-05 | Tricoya Tech Ltd | METHOD FOR WOOD ACETILATION |
ES2660426T3 (en) * | 2015-11-18 | 2018-03-22 | SWISS KRONO Tec AG | OSB wood-oriented material board (oriented strand board) with improved properties and production process |
PT3178622T (en) | 2015-12-07 | 2018-10-30 | SWISS KRONO Tec AG | Method of manufacturing of wood material board with reduced emission of volatile organic compounds (vocs) |
DK201800137A1 (en) * | 2018-03-28 | 2019-10-02 | Danish Wood Technology A/S | Treatment of wood |
CN111251400B (en) * | 2020-01-16 | 2022-04-26 | 北京市飞宇商贸有限公司 | Manufacturing method of redwood furniture |
US20220371219A1 (en) * | 2021-05-20 | 2022-11-24 | Washington State University | Thermally modified composite wood-strand products for construction and other applications |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995023168A1 (en) * | 1994-02-24 | 1995-08-31 | A-Cell Acetyl Cellulosics Ab | Acetylation of lignocellulosic materials |
US6632326B1 (en) * | 1999-09-30 | 2003-10-14 | Yamaha Corporation | Modifying method for wood elements |
GB2456915A (en) * | 2008-02-01 | 2009-08-05 | Titan Wood Ltd | A process for the acetylation of wood |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4388378A (en) * | 1980-12-05 | 1983-06-14 | United States Gypsum Company | Thermoplastic hardboard from acetylated mat |
JP3090067B2 (en) * | 1996-10-30 | 2000-09-18 | ヤマハ株式会社 | Wood panel and method of manufacturing the same |
-
2011
- 2011-02-04 PE PE2012001164A patent/PE20130617A1/en active IP Right Grant
- 2011-02-04 AU AU2011212184A patent/AU2011212184B2/en active Active
- 2011-02-04 EP EP11704089A patent/EP2531561A1/en active Pending
- 2011-02-04 JP JP2012551691A patent/JP2013518743A/en active Pending
- 2011-02-04 US US13/577,157 patent/US8865318B2/en active Active
- 2011-02-04 CN CN201180009580.5A patent/CN102822282B/en active Active
- 2011-02-04 BR BR112012019630-8A patent/BR112012019630B1/en active IP Right Grant
- 2011-02-04 KR KR1020127023011A patent/KR101921340B1/en active IP Right Grant
- 2011-02-04 SG SG2012057915A patent/SG183181A1/en unknown
- 2011-02-04 RU RU2012137514/05A patent/RU2569536C2/en active
- 2011-02-04 WO PCT/GB2011/050202 patent/WO2011095824A1/en active Application Filing
- 2011-02-04 CA CA2788597A patent/CA2788597C/en active Active
- 2011-02-04 NZ NZ60167511A patent/NZ601675A/en unknown
- 2011-02-04 MX MX2012009021A patent/MX336534B/en unknown
- 2011-04-02 UA UAA201210423A patent/UA118832C2/en unknown
-
2012
- 2012-08-03 CO CO12131155A patent/CO6571904A2/en not_active Application Discontinuation
- 2012-08-03 CL CL2012002179A patent/CL2012002179A1/en unknown
- 2012-08-24 CR CR20120441A patent/CR20120441A/en unknown
- 2012-08-31 EC ECSP12012133 patent/ECSP12012133A/en unknown
-
2015
- 2015-09-25 JP JP2015188344A patent/JP6262180B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995023168A1 (en) * | 1994-02-24 | 1995-08-31 | A-Cell Acetyl Cellulosics Ab | Acetylation of lignocellulosic materials |
US6632326B1 (en) * | 1999-09-30 | 2003-10-14 | Yamaha Corporation | Modifying method for wood elements |
GB2456915A (en) * | 2008-02-01 | 2009-08-05 | Titan Wood Ltd | A process for the acetylation of wood |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9453302B2 (en) | 2011-06-10 | 2016-09-27 | Titan Wood Limited | Wood fibre acetylation |
EA037317B1 (en) * | 2011-09-28 | 2021-03-11 | Тайтен Вуд Лимитед | Panels of medium density fibreboard |
WO2013045551A1 (en) | 2011-09-28 | 2013-04-04 | Titan Wood Limited | Panels of medium density fibreboard |
JP2018027697A (en) * | 2011-09-28 | 2018-02-22 | チタン ウッド リミテッド | Medium density fiber-board panel |
JP2018086853A (en) * | 2012-02-07 | 2018-06-07 | タイタン ウッド リミテッド | Method of acetylating wood and acetylated wood |
JP2015508027A (en) * | 2012-02-07 | 2015-03-16 | タイタン ウッド リミテッド | Method for acetylating wood and acetylated wood |
JP2018134869A (en) * | 2012-05-22 | 2018-08-30 | タイタン ウッド リミテッド | Reactor system and process for modification of wood |
US11052568B2 (en) | 2012-05-22 | 2021-07-06 | Titan Wood Limited | Reactor system and process for wood modification |
WO2014036204A1 (en) * | 2012-08-29 | 2014-03-06 | Eastman Chemical Company | Moisturized acetylated wood and methods for making the same |
EP2961789B1 (en) * | 2013-02-26 | 2020-06-03 | Tricoya Technologies Limited | Process for manufacturing products from acetylated wood fibre |
US20160002415A1 (en) * | 2013-02-26 | 2016-01-07 | Medite Europe Limited | Acetylated wood fibre |
GB2511120B (en) * | 2013-02-26 | 2017-06-21 | Medite Europe Ltd | Acetylated wood fibre |
GB2511121B (en) * | 2013-02-26 | 2017-10-04 | Medite Europe Ltd | Process for manufacturing products from acetylated wood fibre |
AU2014222843B2 (en) * | 2013-02-26 | 2018-01-04 | Tricoya Technologies Limited | Process for manufacturing products from acetylated wood fibre |
US11912833B2 (en) | 2013-02-26 | 2024-02-27 | Tricoya Technologies Limited | Acetylated wood fibre |
GB2511121A (en) * | 2013-02-26 | 2014-08-27 | Medite Europ Ltd | Process for manufacturing products from acetylated wood fibre |
GB2511120A (en) * | 2013-02-26 | 2014-08-27 | Medite Europ Ltd | Acetylated wood fibre |
AU2021200917B2 (en) * | 2013-02-26 | 2021-12-23 | Tricoya Technologies Limited | Acetylated wood fibre |
EP2961790A1 (en) * | 2013-02-26 | 2016-01-06 | Medite Europe Limited | Acetylated wood fibre |
US11015027B2 (en) | 2013-02-26 | 2021-05-25 | Medite Europe Limited | Process for manufacturing products from acetylated wood fibre |
WO2014195860A1 (en) * | 2013-06-03 | 2014-12-11 | Chemconserve B.V. | Modified wood fibres for manufacture in composites |
US11338468B2 (en) | 2015-04-13 | 2022-05-24 | Tricoya Technologies Ltd. | Method for continuous acetylation of wood elements |
RU2725674C2 (en) * | 2015-04-13 | 2020-07-03 | Трикойа Текнолоджис Лтд | Method for continuous acetylation of elements from wood |
WO2016166180A1 (en) * | 2015-04-13 | 2016-10-20 | Tricoya Technologies Ltd | Method for continuous acetylation of wood elements |
CN107666994A (en) * | 2015-04-13 | 2018-02-06 | 特里高亚科技有限公司 | The continuous acetylation process of wood elements |
CN106042110A (en) * | 2016-06-01 | 2016-10-26 | 江苏科技大学 | Production process for flame-retardant wood board |
US11697221B2 (en) | 2016-06-23 | 2023-07-11 | Tricoya Technologies Ltd | Cooling acetylated wood elements |
WO2019197041A1 (en) | 2018-04-13 | 2019-10-17 | Tricoya Technologies Ltd | Acetylated wood and method of making same |
EP4234190A2 (en) | 2018-04-13 | 2023-08-30 | Tricoya Technologies Limited | Acetylated wood and method of making same |
WO2020157333A1 (en) | 2019-02-01 | 2020-08-06 | Tricoya Technologies Ltd | Boards from acetylated rubberwood |
EP3741793A1 (en) | 2019-05-22 | 2020-11-25 | Basf Se | Fibre mouldings |
US11499021B2 (en) | 2019-05-22 | 2022-11-15 | Basf Se | Fiber molding |
WO2022023452A1 (en) | 2020-07-28 | 2022-02-03 | Titan Wood Limited | Purification of wood acetylation fluid |
WO2024100210A1 (en) | 2022-11-09 | 2024-05-16 | Tricoya Technologies Ltd | Purification of acetic acid by heteroazeotropic distillation with water |
Also Published As
Publication number | Publication date |
---|---|
MX336534B (en) | 2016-01-21 |
US20130209822A1 (en) | 2013-08-15 |
KR20130009759A (en) | 2013-01-23 |
PE20130617A1 (en) | 2013-06-23 |
AU2011212184A1 (en) | 2012-08-30 |
KR101921340B1 (en) | 2018-11-22 |
JP2013518743A (en) | 2013-05-23 |
US8865318B2 (en) | 2014-10-21 |
JP2016027958A (en) | 2016-02-25 |
JP6262180B2 (en) | 2018-01-17 |
CA2788597C (en) | 2018-09-18 |
UA118832C2 (en) | 2019-03-25 |
CO6571904A2 (en) | 2012-11-30 |
BR112012019630B1 (en) | 2020-10-20 |
NZ601675A (en) | 2014-02-28 |
CL2012002179A1 (en) | 2013-01-11 |
AU2011212184B2 (en) | 2014-12-04 |
CN102822282A (en) | 2012-12-12 |
SG183181A1 (en) | 2012-09-27 |
CN102822282B (en) | 2016-03-02 |
EP2531561A1 (en) | 2012-12-12 |
CR20120441A (en) | 2013-01-24 |
MX2012009021A (en) | 2012-11-29 |
CA2788597A1 (en) | 2011-08-11 |
RU2569536C2 (en) | 2015-11-27 |
BR112012019630A2 (en) | 2016-05-03 |
ECSP12012133A (en) | 2012-12-28 |
RU2012137514A (en) | 2014-03-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2788597C (en) | Process for the acetylation of wood elements | |
US20240042647A1 (en) | Panels of medium density fibreboard | |
Islam et al. | Effect of coupling reactions on the mechanical and biological properties of tropical wood polymer composites (WPC) | |
Rahman et al. | Some physical and mechanical properties of bamboo mat-wood veneer plywood | |
Malanit et al. | The gluability and bonding quality of an asian bamboo (" dendrocalamus asper") for the production of composite lumber | |
Febrianto et al. | Development of oriented strand board from acacia wood (Acacia mangium Willd): Effect of pretreatment of strand and adhesive content on the physical and mechanical properties of OSB | |
Wang et al. | Mechanical properties of acetylated birch plywood loaded parallel to the face grain | |
Mohebby et al. | Springback in acetylated wood based composites | |
KR20110097289A (en) | Wood panel using natural adhesive and fabricating method the same | |
JP5828673B2 (en) | Wood fiber board, wood composite board and floor material using the wood fiber board, and methods for producing them | |
AU2020215280A1 (en) | Boards from acetylated rubberwood | |
Karim et al. | Strength properties of mixed cocopeat fibres and Merawan Siput Jantan (Hopea odorata spp.) bonded with partial rubber latex adhesive and nano-SiO2 in particleboard manufacturing | |
CN217072695U (en) | Plywood sheet | |
CN112659279B (en) | Wooden recombinant material and preparation method thereof | |
Rahaman et al. | Suitability of Medium Density Fiber Board Made From Rubber Wood for Household and Industrial Use | |
Alfareza et al. | The effect of heating temperature on the physical and mechanical characteristics of plybamboo prepared from betung bamboo (Dendrocalamus asper) | |
Alia Syahirah et al. | Bonding and Finishing Properties of Bamboo Composite | |
Tamat et al. | Comparative evaluation of bending properties of Kelempayan (Neolamarckia cadamba) based particleboard prepared using different methods | |
Zoolagud | Recent Developments in Bamboo Board Manufacture and Future Research Needs |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180009580.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11704089 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2788597 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012002179 Country of ref document: CL Ref document number: 2011212184 Country of ref document: AU Ref document number: 2012551691 Country of ref document: JP Ref document number: 12131155 Country of ref document: CO Ref document number: 001164-2012 Country of ref document: PE Ref document number: MX/A/2012/009021 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1201003955 Country of ref document: TH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 6862/DELNP/2012 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: CR2012-000441 Country of ref document: CR |
|
ENP | Entry into the national phase |
Ref document number: 2011212184 Country of ref document: AU Date of ref document: 20110204 Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20127023011 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: A201210423 Country of ref document: UA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012137514 Country of ref document: RU Ref document number: 2011704089 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13577157 Country of ref document: US |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012019630 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012019630 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120806 |