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WO2004106023A1 - Substances et procedes destines au traitement du bois d'oeuvre et d'autres produits du bois - Google Patents

Substances et procedes destines au traitement du bois d'oeuvre et d'autres produits du bois Download PDF

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Publication number
WO2004106023A1
WO2004106023A1 PCT/US2003/012341 US0312341W WO2004106023A1 WO 2004106023 A1 WO2004106023 A1 WO 2004106023A1 US 0312341 W US0312341 W US 0312341W WO 2004106023 A1 WO2004106023 A1 WO 2004106023A1
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WO
WIPO (PCT)
Prior art keywords
wood
lumber
product
treated
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2003/012341
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English (en)
Inventor
Toreki William
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Quick Med Technologies Inc
Original Assignee
Quick Med Technologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Quick Med Technologies Inc filed Critical Quick Med Technologies Inc
Priority to AU2003228626A priority Critical patent/AU2003228626A1/en
Priority to CA002523046A priority patent/CA2523046A1/fr
Anticipated expiration legal-status Critical
Publication of WO2004106023A1 publication Critical patent/WO2004106023A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • B27K3/156—Combined with grafting onto wood fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • CCA chromated copper arsenate
  • U.S. Patent Application No. 09/965,740 teaches the use of quaternary ammonium-containing polymers grafted onto cellulose substrates as absorbent antimicrobial surfaces.
  • Cellulose is one of the principal components of wood.
  • the method described in the above patent application is applicable to the treatment of wood in order to render it resistant to microbial attack.
  • Evidence for the efficacy of this method for the prevention of decay by wood-destroying fungi is presented herein. It has also been found (unexpectedly) that wood treated in this manner is also resistant to destruction by termites.
  • Preservative treatment of wood is usually done by using pressure to force the liquid preservative solution into the pores of the wood. A vacuum may be applied prior to introduction of the treatment solution in order to increase penetration.
  • the active agents (such as CCA) are generally dissolved in a solvent.
  • the solutions are generally of low viscosity in order to facilitate penetration of the treatment. Treatments may be classified as waterborne, or oilborne. A useful summary of the various chemical systems, application methods, efficacy, and other considerations related to wood preservation is given in: Forest Products Laboratory. 1999. Wood handbook - Wood as an engineering material. Gen. Tech. Rep. FPL-GTR-113. Madison, WI: U.S. Department of Agriculture, Forest Service, Forest Products Laboratory. 463 p.
  • Arsenic-containing formulations such as CCA
  • CCA are waterborne treatments. Although most of the toxic chemical is retained in the treated wood for a long period of time, some leaching does occur since the toxic agents are water-soluble. Waterborne systems are generally preferable to solvent based (oilborne) preservative systems for economic reasons, but also because the oil- based solvent themselves must be considered as pollutants.
  • Pentachlorophenol is another common oilborne preservative. It is applied to wood using petroleum-based solvents. It is an EPA restricted-use pesticide. It is toxic, and should not be used where human, plant, or animal contact is likely.
  • Copper napthenate is another oilborne preservative, and although it is not a restricted-use pesticide, it is toxic and should be handled accordingly.
  • Bis(tri-n-butyltin) oxide is another oilborne preservative. Organotin compounds are known to be highly toxic, and their use in marine applications has been banned.
  • Waterborne preservatives other than arsenic-containing systems, have also been used for wood preservation. Many of these systems rely on the antimicrobial activity of metals such as chromium or copper. Chromium is known to be an extremely toxic pollutant, and it use is undesirable. Copper is a metal found in natural deposits and widely used in household plumbing materials. Copper is an essential nutrient, required by the body in very small amounts. However, if the level of contamination is above the MCL in water or food supply, then people exposed to it can be affected by stomach and intestinal distress, liver and kidney damage and anemia, (see, for instance: Toxicological Profile for Copper, December 1990 Update, Agency for Toxic Substances and Disease Registry, United States Public Health Service). Most of the contamination is due to copper mining and smelting operations and municipal incineration. As such, the use of copper in treated wood should be discouraged.
  • Didecyldimethylammonium chloride also called alkyl ammonium compound (AAC)
  • AAC alkyl ammonium compound
  • the subject invention is based on the formation of composite or graft copolymer materials formed between wood and polymers that contain quaternary ammonium groups.
  • an aqueous solution of quaternary monomer, catalyst or polymerization initiator, and (optionally) crosslinking agent is impregnated into the pores of the wood.
  • the wood or wood- containing product becomes fully saturated with said solution.
  • Reaction of the catalyst causes polymerization of the monomer along with grafting to form covalently bonded wood/quaternary composites.
  • the addition of crosslinking agent serves to increase the degree of branching of the polymer, thus providing additional bioactive function.
  • the impregnation of the wood to be treated is assisted by the appropriate application of vacuum and/or pressure.
  • Heating may optionally be applied to the system in order to increase the rate of the polymerization reaction.
  • a washing step may be employed after polymerization in order to remove soluble components such as quaternary homopolymer.
  • pre-formed antimicrobial polymer may be infused into the lumber to confer resistance to termite infestation, wood rot, microbial decay, or to confer other beneficial properties on the lumber. Conference of resistance to termites and microbes may also be produced by the presence of antimicrobial groups within the interstices of the wood without necessarily being bound to the wood structure.
  • the monomers used in the practice of this invention preferably contain polymerizable vinyl or allyl groups that can be polymerized by free radical polymerization.
  • the monomers also contain quaternary ammonium groups in order to provide an antimicrobial effect.
  • Quaternary ammonium compounds are known to show an antimicrobial effect against a wide variety of microorganisms including fungi, bacteria, and some viruses. It may not be expected that quaternary ammonium compounds would be toxic to termites and other wood-destroying insects. It is known, however, that the digestive process of termites relies heavily on the action of numerous microorganisms found in the termite gut.
  • the quaternary polymers utilized in the practice of this invention are of low toxicity. They also pose a very low risk for pollution and environmental concerns. Many of the polymers useful in the practice of this invention are widely used as flocculating agents in wastewater treatment. Examples of some monomers useful in the practice of this invention are disclosed in application no. 09/965,740.
  • Some catalysts that are useful in the practice of this invention include peroxides, azo compounds, and cerium (IV) salts, preferably those compounds that are soluble in aqueous solutions. Examples of some of these catalysts are: (2,2'-azobis(2-methylpropionamidine) dihydrochloride (V-50), hydrogen peroxide, sodium persulfate, and cerium( ⁇ V) ammonium nitrate.
  • wood in the form of lumber, wood-pulp, and wood-derived products may be treated to confer resistance to microbes, including but not limited to fungi, bacteria and the like, as well as to certain insects, such as termites, which may depend on the action of microbes in their digestion of wood-based foodstuffs.
  • quaternary amine containing polymers may be formed in-situ, by provision of appropriate conditions for quaternary amine monomers to polymerize after being impregnated into the wood. Alternatively, or in addition, pre-formed quaternary amine containing polymer may be infused into the interstices of the wood.
  • the polymer is at least partially bonded to the cellulosic substrate of the wood. Where pre-formed, the polymer will take substantially longer to diffuse out of the wood than if quaternary amine monomers are used to protect the wood. Furthermore, other compounds may be included with the polymer in formulating an optimal composition for protecting wood. Inclusion of copper, chromium, organic antimicrobials and the like may be used to advantage in combination with the methods and products taught according to this invention. Utilization of this invention in combination with a product such as CCA may permit effective control of lumber decay, while at the same time vastly decreasing the amount of CCA needed to provide the same level of lumber protection heretofore only achievable using much higher levels of CCA.
  • Example 1 Treatment of wood and lumber products according to this invention will provide significant protection against wood-destroying fungi and insects. It is also likely that mechanical properties of the wood will also be improved, particularly at high grafting levels. Representative examples of methods used in the practice of this invention are given below, along with supporting data to confirm anti-fungal and anti-termite efficacy.
  • Example 1 Treatment of wood and lumber products according to this invention will provide significant protection against wood-destroying fungi and insects. It is also likely that mechanical properties of the wood will also be improved, particularly at high grafting levels. Representative examples of methods used in the practice of this invention are given below, along with supporting data to confirm anti-fungal and anti-termite efficacy.
  • Example 1 Example 1 :
  • Yellow pine sapwood, and poplar boards were purchased at a local building supply store and cut into 3 / 4 inch cubes. Growth ring density of the pine was approximately 4 to 6 rings per centimeter. Wood was stored indoors at room temperature for several days prior to treatment. Wood samples were dried to constant weight under vacuum to establish baseline conditions. The average weight of the pine blocks was 4.2 grams per block, while the average weight of the poplar blocks was 3.6 grams per block.
  • the monomer used was Ageflex FM1Q75MC ([2-(methacroyloxy)ethyl]trimethylammonium chloride, 75 wt% solution in water, Ciba Specialty Chemicals Corporation), also abbreviated as TMMC.
  • Catalysts were either CAN (ammonium cerium( ⁇ V) nitrate), SPS (sodium persulfate), or V-50.
  • Crosslinking agents were either SR344 (polyethylene glycol diacrylate, Sartomer Company), glycerol, or ethoxylated 15 trimethylolpropane triacrylate (SR 9035 - Sartomer Company).
  • Samples of wood treated as taught in Example 1 were inoculated with a white-rot wood destroying fungus, along with untreated controls. After 10 days incubation, the surface of untreated blocks was greater than 90% covered with a layer of fungal growth. The treated blocks were virtually free of any visible fungal growth. Photographs were taken of these samples in order to provide a permanent verification these experimental results. Samples of wood treated according to the above formulations were sent to The Mississippi Forest Products Laboratory at Mississippi State University for testing according to the AWPA Standard El 0-91 "Standard Method of Testing Wood Preservatives by Laboratory Soil-Block Cultures". . The average weight loss of the treated wood blocks (4 different treatment levels), after exposure to four different wood-destroying fungi is summarized below:
  • Samples of wood treated in the manner described Example 1 were subjected to a modified version of the AWPA Standard El -97, "Standard Method for the Laboratory Evaluation to Determine Resistance to Subterranean Termites".
  • Five jars containing pine blocks treated by the above process, and five jars containing untreated pine blocks were tested against termites ⁇ Reticulitermes flavipes). After 10 days, significant destruction of the untreated wood by insect activity was observed; whereas, the treated samples were completely intact with no evidence of insect activity.
  • Samples of wood treated according to the above formulations were sent to The Mississippi Forest Products Laboratory at Mississippi State University for testing according of the AWPA Standard El -97, "Standard Method for the Laboratory Evaluation to Determine Resistance to Subterranean Termites”.
  • TMMC Monomer - [2-(methacryloyloxy)ethyl]trimethyl ammonium chloride
  • SPS sodium persulfate
  • SR9035 Ethoxylated trimethylolpropane triacrylate esters
  • Treating solutions were prepared by adding the monomer, initiator and crosslinker (in this order) into water. Special care was taken to ensure that each ingredient was completely dissolved before the next ingredient was added. Argon (Ar) gas was sparged into the solution to purge oxygen during the whole solubilization process. For each formulation, 3500 grams of solution were prepared. The components of each system are given in the following table.

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

Abstract

L'invention concerne un nouveau traitement du bois offrant une résistance contre les termites et d'autres insectes lignivores, ainsi qu'une résistance contre les champignons et d'autres microbes qui attaquent le bois. L'invention concerne plus précisément un traitement du bois consistant à traiter le bois à l'aide d'une composition antimicrobienne contenant un polymère à base d'ammonium quaternaire.
PCT/US2003/012341 2002-04-21 2003-04-21 Substances et procedes destines au traitement du bois d'oeuvre et d'autres produits du bois Ceased WO2004106023A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003228626A AU2003228626A1 (en) 2002-04-21 2003-04-21 Materials and methods for treating lumber and wood products
CA002523046A CA2523046A1 (fr) 2002-04-21 2003-04-21 Substances et procedes destines au traitement du bois d'oeuvre et d'autres produits du bois

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US37454302P 2002-04-21 2002-04-21
US60/374,543 2002-04-21

Publications (1)

Publication Number Publication Date
WO2004106023A1 true WO2004106023A1 (fr) 2004-12-09

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AU (1) AU2003228626A1 (fr)
CA (1) CA2523046A1 (fr)
WO (1) WO2004106023A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB818412A (en) * 1954-07-23 1959-08-19 Tee Pak Inc Polymerization process
GB1461909A (en) * 1973-08-21 1977-01-19 Ici Ltd Biocidal compositions
DD147949A1 (de) * 1979-12-06 1981-04-29 Jochen Rusche Verfahren zur herstellung schwerloeslicher metallsalze polymerer quartaerer ammoniumverbindungen
US4379890A (en) * 1980-07-11 1983-04-12 Chemische Werke Huels, Aktiengesellschaft Water-soluble polymers carrying quaternary ammonium groups, their preparation and use
WO1991012282A1 (fr) * 1990-02-14 1991-08-22 H.B. Fuller Licensing & Financing Inc. Copolymeres avec action anti-microbienne inherente
EP0493970A1 (fr) * 1991-01-03 1992-07-08 Rohm And Haas Company Sels d'ammonium quaternaires polymériques antimicrobiens
JPH04217649A (ja) * 1990-12-20 1992-08-07 Mitsui Toatsu Chem Inc 不飽和第四級アンモニウム塩の製造方法
WO1998021253A1 (fr) * 1996-11-14 1998-05-22 Röhm Gmbh Polymeres a proprietes antimicrobiennes

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB818412A (en) * 1954-07-23 1959-08-19 Tee Pak Inc Polymerization process
GB1461909A (en) * 1973-08-21 1977-01-19 Ici Ltd Biocidal compositions
DD147949A1 (de) * 1979-12-06 1981-04-29 Jochen Rusche Verfahren zur herstellung schwerloeslicher metallsalze polymerer quartaerer ammoniumverbindungen
US4379890A (en) * 1980-07-11 1983-04-12 Chemische Werke Huels, Aktiengesellschaft Water-soluble polymers carrying quaternary ammonium groups, their preparation and use
WO1991012282A1 (fr) * 1990-02-14 1991-08-22 H.B. Fuller Licensing & Financing Inc. Copolymeres avec action anti-microbienne inherente
JPH04217649A (ja) * 1990-12-20 1992-08-07 Mitsui Toatsu Chem Inc 不飽和第四級アンモニウム塩の製造方法
EP0493970A1 (fr) * 1991-01-03 1992-07-08 Rohm And Haas Company Sels d'ammonium quaternaires polymériques antimicrobiens
WO1998021253A1 (fr) * 1996-11-14 1998-05-22 Röhm Gmbh Polymeres a proprietes antimicrobiennes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199238, Derwent World Patents Index; Class A41, AN 1992-312263, XP002254002 *

Also Published As

Publication number Publication date
AU2003228626A1 (en) 2005-01-21
CA2523046A1 (fr) 2004-12-09

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