Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
  • A01N59/20—Copper
• • 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
• • 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
  • B27K3/16—Inorganic impregnating agents
  • B27K3/22—Compounds of zinc or copper
• • 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

Definitions

• This invention relates to wood preservative and waterproofing compositions containing an amine oxide and an aqueous copper amine complex
• Chromated copper arsenate is commonly employed as a wood preservative
• the chromium oxidizes the wood and generates sites for fixing the copper and arsenic to the wood
• copper is a highly effective wood preservative, some fungi are resistant to its biocidal activity
• the arsenic serves to control fungi that are tolerant to copper and protect the wood against wood destroying insects
• the present invention provides a composition composing an amine oxide and an aqueous copper amme complex
• Another embodiment of the present invention is a method for preserving and/or waterproofing a wood substrate by contacting the composition with the wood substrate
• Yet another embodiment is an article comprising a wood substrate and the composition of the present invention.
• composition has high efficacy against fungi, including copper tolerant fungi such as brown rot and soft rot. Also, the composition is phase stable at high concentrations without the need for polyamines or other stabilizers known in the prior art.
• the amine oxide in the composition may impart waterproofing properties.
• the composition of the present invention is typically free of ionic halides, in particular chlorides, and is environmentally friendly.
• the present invention provides a composition comprising an amine oxide and an aqueous copper amine complex.
• the amine oxide may be a trialkylamine oxide; N-alkylated cyclic amine oxide; a dialkylpiperazine di-N-oxide; an alkyldi(poly(oxyalkylene))amine oxide; a dialkylbenzylamine oxide; a fatty acylaminopropyldimefhylamine oxide; a diamine dioxide; a triamine trioxide; and any combination of any of the foregoing.
• Preferred trialkylamine oxides have the formula R'R 2 R 3 N ⁇ O, where R 1 is a linear, branched, cyclic or any combination thereof C 6 to C 40 saturated or unsaturated group; and R 2 and R 3 independently are linear, branched, or any combination thereof C, to C 40 saturated or unsaturated groups.
• R 1 , R 2 , and R 3 independently may be alkyl, alkenyl, or alkynyl groups.
• R 1 is preferably a C g to C 40 group.
• R 1 is a linear, branched, cyclic or any combination thereof C 8 to C 22 saturated or unsaturated group, such as coco, hydrogenated tallow, soya, decyl, and hexadecyl; and R 2 and R 3 independently are linear, branched, or any combination thereof C, to C 22 saturated or unsaturated groups, such as coco, hydrogenated tallow (which is typically about 70-75% by weight of C 18 alkyl, about 20-25% by weight of C 16 alkyl, and traces of lower derivatives), soya, decyl, and hexadecyl.
• C 8 to C 22 saturated or unsaturated group such as coco, hydrogenated tallow, soya, decyl, and hexadecyl
• R 2 and R 3 independently are linear, branched, or any combination thereof C, to C 22 saturated or unsaturated groups, such as coco, hydrogenated tallow (which is typically about 70-75% by weight of C 18 alkyl, about
• a preferred trialkylamine oxide is a dialkylmethylamine oxide having the formula R'R 2 CH 3 N ⁇ 0, where R 1 and R 2 are defined as above.
• Another preferred trialkylamine oxide is an alkyldimethylamine oxide having the formula R'(CH 3 ) 2 N ⁇ 0, where R 1 is defined as above.
• Suitable alkyldimethylamine oxides include, but are not limited to, a C 10 alkyldimethylamine oxide, a C I2 -C 14 alkyldimethylamine oxide, a C 16 -C I8 alkyldimethylamine oxide, and any combination of any of the foregoing.
• Preferred N-alkylated cyclic amine oxides have the formula R 4 R 5 R 6 N ⁇ 0 where R 4 is defined as R 1 above and R 5 and R 6 are linked to form a cyclic group.
• the cyclic group typically contains from about 4 to about 10 carbon atoms and may optionally contain oxygen, sulfur, nitrogen, or any combination of any of the foregoing.
• More preferred N- alkylated cyclic amine oxides include, but are not limited to, an alkylmorpholine N-oxide, a dialkylpiperazine di-N-oxide, and any combination of any of the foregoing.
• Preferred alkylmorpholine N-oxides have the formula
• R 7 is defined as R 1 above.
• Preferred dialkylpiperazine di-N-oxides have the formula
• R 8 is defined as R 1 above and R 9 is defined as R 2 above.
• Preferred alkyldi(poly(oxyalkylene))amine oxides have the formula
• R 10 is defined as R 1 above; R u and R 12 independently are H or CH 3 ; and m and n independently are integers from about 1 to about 10.
• Preferred dialkylbenzylamine oxides have the formula R ⁇ R 1 'R 12 N ⁇ 0, where R 10 is defined as R 1 above; R u is defined as R 2 above; and R 12 is benzyl. More preferred dialkylbenzylamine oxides include, but are not limited to, alkylbenzylmethylamine oxides having the formula R'°R 12 CH 3 N ⁇ O where R 10 and R 12 are defined as above. Preferred fatty acylaminodimethylpropylamine oxides have the formula
• R' 4 is defined as R 1 above; and m is an integer from about 1 to about 10.
• Preferred triamine trioxides have the formula
• R 15 is defined as R 1 above; and m and n independently are integers from about 1 to about 10.
• Long chain (C 16 or greater) amine oxides such as hexadecylamine oxides, octadecyldimethylamine oxides, and hydrogenated tallow amine oxides, are particularly preferable for imparting waterproofing properties to the composition.
• Short chain (C 14 and shorter) amine oxides such as decyldimethylamine oxides, dodecyldimethylamme oxides, and tetradecyldimethylamine oxides, aide in solubilizing the aqueous copper amine complex and long chain amine oxides, and are efficient stabilizers.
• the composition contains a mixture of C 15 -C 18 long chain amine oxides to impart waterproofing properties and C 10 -C 14 short chain amine oxides to solubilize the long chain amine oxides.
• a mixture comprises at least 50%> by weight of long chain amine oxide based upon 100%) total weight of amine oxides.
• a blend of long chain and short chain amine oxides is also contemplated in one embodiment of the present invention.
• the long chain amine oxides may be blended with the short chain amine oxides in a ratio of about from about 1 :10 to 10:1 in order to yield a stable preservative solution as described herein.
• a mixture of long chain (e.g., C 16 ) and short chain (e.g., C I2 ) amine oxides in a ratio of from about 1 : 1 to about 5: 1 and particularly a ratio of about 5:2 provides the desired dissolution of copper amine complex to provide a stable solution.
• the appropriate ratio of long to short chain amine oxides can be readily determined by those of skill in the art using methods provided herein to test solubility and stability of the solutions.
• the copper amine complex generally contains a water soluble amine. Suitable copper amine complexes include, but are not limited to, ammonium/copper complexes, ethanolamine/copper complexes, diethanolamine/copper complexes, triethanolamine/copper complexes, diethylamine/copper complexes, ethylene diamine/copper complexes, or any combination of any of the foregoing.
• the weight ratio of copper (expressed as copper oxide) to amine oxide in the composition generally ranges from about 1 :0.01 to about 1 :50 and preferably ranges from about 1:0.5 to about 1 :2. In embodiments of the composition which include at least two amine oxides, the weight ratio of copper (expressed as copper oxide) to total amine oxide preferably ranges from about 1 : 1 to about 1 :2.
• the composition may further comprise a fatty amine having at least one C 8 -C 40 alkyl group to further enhance the wood preserving and waterproofing performance of the composition.
• Suitable fatty amines include, but are not limited to, dialkylmethylamines; alkyldimethylamines and in particular (C 8 to C 18 ) alkyldimethylamines; dialkylamines (i.e. secondary amines); alkyl propylene diamines; and any combination of any of the foregoing.
• a non-limiting example of a suitable dialkylmethylamine is N,N-dioctyl-N-methylamine.
• alkyldimethylamines include, but are not limited to, N-lauryl-N,N- dimethylamine, N-dodecyl-N,N-dimethylamine, N-hexadecyl-N,N-dimethylamine, N- octadecyl-N,N-dimethylamine, cocodimethylamine, hydrogenated tallow dimethyl amine, and any combination of any of the foregoing.
• a non-limiting example of a dialkylamine is N,N- dioctylamine.
• alkyl propylene diamines examples include, but are not limited to, vV-dodecyl propylene diamine, /V-coco propylene diamine, and any combination of any of the foregoing. While most prior art copper compositions which contain fatty amines have low phase stability and require polyamines and other adjuvants to increase phase stability, compositions of the present invention which include fatty amines have high phase stability and do not require polyamines or other adjuvants.
• the weight ratio of amine oxide to fatty amine in the composition broadly ranges from about 4:1 to about 1:4.
• a preferred embodiment of the invention has a weight ratio of cocodimethylamine oxide to cocodimethylamine or V-dodecyl propane diamine of about 1 :1.
• the preferred weight ratio of copper (expressed as copper oxide) to amine oxide to fatty amine is about 2:1:1.
• the composition is typically substantially free of ionic halides and preferably contain less than about 10 ppm (w/w) of ionic halides.
• ammonia copper quats in wood treating solutions generally contain about 500 ppm chloride.
• the composition may include a solvent (in addition to water), such as water miscible solvents including, but not limited to, alcohols, such as ethanol and glycols (e.g. ethylene glycol); esters; ethers, such as ethyl ether; polyethers; amine; and any combination of the foregoing.
• composition when in concentrated form, preferably contains from about 5 to 30%) by weight, and preferably from about 10 to 20% o by weight, of combined amine oxide and copper amine complex (excluding water), based upon 100% weight of total composition.
• the concentrate may be diluted to a range of about 0.1 to about 5% for treating wood.
• Use dilutions of the composition typically comprise a biocidally effective amount of the copper amine complex and a preservative enhancing and/or waterproofing effective amount of the amine oxide.
• Use dilutions preferably comprise from about 0.5 to about 5.0%> by weight of amine oxide and from about 0.05 to about 1.0%> by weight of copper (expressed as copper oxide), based upon 100%> weight of total composition.
• compositions may be included in the composition as known to one of ordinary skill in the art.
• biocides, fungicides and insecticides may be include in the composition. Any organic insecticide or fungicide that can be solubilized by an aqueous amine oxide solution is suitable for use in the present composition.
• Suitable insecticides include, but are not limited to, chloropyrifos, folpet, captafol, captan, pyrethroids, and any combination of any of the foregoing.
• Suitable fungicides include, but are not limited to, iodopropargyl butylcarbamate, tributyltin oxide, 2-(thiocyanomethylthio)benzothiazole, iodo- sulfones, azoles, isothiazalones, and any combination of any of the foregoing.
• the weight ratio of amine oxide to biocide. fungcide, or insecticide ranges from about 1 :0.01 to about 1 :0.25 and preferably is aobout
• the composition may contain cocodimethylamine oxide and chlorpyrifos at a weight ratio of about 1:0.1.
• the composition of the present invention may be prepared by mixing the aqueous copper amine complex, amine oxide, solvents, and adjuvants.
• the mixture may be heated, e.g., to a temperature of from about 50 to about 60° C, and/or stirred to expedite mixing.
• a preferred method of preparing the composition is to mix the concentrated copper amine complex with the amine oxide followed by stirring and optional warming until the mixture is uniform.
• Water miscible solvents such as alcohols, glycols, ethers, and the like, may be used to hasten solution of the components.
• the copper amine complex may be prepared by methods known in the art.
• U.S . Patent No.4,622,248 describes forming copper amine complexes by dissolving copper oxide in ammonia in the presence of ammonia bicarbonate.
• U.S. Patent No.4,622,248 also discloses an alternative method of preparing copper amine complexes by dissolving a mixture of copper carbonate and copper hydroxide in ethanolamine and water.
• the complexing amine and copper need to be charged to meet the 4 to 1 (molar) stoichiometry and thus the weight ratio of reagents will be different for each complexing amine.
• each amine group may be counted in the calculation.
• Another embodiment of the present invention is a method for preserving and/or waterproofing a wood substrate by contacting a wood substrate with the composition of the present invention.
• the composition may be applied by any wood treating method known to one of ordinary skill in the art including, but not limited to, brushing, dipping, soaking, vacuum impregnation (e.g. double vacuum technique), and pressure treatment using various cycles.
• Example 1 An aqueous solution of ammoniated copper carbonate was prepared by mixing 10 g of copper oxide (CuO) in 27 g of ammonia, 17 g of ammonium carbonate, and 46 g of water and stirring to yield 100 g of 10%o (by weight) CuO concentrate.
• CuO copper oxide
• the solutions were prepared by mixing one of the prepared copper mixtures (I) or (IT) with the amine oxides and adjuvants listed in Table 1. Hot tap water and/or stirring was occasionally performed to hasten mixing of the components.
• ACQs Copper Quats
• DDAC is N,N-didecyl-N,N-dimethylammonium chloride.
• Example 2 The following experiments were performed to determine the wood treating properties of the compositions of the invention. The following solutions were prepared:
• Barlox ® 16S which is a 30%o (w/w) aqueous solution of hexadecyldimethylamine oxide available from Lonza, Inc.; 107 grams of Barlox ® 12 (32 g of dodecyldimethylamine oxide); and 500 g of deionized water. 480 g of ammoniated copper carbonate concentrate prepared as in Example 1 (i.e. solution (I)) was mixed with the aqueous amine oxide solution to yield a concentrated solution.
• solution (I) ammoniated copper carbonate concentrate prepared as in Example 1
• This solution was diluted with 6650 grams of deionized water and the resulting solution (containing 0.6% copper oxide, 1.0%o hexadecyldimethylamine oxide, and 0.4%) dodecyldimethylamine oxide) was used to treat wood in a pressure cylinder.
• Example 2(B) 480 g of copper ehanolamine solution prepared as in Example 1 (i.e. solution (XT)) was mixed with the aqueous amine oxide (precursor) solution prepared in Example 2(B) to yield a concentrated solution.
• This solution was diluted with 6650 grams of deionized water and the resulting solution (containing 0.6%> copper oxide, 1.0% hexadecyldimethylamine oxide, and 0.4% dodecyldimethylamine oxide) was used to treat wood in a pressure cylinder.
• D Copper ammonia/Dodecyldimethylamine oxide/Fatty amine treating solution
• the agar plate method (Archer et al., Forest Products Journal, 1995 , 45 : 1 ) was used to assess performance of the wood preservative compounds against fungal growth on wood.
• the principle of the test is to assess the retardation of a test organism on agar treated with the preservative.
• the method compares the rate of growth on the fungi on an agar medium that is impregnated with various levels of the test compound.
• a dose response is obtained which relates how the particular chemical combinations will retard fungal growth on a natural media.
• the concentration at which 50%> retardation of the growth of the particular fungi is defined as the IC 50 and is a useful value to compare preservative systems.
• the compositions in Table 3 below were tested against P. placenta, which is a copper tolerant brown rot fungus, and C. globosum, which is a soft rot fungus, according to this method. The results are shown in Table 3 below.
• Table 3 shows that the copper only system required 150 ppm copper (expressed as copper oxide) to control either of these fungi. Furthermore, the compositions of the present invention, which are halide free, performed at least as well as prior art amine copper quats containing DDAC.
• Example 4 The following experiment was performed to evaluate the waterproofing properties of the compositions of the present invention. 1/4" x 3/4" x 6" ponderosa pine end grain wafers were treated with the test solutions prepared in Example 1 using a double vacuum method. Each wood sample was evacuated in a vacuum desiccator to about -80kPa pressure. A test solution was injected into the chamber and the vacuum was released with air. Excess solution was blotted from the wood sample and the wood was returned to the desiccator on a small rack. Vacuum was drawn again to remove liquid from the wood ("kickback" solution). Samples that were subjected to weathering were placed on a flat surface outside and exposed to natural environmental weather conditions for 90 days. The results are shown in Table 4.

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• Life Sciences & Earth Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Inorganic Chemistry (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Chemical And Physical Treatments For Wood And The Like (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2000
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