WO2023154469A1

WO2023154469A1 - Stabilized copper-amine donor aqueous solution with improved penetration and anti-leaching capabilities

Info

Publication number: WO2023154469A1
Application number: PCT/US2023/012818
Authority: WO
Inventors: Meihua Yang; Min Chen
Original assignee: Troy Technology Ii, Inc.
Priority date: 2022-02-11
Filing date: 2023-02-10
Publication date: 2023-08-17

Abstract

An aqueous preservative composition for cellulose-based materials is provided. The aqueous composition includes, based on the total dry weight of the aqueous composition: a) from 25 to 37 wt% of at least one copper-containing substance; b) from 49 to 62 wt% of at least one amine donor comprising at least one alkanolamine, ammonium hydroxide, or a mixture thereof; and c) from 10 to 26 wt% of at least one buffering agent comprising at least one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, calcium bicarbonate, or a mixture thereof. Methods of preparing the aqueous preservative composition for cellulose-based materials are also provided.

Description

STABILIZED COPPER-AMINE DONOR AQUEOUS SOLUTION WITH IMPROVED PENETRATION AND ANTI-LEACHING CAPABILITIES CROSS-REFERENCE TO RELATED APPLICATION The present application is related and claims priority to Provisional Patent Application No. 63/309,072 filed in the United States Patent & Trademark Office on February 11, 2022, which is incorporated by reference in its entirety for all purposes. FIELD OF THE INVENTION Antimicrobial treatments for cellulose-containing substrates having improved penetration and reduced leaching and methods of preparing such solutions. BACKGROUND Cellulose-containing materials, such as wood, that are used for construction for both outdoor and indoor use, especially in damp conditions, are susceptible to microbial attack. Such attack decreases the attractive appearance and use life of these materials. Efforts to mitigate this microbial attack include treating these substrates with aqueous copper-amine solutions. The copper complex is typically produced commercially by the dissolution of basic copper carbonate in a solution of monoethanolamine (MEA), followed by further carbonation. The carbonation or gas sparging adds complexity to the production process and increases the costs for production. The use of carbon dioxide or air, added to aqueous alkanolamine or aqueous ammonia compositions, is currently the preferred method in the industry of dissolving copper and forming the desired copper complexes that are useful in wood preservation and fungicidal formulations. This production method is inefficient and time-consuming. Another problem with such treatment compositions is that they tend to leach from the treated substrate over time, leading to a loss of resistance to microbial attack. US 6,843,837 discloses a method and a wood preserving composition including a metal compound, complexing agents, and a vinyl-based polymer. The vinyl-based polymer is necessary to prevent leaching for the composition from treated wood. US 6,905,531 discloses a process for producing a copper-containing aqueous solution, in which a copper mass is dissolved in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (HMEA)₂CO₃. The leach liquor is produced by partially carbonating the monoethanolamine using a sparging method. US 7,476,371 discloses a process for producing a copper-containing aqueous solution, in which a copper mass is dissolved in the presence of air in an aqueous leach liquor containing monoethanolamine. US 8,747,908 discloses wood preservative compositions including dispersions of micronized metal or metal compounds. US 2006/0078686 discloses a method of preserving wood with solutions that are injected into wood. The method includes adding a basic component to an aqueous copper amine preservative solution in an amount sufficient to prevent copper precipitation during injection. Accordingly, methods of producing copper-based aqueous copper-amine solutions for antimicrobial treatment of cellulosic materials without the step of sparging or bubbling carbon dioxide or air into an aqueous solution are needed. Such antimicrobial solutions that resist leaching and provide effective antimicrobial activity after period of time in damp or wet conditions are also desired. SUMMARY Example aspects of the present disclosure solve the above-mentioned problems by providing an aqueous preservative composition for cellulosic materials. The preservative composition may include a buffering agent, without or in addition to carbon dioxide added by a step of bubbling or sparging or otherwise intentionally dissolving air or carbon dioxide gas into an aqueous dispersion or solution. Example aspects of the present disclosure further encompass a method to produce copper-MEA aqueous solution without carbonation, but instead using buffering agents (such as ammonium bicarbonate, ammonium carbonate or a mixture of these compounds) to produce the solution. The addition of the buffering agent may additionally improve homogeneity and stability of the copper solution. Surprisingly, the inventive composition may provide enhanced penetration and less leaching than a composition made using a bubbling or sparging carbonation process. The addition of buffering agent (such as, ammonium bicarbonate, ammonium carbonate or a mixture of these compounds) may also increase copper penetration and reduce leaching of copper from treated wood. In an example embodiment, the aqueous preservative composition for cellulosic materials comprises, consists of or consists essentially of the following components, based on the total weight of the composition (with water): a) from 0.01 to 30 wt% of at least one copper-containing substance; b) from 0.01 to 50 wt% of at least one amine donor comprising, consisting of, or consisting essentially of at least one alkanolamine, ammonium hydroxide, or a mixture thereof; c) from 0.002 to 25 wt% of at least one buffering agent comprising, consisting of, or consisting essentially of at least one of ammonium carbonate, ammonium bicarbonate, calcium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, or a mixture thereof; and d) water. In another example embodiment, the aqueous preservative composition for cellulosic materials comprises, consists of or consists essentially of the following components, based on the total dry weight of the composition (without water): a) from 25 to 37 wt% of at least one copper-containing substance; b) from 49 to 62 wt% of at least one amine donor comprising, consisting of, or consisting essentially of at least one alkanolamine, ammonium hydroxide, or a mixture thereof; and c) from 10 to 26 wt% of at least one buffering agent comprising, consisting of, or consisting essentially of at least one of ammonium carbonate, ammonium bicarbonate, calcium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, or a mixture thereof. In an example embodiment, the aqueous preservative composition for cellulosic materials is produced according to the following method: i) combining at least one copper-containing substance and water to provide a wetted copper-containing substance; ii) adding at least one amine donor comprising, consisting of, or consisting essentially of at least one alkanolamine, ammonium hydroxide, or a mixture thereof, to the wetted copper-containing substance, the at least one amine donor being added at a rate to maintain a temperature T1 of the wetted copper-containing substance during the addition step, to form an aqueous copper-amine complex solution; iii) maintaining the aqueous copper-amine complex solution at temperature T2 for a time t1; iv) at the end of the time t1, adding at least one buffering agent to the aqueous copper-amine complex solution; v) after the buffering agent is added, maintaining the aqueous preservative composition for cellulose-based material at a temperature T3 for a time t2; vi) at the end of time t2, cooling the aqueous preservative composition for cellulose-based material to a temperature T4, wherein T4 is less than T3; and vii) filtering the cooled aqueous preservative composition for cellulose-based materials to obtain the aqueous preservative composition for cellulose-based materials. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1A shows Douglas fir samples treated with a composition according to an example embodiment of the present disclosure; and Figure 1B shows Douglas fir samples treated with a composition made with a process using a bubbling or sparging carbonation method. DETAILED DESCRIPTION As used herein, all percents are weight percents unless stated otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention is related. As used in this application and in the claims, the singular forms “a”, “an”, and “the” include the plural forms unless the context clearly dictates otherwise. Additionally, the term “includes” means “comprises”. The methods and compositions of the present disclosure, including components thereof, can comprise, consist of, or consist essentially of the essential elements and limitations of the embodiments described herein, as well as any additional or optional ingredients, components or limitations described herein or otherwise useful in preservative compositions. Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, percentages, and so forth, as used in the specification or claims are to be understood as being modified by the term “about”. Accordingly, unless otherwise indicated, implicitly or explicitly, the numerical parameters set forth are approximations that may depend on the desired properties sought and/or limits of detection under standard test conditions/methods. When directly and explicitly distinguishing embodiments from discussed prior art, the embodiment numbers are not approximates unless the word “about” is recited. As used herein, “optional” or “optionally” means that the subsequently described material, event or circumstance may or may not be present or occur, and that the description includes instances where the material, event or circumstance is present or occurs and instances in which it does not. As used herein, “w/w%” and “wt%” mean by weight as relative to another component or a percentage of the total weight in the composition. The term “about” is intended to mean approximately, in the region of, roughly, or around. When the term “about” is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the numerical values set forth. Unless otherwise indicated, it should be understood that the numerical parameters set forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, numerical parameters should be read in light of the number of reported significant digits and the application of ordinary rounding techniques. The term “substantially free of” when used to describe the amount of substance in a material is not to be limited to entirely or completely free of and may correspond to a lack of any appreciable or detectable amount of the recited substance in the material. Thus, e.g., a material is “substantially free of” a substance when the amount of the substance in the material is less than the precision of an industry-accepted instrument or test for measuring the amount of the substance in the material. In certain example embodiments, a material may be “substantially free of” a substance when the amount of the substance in the material is less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.5%, or less than 0.1% by weight of the material. Here and throughout the specification and claims, range limitations are combined and interchanged, such ranges are identified and include all the sub-ranges contained therein unless context or language indicates otherwise. For example, all ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. Cellulose-based materials or cellulosic materials are materials or substrates including cellulose as a constituent, especially those used as construction materials. Non- limiting examples include wood, plywood, particle board, paper, bamboo, or drywall. Cotton, linen, jute, hessian, hemp, sisal or other bast fiber-based ropes, cords, or fabrics are also contemplated. As used herein, the terms “cellulose-based” and “cellulosic” are considered to be interchangeable. According to certain example embodiments, an aqueous preservative composition for cellulose-based material is provided. The preservative composition comprises, consists of, or consists essentially of the following components based on the total weight of the composition (with water): a) from 0.01 to 30 wt% of at least one copper-containing substance; b) from 0.01 to 50 wt% of at least one amine donor comprising, consisting of, or consisting essentially of at least one alkanolamine, ammonium hydroxide, or a mixture thereof; c) from 0.002 to 25 wt% of at least one buffering agent comprising, consisting of, or consisting essentially of at least one of ammonium carbonate, ammonium bicarbonate, calcium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, or a mixture thereof; and d) water. According to another example embodiment, the composition comprises, consists of or consists essentially of the following components, based on the total dry weight of the composition (without water). a) from 25 to 37 wt% of at least one copper-containing substance; b) from 49 to 62 wt% of at least one amine donor comprising, consisting of, or consisting essentially of at least one alkanolamine, ammonium hydroxide, or a mixture thereof; and c) from 10 to 26 wt% of at least one buffering agent comprising, consisting of, or consisting essentially of at least one of ammonium carbonate, ammonium bicarbonate, calcium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, or a mixture thereof.

Copper-containing substance a) The aqueous cellulose-based material preservative composition may comprise, consist of or consist essentially of at least one copper-containing substance. According to certain example embodiments, the copper-containing substance includes a copper salt. The copper salt may include at least one of a copper (I) salt, a copper (II) salt, a copper (III) salt, a copper (IV) salt, or a mixture thereof. The copper-containing substance may comprise, cosist of, or consist essentially of at least one of metallic copper, copper(II)sulfate, copper(II)carbonate hydroxide Cu2CO₃(OH)₂, basic copper carbonate, copper(II) carbonate CuCO₃, Cu(I)Cl, Cu(II)Cl2, Cu(I)₂O, Cu(II)O, Cu(III)₂O3, Cu(IV)O2, copper(II) fluoride, copper(II) benzoate dehydrate, copper acetoarsenite, copper(I)iodide CuI, copper(I) cyanide CuCN, copper(I) thiocyanate CuSCN, copper(I) sulfate Cu₂SO₄, copper(I) sulfide Cu₂S, copper(I) acetylide Cu₂C₂, copper(I) bromide CuBr, copper(I) fluoride CuF, copper(I) hydroxide CuOH, copper(I) hydride CuH, copper(I) nitrate CuNO₃, copper(I) phosphide Cu₃P, copper(I) thiophene-2-carboxylate C5H3CuO2S, copper(I) t-butoxide C16H36Cu4O4, copper(II) hydroxide Cu(OH)₂, copper(II) nitrate Cu(NO3)₂, copper(II) acetate Cu(OAc)₂, copper(II) fluoride CuF2, copper(II) fluoride dihydrate, copper(II) bromide CuBr2, copper(II) chlorate Cu(ClO3)₂, copper(II) arsenate Cu₃(AsO₄)₂, copper(II) azide Cu(N₃)₂, copper(II) acetylacetonate Cu(O₂C₅H₇)₂, copper(II) aspirinate C₃₆H₂₈Cu₂O₁₆, copper(II) cyanurate CuC₃HN₃O₃, copper(II) glycinate Cu(H₂NCH₂CO₂)₂, copper(II) phosphate Cu₃(PO₄)₂, copper(II) perchlorate Cu(ClO₄)₂, copper(II) selenite CuSeO3, copper(II) sulfide CuS, copper(II) thiocyanate Cu(SCN)₂,copper(II) triflate Cu(OSO2CF3)₂, copper(II) tetrafluoroborate Cu(BF4)₂, copper(II) acetate triarsenite, Cu(C2H3O2)₂·3Cu(AsO2)₂, copper(II) benzoate Cu(C6H5CO2)₂, copper(II) arsenite AsCuHO3, copper(II) chromite Cu2Cr2O5, copper(II) gluconate C₁₂H₂₂CuO₁₄, copper(II) peroxide CuO₂, copper(II) usnate C₁₈H₁₄CuO₇, or a combination thereof. According to an example embodiment, the at least one copper-containing substance comprises, consists of, or consists essentially of at least one of metallic copper, copper(II)sulfate, copper(II) hydroxide Cu(OH)₂, copper(II)carbonate hydroxide Cu2CO₃(OH)₂, copper(II) carbonate CuCO₃, Cu(I)Cl, Cu(II)Cl2, Cu(I)₂O, Cu(II)O, Cu(III)₂O3, Cu(IV)O2, or a mixture thereof. According to another example embodiment, the copper-containing substance comprises, consists of, or consists essentially of at least one of copper carbonate, copper hydroxide, basic copper carbonate, copper sulfate, copper chloride, copper oxide, or a combination thereof. The aqueous preservative composition may include from 0.01 to 30 wt% of the copper-containing substance, based on the total weight of the aqueous composition. The preservative composition may include from 9 to 20 wt% of the copper-containing substance, based on the total weight of the aqueous composition. The aqueous preservative composition may include from 7 to 25 wt%, from 5 to 20 wt% or from 6 to 12 wt% of the copper-containing substance, based on the total weight of the aqueous composition. The aqueous preservative composition may include from 25 to 37 wt% of the copper-containing substance, based on the total dry weight of the composition. According to other example embodiments, the aqueous preservative composition may include from 25 to 35 wt%, from 26 to 33 wt%, or from 27 to 30 wt% of the copper- containing substance, based on the total dry weight of the aqueous composition. According to some example embodiments, the aqueous preservative composition may include at least 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, or 36 wt% of the copper- containing substance based on the total dry weight of the aqueous composition. According to some example embodiments, the aqueous preservative composition may include at most 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, or 26 wt% of the copper- containing substance. Amine donor b) The aqueous cellulose-based material preservative composition may comprise, consist of or consist essentially of at least one amine donor. The at least one amine donor may comprise, consist of or consist essentially of at least one water-soluble or water-dispersible organic amine or ammonium hydroxide, or a combination thereof. According to certain example embodiments, the organic amine includes at least one primary and/or secondary amine group. The organic amine may include more than one amine group. According to some example embodiments, the amine may be a primary amine. According to an example embodiment, the amine donor may be an alkanolamine. The alkanolamine may include at least one primary amine group. According to an example embodiment, the at least one amine donor may be an alkanolamine that includes at least one primary hydroxyl group. According to an example embodiment, the at least one amine donor may be an alkanolamine including at least one primary amine group and at least one primary hydroxyl group. According to an example embodiment, the at least one amine donor may be an alkanolamine that includes at least one C1-C6 alkanolamine that includes at least one primary amine group and at least one primary hydroxyl group. According to certain example embodiments, the amine donor may be at least one of ammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, monomethanolamine, dimethanolamine, trimethanolamine, 2-amino-2-methyl-1- propanol, valinol, N-methylethanolamine, aminomethyl propanol, or a mixture thereof. According to an example embodiment, the amine donor is monoethanolamine. According to an example embodiment, the amine donor is ammonium hydroxide. The aqueous preservative composition may include from 0.01 to 50 wt% of the amine donor, based on the total (wet) weight of the composition. According to certain example embodiments, the aqueous preservative composition may include from 25 to 45 wt%, from 30 to 40 wt%, or from 33 to 37 wt% of the amine donor, based on the total dry weight of the aqueous composition. The aqueous preservative composition may include from 49 to 62 wt% of the amine donor, based on the total dry weight of the composition. According to certain example embodiments, the aqueous preservative composition may include from 49 to 62 wt%, from 50 to 60 wt%, or from 53 to 58 wt% of the amine donor, based on the total dry weight of the composition. According to some example embodiments, the aqueous preservative composition may include at least 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60 or 61 wt% of the amine donor, based on the total dry weight of the aqueous composition. According to an example embodiment, the aqueous preservative composition may include at most 62, 61, 60, 59, 58, 57, 56, 55, 54, 53, 52, 51, or 50 wt% of the amine donor, based on the total dry weight of the aqueous composition. Weight ratio of amine donor to copper in the copper-containing substance The weight ratio, based on the dry weights, of the at least one amine donor to the copper in the copper-containing substance in the aqueous cellulose-based material preservative composition may be from 3:1 to 4:1. The weight ratio of the amine donor to the copper in the copper-containing substance may be at least 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, or at least 3.9:1 based on the dry weights. The weight ratio of the amine donor to the copper in the copper-containing substance may be at most 4:1, 3.9:1, 3.8:1, 3.7:1, 3.6:1, 3.5:1, 3.4:1, 3.3:1, 3.2:1, or at most 3.1:1 based on the dry weights. The weight ratio of the amine donor to the copper in the copper- containing substance may be from 3.25:1 to 3.75:1, or from 3.4:1 to 3.6:1, based on the dry weights. Buffering agent c) The buffering agent may comprise, consist of or consist essentially of at least one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, calcium bicarbonate, or a mixture thereof. The aqueous cellulose-based material preservative composition may have a pH of from 9-12. The pH of the aqueous preservative composition may be from 10 to 11, or from 9 to 11, or from 10 to 12. The aqueous preservative composition may include 0.002 to 25 wt% of the buffering agent, based on the total (wet) weight of the aqueous composition. The preservative composition may include from 5 to 20 wt%, from 2 to 15 wt%, from 5 to 15 wt%, or from 10 to 15 wt% of the buffering agent, based on the total weight of the composition. The aqueous preservative composition may include 10 to 26 wt% of the buffering agent, based the total dry weight of the composition. According to certain example embodiments, the aqueous preservative composition may include 10 to 22 wt%, 12 to 20 wt%, or 14 to 18 wt % of the buffering agent, based the total dry weight of the composition. According to some example embodiments the aqueous preservative composition may include at least 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25 wt %of the buffering agent, based the total dry weight of the composition. According to some example embodiments the aqueous preservative composition may include at most 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, or 11 wt % of the buffering agent, based the total dry weight of the composition. Additional antimicrobial substances The aqueous cellulose-based material preservative composition may further include at least one additional antimicrobial substance. Non-limiting examples of suitable such substances are quaternary amines (Quats), azoles, and polymeric betaine, to increase protection against copper tolerant fungi. The American Wood Protection Association (AWPA) Book of Standards (BOS) provides guidelines regarding the use of aqueous copper-MEA solutions. When using with quaternary amines for Alkaline Copper Quat - Type A (ACQ-A), the mixing ratio of the present invention compositions to didecyldimethyl ammonium chloride (DDAC) may be 1 to 1 in terms of the copper- containing substance, such as copper oxide, to DDAC, based on their dry weights. When using with quaternary amines for Alkaline Copper Quat - Type C (ACQ-C), the mixing ratio of the present invention compositions to benzalkonium chloride (BAC) may be 2 to 1 in terms of the copper-containing substance, such as copper oxide, to BAC, based on their dry weights. When using with quaternary amines for Alkaline Copper Quat - Type D (ACQ-D), the mixing ratio of the present invention compositions to DDAC may be 2 to 1 in terms of copper-containing substance, such as copper oxide, to DDAC, based on their dry weights. When using with azoles for Copper Azole - Type B (CA-B), the mixing ratio of the present invention compositions to tebuconazole may be 96 to 4 in terms of copper in the copper-containing substance to tebuconazole, based on their dry weights. When using with azoles for Copper Azole - Type C (CA-C), the mixing ratio of the present invention compositions to tebuconazole to propiconazole may be 96 to 2 to 2 in terms of copper in the copper-containing substance to tebuconazole to propiconazole, based on their dry weights. When using with polymeric betaine for Alkaline Copper Betaine Type B (KDS-B), the mixing ratio, based on weight, of the present invention compositions to didecyl polyoxyethyl ammonium borate (DPAB) may be 2.1 to 1 in terms of copper- containing substance such as copper oxide to DPAB, based on their dry weights. In certain example embodiments, the aqueous preservative composition additive composition may be substantially free of other materials not specifically recited above. Concentrates: Generally, a concentrate according to example aspects of the present invention preservative may be prepared first and then mixed with co-biocides at the above- mentioned ratios. The concentrate according to example aspects of the present inventive composition and any co-biocides is then diluted about 1 to 100 times to the working solution strength by addition of water. In other words, the ready-to-use treating solution, after dilution may contain about 0.01 to 8 weight percent of copper (based on the copper in the copper-containing substance, i.e., excluding the counterions for the copper in the copper-containing substance) based on the total weight of the aqueous composition. The ready-to-use treating solution can be applied to wood or other cellulosic material substrate by conventional treating methods such as, but not limited to immersion, brush, spray, vacuum, or pressure treatment. Methods of Preparation An example method of preparing an aqueous preservative composition for cellulose-based materials is provided. The aqueous preservative composition for cellulosic materials may be produced according to the following method: i) combining at least one copper-containing substance and water to provide a wetted copper-containing substance. ii) adding at least one amine donor comprising, consisting of, or consisting essentially of at least one alkanolamine, ammonium hydroxide, or a mixture thereof, to the wetted copper-containing substance, the at least one amine donor being added at a rate to maintain a temperature T1 of the wetted copper-containing substance during the addition step, to form an aqueous copper-amine complex solution; iii) maintaining the aqueous copper-amine complex solution at temperature T2 for a time t1; iv) at the end of the time t1, adding at least one buffering agent to the aqueous copper-amine complex solution, forming the aqueous preservative composition for cellulose-based materials; v) after the buffering agent is added, maintaining the aqueous preservative composition for cellulose-based material at a temperature T3 for a time t2; vi) at the end of time period t2, cooling the aqueous preservative composition for cellulose-based material to a temperature T4, wherein T4 is less than T3; and vii) filtering the cooled aqueous preservative composition for cellulose-based materials. T1 may be 75 °C or less. T1 may be 70 °C or less, 65 °C or less, 60 °C or less, or 55°C or less. T2 may be from 50 °C to 75 °C, or from 55 °C to 70 °C, or from 60 °C to 65 °C. T3 may be from 50 °C to 75 °C, or from 55 °C to 70 °C, or from 60 °C to 65 °C. T4 may be less than 50 °C, less than 45 °C, less than 40 °C, less than 35 °C, less than 30 °C, or less than 25 °C. t1 may be 30 minutes or more, 45 minutes or more, 1 hour or more, 2 hours or more or even longer. t2 may be 30 minutes or more, 45 minutes or more, 1 hour or more, 2 hours or more or even longer. Use of the Composition: An example method of preserving cellulose-based materials is provided. The method may comprise, consist of or consist essentially of applying, to the cellulose- based material, a preservative composition including the aqueous preservative composition for cellulose-based materials according to example aspects of the present disclosure. Non-limiting examples of methods for applying the aqueous composition to the cellulose-based material may include immersion, brush, spray, sponge, flow coating, vacuum, or pressure treatment. The composition may be applied to bare, painted or stained substrates. After treatment, the substrate may be painted or stained. The substrate may be wet or dry prior to applying the preservative composition. One or more applications of the aqueous composition may be applied to the substrate. As would be understood by a skilled person, the water in the aqueous preservative composition may at least partially evaporate after being applied to the substrate. Treated Articles: A treated article comprising, consisting of or consisting essentially of a cellulose- based material may also also provided. The aqueous preservative composition according to example aspects of the present disclosure may be adsorbed on and/or absorbed in the cellulose-based material. The cellulose-based material may comprise, consist of or consist essentially of at least one of wood, plywood, particle board, paper, bamboo, drywall, cotton, linen, jute, sisal, or hemp. As would be understood by a skilled person, water in the aqueous preservative composition would at least partially or even completely evaporate from the treated article. The preceding description is exemplary in nature and is not intended to limit the scope, applicability or configuration of the disclosure in any way. Various changes to the described embodiments may be made in the function and arrangement of the elements described herein without departing from the scope of the disclosure. EXAMPLES The following examples will serve to illustrate the invention and preferred embodiments thereof. All parts and percentage in said examples and elsewhere in the specification are by weight unless otherwise indicated. These examples are presented to illustrate the invention and are not intended to limit the invention in any way. Moreover, it will be understood that the compositions described in the examples may be substantially free of any substance not expressly described. To show the reproducibility of the method to produce the preservative composition for cellulosic materials according to example aspects of the present invention, the following examples are provided. All pressures are gauge unless stated otherwise. Ambient temperature is approximately 20- 25 °C. Ambient relative humidity is approximately 50%. Example 1 Water (1581.75 g) and basic copper carbonate (826.2 g) were added to a 5 liter 4-neck reaction flask equipped with mechanic stirrer, thermometer, addition funnel, and condenser. This reaction mixture was stirred at 250 RPM for 10 minutes until all solids were wetted. While stirring, monoethanolamine (MEA) (1624.05 g) at room temperature (approximately 20-25 °C) was dripped into the reaction mixture via an addition funnel over a period of 25 minutes. The temperature of the reaction mixture was monitored and the temperature was kept below 60 °C by controlling the addition rate of the MEA. When the MEA addition was complete, the reaction mixture was maintained at 55 °C for one hour while stirring at 250 RPM. Then, ammonium bicarbonate (468.00 g) was added and the temperature maintained at 55 °C for another one hour. The reaction mixture was cooled to 30 °C while stirring at 250 RPM. Filter aid Celite 535 (1 wt%) was added to the mixture and the mixture was filtered. The yield was 96.4% with the final copper-MEA solution containing 9.97 wt % copper (i.e., exclusive of the counterion in the basic copper carbonate). Example 2 Water (312 g) and copper hydroxide (162 g) were added to a 2 liter 4-neck reaction flask equipped with mechanical stirrer, thermometer, addition funnel, and condenser. This reaction mixture was stirred at 250 RPM for 10 minutes until all solids were wetted. While stirring, monoethanolamine (MEA) (316 g) at room temperature (approximately 20-25 °C) was dripped into the reaction mixture via an addition funnel over a period of 15 minutes. The temperature of the reaction mixture was monitored and the temperature was kept below 60 °C by controlling the addition rate of the MEA. When the MEA addition was complete, the reaction mixture was maintained at 55 °C for one hour while stirring at 250 RPM. Then ammonium bicarbonate (165 g) was added and the temperature maintained at 55 °C for another one hour. The reaction mixture was cooled to room temperature (approximately 20-25 °C) while stirring at 250 RPM. Filter aid Celite 535 (1 wt%) was added to the mixture and the mixture was filtered. The yield was 98.9% with the final copper-MEA solution containing 10.23 wt% copper (i.e., exclusive of the counterion in the basic copper hydroxide). Example 3 Water (76.5 g) and basic copper carbonate (36.72 g) were added to a 250 mL 4- neck reaction flask equipped with mechanical stirrer, thermometer, addition funnel, and condenser. This reaction mixture was stirred at 250 RPM for 10 minutes until all solids were wetted. While stirring, monoethanolamine (MEA) (72.18 g) at room temperature (approximately 20-25 °C) was dripped into the reaction mixture via an addition funnel over a period of 15 minutes. The temperature of the reaction mixture was monitored and the temperature was kept below 60 °C by controlling the addition rate of the MEA. When the MEA addition was complete, the reaction mixture was maintained at 55 °C for one hour while stirring at 250 RPM. Then potassium bicarbonate (14.6 g) was added and the temperature maintained at 55 °C for another one hour. The reaction mixture was cooled to room temperature (approximately 20-25 °C) while stirring at 250 RPM. Filter aid Celite 535 (1 wt%) was added to the mixture and the mixture was filtered. The yield was 97.2% with the final copper-MEA solution containing 10.22 wt% copper (i.e., exclusive of the counterion in the basic copper carbonate). Example 4 Water (78.9 g) and basic copper carbonate (36.72 g) were added to a 250 mL 4- neck reaction flask equipped with mechanical stirrer, thermometer, addition funnel, and condenser. This reaction mixture was stirred at 250 RPM for 10 minutes until all solids were wetted. While stirring, monoethanolamine (MEA) (72.18 g) at room temperature (approximately 20-25 °C) was dripped into the reaction mixture via an addition funnel over a period of 15 minutes. The temperature of the reaction mixture was monitored and the temperature was kept below 60 °C by controlling the addition rate of the MEA. When the MEA addition was complete, the reaction mixture was maintained at 55 °C for one hour while stirring at 250 RPM. Then sodium bicarbonate (12.2 g) was added and the temperature maintained at 55 °C for another one hour. The reaction mixture was cooled to room temperature (approximately 20-25 °C) while stirring at 250 RPM. Filter aid Celite 535 (1 wt%) was added to the mixture and the mixture was filtered. The yield was 96.7% with the final copper-MEA solution containing 10.17 wt% copper (i.e., exclusive of the counterion in the basic copper carbonate). Example 5 Water (83.33 g) and copper hydroxide (32.4 g) were added to a 250 mL 4-neck reaction flask equipped with mechanical stirrer, thermometer, addition funnel, and condenser. This reaction mixture was stirred at 250 RPM for 10 minutes until all solids were wetted. While stirring, monoethanolamine (MEA) (72.18 g) at room temperature (approximately 20-25 °C) was dripped into the reaction mixture via an addition funnel over a period of 15 minutes. The temperature of the reaction mixture was monitored and the temperature was kept below 60 °C by controlling the addition rate of the MEA. When the MEA addition was complete, the reaction mixture was maintained at 55 °C for one hour while stirring at 250 RPM. Then sodium bicarbonate (12.2 g) was added and the temperature maintained at 55 °C for another one hour. The reaction mixture was cooled to room temperature (approximately 20-25 °C) while stirring at 250 RPM. Filter aid Celite 535 (1 wt%) was added to the mixture and the mixture was filtered. The yield was 97.2% with the final copper-MEA solution containing 10.22 wt% copper (i.e., exclusive of the counterion in the basic copper hydroxide). Example 6 To evaluate the penetration performance of the compositions according to example aspects of the present disclosure compared to commercial copper-MEA solution prepared using a carbonation (sparging) method, the following process was conducted. The Example 1 or Example 2 solution was diluted with water to prepare a 1.03 wt% copper (i.e., exclusive of the counterion in the copper-containing substance) ready- to-use treating solution. A commercially produced copper-MEA concentrate (produced using conventional bubble-in or sparging carbonation technology) with water to provide a comparative 1.03 wt% copper (i.e., exclusive of the counterion in the copper- containing substance) ready-to-use treating solution. A charge of five pieces of wood was sealed into the treating cylinder. A preliminary vacuum of 24 inches mercury was applied for 20 minutes to remove air from the cylinder and from the wood samples. The ready-to-use preservative from diluted Example 1, Example 2, or the comparative solution at ambient temperature (20-25 °C) were admitted to the cylinder to break the vacuum. After the cylinder was filled, pressure at 135 psi was applied for one hour. When the 1-hour pressure period was complete, the preservative was withdrawn from the cylinder and stored for re-use. Then a second round of vacuum at 24 inches of mercury was applied for 10 minutes. The preservative (diluted Example 1, Example 2 or the comparative) at ambient temperature was admitted to the cylinder to break the vacuum. After the cylinder was filled, pressure at 135 psi was applied for another one hour. When the 1-hour pressure period was completed, the preservative was withdrawn from the cylinder. Then a final vacuum of 24 inches of mercury was applied for 5 minutes. These steps were repeated to test the Example 2 preservative and the commercially produced copper-MEA preservative. All of the treated wood samples were then exposed to atmospheric conditions (approximately 20-25 °C, one atmosphere, ambient humidity) for conditioning. Example 7 To evaluate the leaching of the copper-MEA preservative compositions from wood, the following solutions A-K were prepared. All of the following weight percents for copper are cited on the basis of the metallic copper, based on the total wet weight of the solution (i.e., exclusive of the counterion in the copper-containing substance). (A) 115.04 g of copper-MEA solution from Example 1 and 4.80 g of 10 wt% azoles (ProTek PT2, Troy Chemical Corporation, Newark, NJ) were mixed and stirred. The resulting concentrate contained 9.57 wt% copper and 0.20 wt% tebuconazole and 0.20 wt% propiconazole. (B) 14.24 g of this Step (A) concentrate was diluted with 785.76 g water by stirring to form a use-dilution solution containing about 0.17 wt% copper, 0.0036 wt% tebuconazole and 0.0036 wt% propiconazole. (C) 34.24 g of the Step (A) concentrate was diluted with 765.76 g water by stirring to form a use-dilution solution containing about 0.41 wt% copper, 0.0086 wt% tebuconazole and 0.0086 wt% propiconazole. (D) 71.36 g of the concentrate from Step (A) was diluted with 728.64 g water by stirring to form a use-dilution solution containing about 0.85 wt% copper, 0.018 wt% tebuconazole and 0.018 wt% propiconazole. (E) 115.04 g of copper-MEA solution from Example (2) and 4.80 g of 10 wt% azoles (ProTek PT2, Troy Chemical Corporation, Newark, NJ) were mixed and stirred. The resulting concentrate contained 9.82 wt% copper and 0.20 wt% tebuconazole and 0.20 wt% propiconazole. (F) 14.24 g of the resulting concentrate from step (E) was diluted with 785.76 g water by stirring to form a use-dilution solution containing about 0.18 wt% copper, 0.0036 wt% tebuconazole and 0.0036 wt% propiconazole. (G) 34.24 g of the resulting concentrate from step (E) was diluted with 765.76 g water by stirring to form a use-dilution solution containing about 0.42 wt% copper, 0.0086 wt% tebuconazole and 0.0086 wt% propiconazole. (H) 71.36 g of the resulting concentrate from step (E) was diluted with 728.64 g water by stirring to form a use-dilution solution containing about 0.86 wt% copper, 0.018 wt% tebuconazole and 0.018 wt% propiconazole. (I) (comparative) 15.76 g commercially produced copper-MEA concentrate (carbonation technology) was diluted with 784.24 g water to form a use-dilution solution containing about 0.17 wt% copper. (J) (comparative) 37.82 g commercially produced copper-MEA concentrate (carbonation technology) was diluted with 762.18 g water to form a use-dilution solution containing about 0.42 wt% copper. (K) (comparative) 78.8 g commercially produced copper-MEA concentrate (carbonation technology) was diluted with 762.18 g water to form a use-dilution solution containing about 0.87 wt% copper. After the use-dilution solutions were prepared, southern yellow pine 2” by 4” board was machined to ¾ inch cubes. The following process was conducted to vacuum- pressure treat the southern yellow pine wood cubes. The following steps were done on 12 cubes each, for solutions (B), (C), (D), (F), (G), (H), (I), (J), and (K). Twelve ¾ inch cubes of southern yellow pine were placed into a 1000 ml glass beaker. A watch glass with weights was placed on top of the cubes. The beaker was placed into a vacuum-pressure vessel. An initial vacuum of 550 mmHg was applied for 10 minutes. Then, 800 g of the prepared use-dilution solutions (B), (C), (D), (F), (G), (H), (I), (J), (K) were each charged to the beaker. A vacuum of 550 mmHg was again applied for 5 minutes and then released. The samples were then allowed to rest at atmospheric pressure for 60 minutes. The block samples were removed from the glass beakers and placed on aluminum trays. The blocks were allowed to condition at atmospheric ambient conditions until their weight was constant. The amount of copper in grams of each set of samples was determined by calculation, based on the weight increase after the vacuum-pressure treatment. The twelve treated blocks for each sample set were randomly separated into two groups of six blocks. One group was retained for no water leaching; and the other group underwent a 2-week water leaching study. The water leaching test was performed according to AWPA E11-16 “Standard method for accelerated evaluation of preservative leaching”. This method provides for the accelerated laboratory evaluation of the leachability of waterborne wood preservatives expressed as a percentage of the original preservative retention. The following process was conducted. Six blocks of each treatment group were impregnated with 300mL deionized water and leached for a 2-week period. The water was changed at periodic intervals during leaching. In this study, the water was changed at the following schedule: 6 hours, 24 hours, 48 hours, 120 hours, 192 hours, 288 hours, and 336 hours. The relative permanence of the preservative composition was then determined by chemical analysis of the leachate samples. The amount of preservative leached is expressed as the ratio of the preservative contained in the leachate to the total preservative present in the six no- water-leaching blocks. The amount of copper active in the leachate was analyzed via copper titration, which is described as follows. Approximately 40-50 grams of test sample were weighed into the bottom of a 250 ml Erlenmeyer flask. To the flask was added 50 ml of methanol, then 0.5 ml (15 drops) of glacial acetic acid were added and the solution was mixed well. Then 10 drops of 0.1% Pyridyl-Azo-Naphthol (PAN) indicator (CAS# 85-85-8 in 95% aqueous ethanol solution) were added. The solution was then titrated with 0.01M EDTA (2,2',2'',2'''-(ethane-1,2-diyldinitrilo)tetraacetic acid), from a wine-red initial color to a yellow end-point with a red/orange transition. Calculations for wt% Cu in the sample material were performed as follows. Weight % Cu=(M*V*6.355)/Wt Where: M is the molarity of the standardized EDTA solution; V is the volume of EDTA solution in mL needed to reach the yellow endpoint; and Wt is the weight of the sample in grams. Table 1 summarizes the weight percent copper leached from copper-MEA compositions according to example aspects of the present invention vs. the commercial copper-MEA solution (produced using bubbling/sparging carbonation technology). Table 1. Percent copper leached from copper-MEA composition of the present invention vs. commercial carbonation technology after 2-week E11 Test Copper Six blocks total Total copper % Copper Average % Donor initial copper (g) (g) in leached Copper

s of the present invention provide lower weight percent copper leached from treated wood than the copper-MEA compositions produced from carbonation technology. The copper- MEA composition according to example aspects of the invention with basic copper carbonate as copper donor (Example 1) had 19.66 wt% copper leached. The composition according to according to example aspects of the invention with copper hydroxide as copper donor (Example 2) had 25.73 wt% of copper leached. In contrast, the copper solution produced with the commercial bubbling/sparging carbonation technology had 32.05 wt% of the copper leached. The test results establish that the addition of buffer agent reduces leach rate of copper from the treated wood compared to the composition produced using the bubbling/sparging carbonation method. Example 8 To compare treatability in laboratory settings, a similar set of experiments as described above for Example 7 were done on Douglas fir, to determine the retention of copper in Douglas fir board. The copper penetration results are summarized in Table 2. Table 2. Treatment Data of Douglas fir with Copper-MEA according to example aspects of the present invention vs. Copper-MEA solution prepared with carbonation technology Charge Preservative Average Volume Average Average # W i ht m³ C r U t k C r

2 Copper-MEA with 886.1 0.0031 2.94 0.18 carbonation h

Average solution uptake and solution retention of treated Douglas fir are calculated using the following equation: ^^{^^} ^{^^^ ൌ^} 1_{000^ ൈ ^} ^{ൈ 1.03%} Wherein:

ACU – Average copper uptake in kilogram per cubic meters. AWC – Average weight difference of Douglas fir before and after pressure- treatment. V – Average volume of Douglas fir specimen in cubic meters. 16 – Unit conversion factor from kilogram per cubic meter to pounds per cubic foot (pcf). To visually evaluate the penetration of copper into treated Douglas fir, AWPA A49-15 “Standard for Determination of Heartwood in Pines and Douglas-Fir” testing was first conducted and then AWPA A69-18 “Standard Method to Determine the Penetration of Copper Containing Preservatives” was conducted. The resulting samples are shown in Figure 1. Figure 1A shows the Douglas fir treated with the composition made according to according to example aspects the invention. Figure 1B shows Douglas fir treated with a composition made with the carbonation (sparging or bubbling) method. Some differences were observed when vacuum-pressure treating Douglas fir with copper-MEA composition according to example aspects of the present invention compared to the copper-MEA composition made with commercial carbonation technology. The average copper uptake was larger for the present composition according to example aspects of the invention than the comparative composition produced using bubbling/sparging carbonation technology. The composition according to example aspects of the invention had a copper uptake of 3.43 kg/m³ (0.21 pounds per cubic foot) compared to a copper uptake of 2.94 kg/m³ (0.18 pounds per cubic foot) for the composition produced using the carbonation/sparging method. The quantitative copper uptake difference is in agreement with the qualitative visual penetration of copper in treated Douglas fir as shown in Figures 1A and 1B. Among the treated lumber samples, the copper-MEA composition according to example aspects of the present invention had 80% penetration conformance (per AWPA T1 standard) vs. 40% for the composition produced using bubbling/sparging carbonation technology. The test results establish that the addition of buffering agent in copper-MEA composition according to example aspects of the present invention improved active penetration and retention of copper in the treated wood.

Claims

What is claimed is: 1. An aqueous preservative composition for cellulose-based materials comprising, based on the total dry weight of the composition: a) from 25 to 37 wt% of at least one copper-containing substance; b) from 49 to 62 wt% of at least one amine donor comprising at least one alkanolamine, ammonium hydroxide, or a mixture thereof; and c) from 10 to 26 wt% of at least one buffering agent comprising at least one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, calcium bicarbonate, or a mixture thereof.

2. The aqueous preservative composition for cellulose-based materials of claim 1 comprising, based on the total weight of the composition: a) from 0.01 to 30 wt% of the at least one copper-containing substance; b) from 0.01 to 50 wt% of the at least one amine donor comprising at least one alkanolamine, ammonium hydroxide, or a mixture thereof; c) from 0.002 to 25 wt% of the at least one buffering agent comprising at least one of ammonium carbonate, ammonium bicarbonate, calcium bicarbonate, or a mixture thereof; and d) water.

3. The aqueous preservative composition for cellulose-based materials of either of claims 1 or 2, wherein the weight ratio of the at least one amine donor to the copper in the copper-containing substance is from 3:1 to 4:1.

4. The aqueous cellulose-based material preservative composition of any one of claims 1 through 3, further comprising at least one antimicrobial substance.

5. The aqueous preservative composition for cellulose-based materials of any one of claims 1 through 4, wherein the at least one copper-containing substance comprises at least one of metallic copper, copper(II)sulfate, copper(II)carbonate hydroxide Cu₂CO₃(OH)₂, copper(II) carbonate CuCO₃, Cu(I)Cl, Cu(II)Cl₂, Cu(I)₂O, Cu(II)O, Cu(III)₂O₃, Cu(IV)O₂, copper(II) fluoride, copper(II) benzoate dehydrate, copper acetoarsenite, copper(I)iodide CuI, copper(I) cyanide CuCN, copper(I) thiocyanate CuSCN, copper(I) sulfate Cu₂SO₄, copper(I) sulfide Cu₂S, copper(I) acetylide Cu₂C₂, copper(I) bromide CuBr, copper(I) fluoride CuF, copper(I) hydroxide CuOH, copper(I) hydride CuH, copper(I) nitrate CuNO₃, copper(I) phosphide Cu₃P, copper(I) thiophene-2- carboxylate C5H₃CuO₂S, copper(I) t-butoxide C₁₆H₃₆Cu₄O₄, copper(II) hydroxide Cu(OH)₂, copper(II) nitrate Cu(NO₃)₂, copper(II) acetate Cu(OAc)₂, copper(II) fluorideCuF₂, copper(II) fluoride dihydrate, copper(II) bromide CuBr₂, copper(II) chlorate Cu(ClO₃)₂, copper(II) arsenate Cu₃(AsO₄)₂, copper(II) azide Cu(N₃)₂, copper(II) acetylacetonate Cu(O₂C₅H₇)₂, copper(II) aspirinate C₃₆H₂₈Cu₂O₁₆, copper(II) cyanurate CuC₃HN₃O₃, copper(II) glycinate Cu(H₂NCH₂CO₂)₂, copper(II) phosphate Cu₃(PO₄)₂, copper(II) perchlorate Cu(ClO4)₂, copper(II) selenite CuSeO3, copper(II) sulfide CuS, copper(II) thiocyanate Cu(SCN)₂, copper(II) triflate Cu(OSO2CF3)₂, copper(II) tetrafluoroborate Cu(BF₄)₂, copper(II) acetate triarsenite, Cu(C₂H₃O₂)₂·3Cu(AsO₂)₂, copper(II) benzoate Cu(C₆H₅CO₂)₂, copper(II) arsenite AsCuHO₃, copper(II) chromite Cu₂Cr₂O₅, copper(II) gluconate C₁₂H₂₂CuO₁₄, copper(II) peroxide CuO₂, copper(II) usnate C₁₈H₁₄CuO₇, or a combination thereof.

6. The aqueous wood preservative composition of any one of claims 1 through 4, wherein the at least one copper-containing substance comprises at least one of metallic copper, copper(II)sulfate, copper(II) hydroxide Cu(OH)₂, copper(II)carbonate hydroxide Cu₂CO₃(OH)₂, copper(II) carbonate CuCO₃, Cu(I)Cl, Cu(II)Cl₂, Cu(I)₂O, Cu(II)O, Cu(III)₂O₃, Cu(IV)O₂, or a mixture thereof.

7. The aqueous preservative composition for cellulose-based materials of any one of claims 1 through 6, wherein the at least one amine donor comprises the alkanolamine and the alkanolamine comprises at least one primary amine group.

8. The aqueous preservative composition for cellulose-based materials of any one of claims 1 through 6, wherein the at least one amine donor comprises the alkanolamine and the alkanolamine comprises at least one primary hydroxyl group.

9. The aqueous preservative composition for cellulose-based materials of any one of claims 1 through 6, wherein the at least one amine donor comprises the alkanolamine and the alkanolamine comprises at least one primary amine group and at least one primary hydroxyl group.

10. The aqueous preservative composition for cellulose-based materials of any one of claims 1 through 9, wherein the at least one amine donor comprises the alkanolamine and the alkanolamine comprises at least one C1-C6 alkanolamine comprising at least one primary amine group and at least one primary hydroxyl group.

11. The aqueous preservative composition for cellulose-based materials of any one of claims 1 through 10, wherein the composition has a pH of from 9-12.

12. The aqueous preservative composition for cellulose-based materials of any one of claims 1 through 11, wherein the buffering agent comprises at least one of ammonium carbonate, ammonium bicarbonate, calcium bicarbonate, or a mixture thereof.

13. A method of preserving cellulose-based materials, the method comprising: applying a preservative composition to the cellulose-based material comprising the aqueous preservative composition for cellulose-based materials of any one of claims 1 through 12.

14. A treated article comprising a cellulose-based material, wherein the composition of any one of claims 1 through 12 is adsorbed on and/or absorbed in the cellulose-based material.

15. The treated article of claim 13 wherein the cellulose-based material comprises at least one of wood, plywood, particle board, paper, bamboo, drywall, cotton, linen, hessian, jute, sisal, or hemp.

16. A method of preparing an aqueous preservative composition for cellulose-based materials, the method comprising: i) combining at least one copper-containing substance and water to provide a wetted copper-containing substance; ii) adding at least one amine donor comprising at least one alkanolamine, ammonium hydroxide, or a mixture thereof, to the wetted copper-containing substance, wherein the at least one amine donor is added at a rate to maintain a temperature T1 of the wetted copper-containing substance during the addition of the at least one amine donor, to form an aqueous copper-amine complex solution; iii) maintaining the aqueous copper-amine complex solution at a temperature T2 for a time period tl; iv) at the end of the time period tl, adding at least one buffering agent to the aqueous copper-amine complex solution, forming the aqueous preservative composition for cellulose-based materials; v) after the buffering agent is added, maintaining the aqueous preservative composition for cellulose-based material at a temperature T3 for a time period t2; vi) at the end of the time period t2, cooling the aqueous preservative composition for cellulose-based materials to a temperature T4, wherein T4 is less than T3; and vii) filtering the aqueous preservative composition for cellulose-based materials.

17. The method of claim 16, wherein Tl is 75 °C or less, T2 is from 50 °C to 75 °C, T3 is from 50 °C to 75 °C, T4 is less than 50 °C, tl is 30 minutes or more and t2 is 30 minutes or more.

18. The method of either one of claims 16 and 17, wherein the weight ratio of the at least one amine donor to the copper in the copper-containing substance is from 3: 1 to 4: 1.

19. The method of any one of claims 16 through 18, wherein the at least one copper- containing substance comprises at least one of metallic copper, copper(II)sulfate, copper(II)carbonate hydroxide Cu₂CO₃(OH)₂, copper(II) carbonate CuCO₃, Cu(I)CI, Cu(II)Cl2, Cu(I)₂O, Cu(II)O, Cu(III)₂O₃, Cu(IV)O₂, copper(II) fluoride, copper(II) benzoate dehydrate, copper acetoarsenite, copper(I)iodide Cui, copper(I) cyanide CuCN, copper(I) thiocyanate CuSCN, copper(I) sulfate Cu₂SO₄, copper(I) sulfide Cu₂S, copper(I) acetylide Cu₂C₂, copper(I) bromide CuBr, copper(I) fluoride CuF, copper(I) hydroxide CuOH, copper(I) hydride CuH, copper(I) nitrate CuNO₃, copper(I) phosphide Cu₃P, copper(I) thiophene-2-carboxylate C₅H₃CuO₂S, copper(I) t-butoxide C₁₆H₃₆Cu₄O₄, copper(II) hydroxide Cu(OH)₂, copper(II) nitrate Cu(NO₃)₂, copper(II) acetate Cu(OAc)₂, copper(II) fluorideCuF₂, copper(II) fluoride dihydrate, copper(II) bromide CuBr₂, copper(II) chlorate Cu(ClO₃)₂, copper(II) arsenate Cu₃(AsO₄)₂, copper(II) azide Cu(N₃)₂, copper(II) acetylacetonate Cu(O2C5H7)2, copper(II) aspirinate C₃₆H₂₈Cu₂O₁₆, copper(II) cyanurate CuC₃HN₃O₃, copper(II) glycinate Cu(H₂NCH₂CO₂)₂, copper(II) phosphate Cu₃(PO₄)₂, copper(II) perchlorate Cu(ClO₄)₂, copper(II) selenite CuSeO₃, copper(II) sulfide CuS, copper(II) thiocyanate Cu(SCN)₂,copper(II) triflate Cu(OSO₂CF₃)₂, copper(II) tetrafluoroborate Cu(BF₄)₂, copper(II) acetate triarsenite, Cu(C₂H₃O₂)₂·3Cu(AsO₂)₂, copper(II) benzoate Cu(C₆H₅CO₂)₂, copper(II) arsenite AsCuHO₃, copper(II) chromite Cu₂Cr₂O₅, copper(II) gluconate C₁₂H₂₂CuO₁₄, copper(II) peroxide CuO₂, copper(II) usnate C₁₈H₁₄CuO₇, or a combination thereof.

20. The method of any one of claims 16 through 19, wherein the at least one copper- containing substance comprises at least one of metallic copper, copper(II)sulfate, copper(II)carbonate hydroxide Cu₂CO₃(OH)₂, copper(II) hydroxide Cu(OH)₂, copper(II) carbonate CuCO₃, Cu(I)Cl, Cu(II)Cl₂, Cu(I)₂O, Cu(II)O, Cu(III)₂O₃, Cu(IV)O₂, or a mixture thereof.

21. The method of any one of claims 16 through 20, wherein the at least one amine donor comprises the alkanolamine and the alkanolamine comprises at least one primary amine group.

22. The method of any one of claims 16 through 20, wherein the at least one amine donor comprises the alkanolamine and the alkanolamine comprises at least one primary hydroxyl group.

23. The method of any one of claims 16 through 20, wherein the at least one amine donor comprises the alkanolamine and the alkanolamine comprises at least one primary amine group and at least one primary hydroxyl group.

24. The method of any one of claims 16 through 23, wherein the at least one amine donor comprises the alkanolamine and the alkanolamine comprises at least one C1-C6 alkanolamine comprising at least one primary amine group and at least one primary hydroxyl group.

25. The method of any one of claims 16 through 24, wherein the composition has a pH of from 9-12.

26. The method of any one of claims 16 through 25, wherein the buffering agent comprises at least one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, calcium bicarbonate, or a mixture thereof.

27. The method of any one of claims 16 through 26, wherein the aqueous preservative composition for cellulose-based materials comprises, based on the dry weight of the aqueous preservative composition for cellulose-based materials: a) from 25 to 37 wt% of the at least one copper-containing substance; b) from 49 to 62 wt% of the at least one amine donor; and c) from 10 to 26 wt% of the at least one buffering agent.