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    • 专利摘要:
    Procedure to prepare a wood preservative composition, which comprises modifying lignin with Na2 B4 O7 or NaNO3 and subsequently with a salt of chromium (II), copper (II), cadmium (II) or zinc (II), for example metal nitrates (Cr (NO3)2, Cu (NO3)2, Cd (NO3)2, Zn (NO 3)2); to the preservative obtainable by this procedure; as well as a procedure to preserve wood; and to preserved wood according to the invention. The preservative of the invention prevents degradation by xylophagous agents and fungi, as well as improves some properties of the wood, such as hygroscopicity and fire resistance. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2800104A1
    申请号:ES201830613
    申请日:2018-06-21
    公开日:2020-12-23
    发明作者:Bouchrika Jalel Labidi；Soares Dos Santos Patricia Bihalva；Darci Alberto Gatto
    申请人:Euskal Herriko Unibertsitatea；
    IPC主号:
    专利说明:

    [0002] FIELD OF THE INVENTION
    [0004] The present invention relates to a modified lignin-based wood preservative composition according to the invention, in order to protect wood against xylophagous agents and fungi, as well as to improve some properties thereof, such as hygroscopicity and fire resistance. .
    [0006] STATE OF THE ART
    [0008] In order to protect the environment, efforts are currently being made to develop cleaner processes and techniques for the production of products that pollute less, as well as to make a rational use of resources, with the reuse of waste and the minimization of the use of materials. For this reason, treatments that manage to increase the useful life of wood are extremely important for the environment, in order to partly prevent deforestation. During its useful life, wood can suffer degradation due to the action of xylophage agents, which varies according to the species and the environmental conditions of use.
    [0010] Wood is exposed to various degradation factors, both biotic and abiotic. These processes are necessary in nature for the replacement of nutrients in the soil, but when it is used for construction or furniture purposes, it is convenient to slow down these degradation processes as much as possible. Therefore, the wood used by the forestry and lumber sectors, in the manufacturing industries of products with higher added value, has a series of limitations in its applications, both indoors and outdoors, especially in the absence of preservation treatments ( eg CCA, chromated copper arsenate). This unfavorable effect means that wood is often replaced by alternative materials, which are not always cheaper or of better quality. However, wood is a material from a renewable source, highly consumed throughout the world, thus having the need to use methods that add commercial value to wood, avoiding restrictions on certain uses. Therefore, treated or preserved wood increases its useful life, and consequently, the consumption and waste of wood is reduced and the deforestation process decreases.
    [0012] The chemical protection of wood is carried out, among others, by means of biocides that contain wood preservatives. These are applied or driven into the wood to form a barrier against the action of rot fungi and insects.
    [0013] It is noteworthy that, at present, some treatments that contain arsenic are being prohibited, such as CCA (chromated copper arsenate), one of the most widely used worldwide, which is a water-soluble preservative, with a fungicidal and insecticide. Due to the potential environmental risk of the use of preservatives that contain arsenic, these components in the European Union are classified as hazardous waste.
    [0015] In the protection of wood, the use of metals such as copper and chromium has been known for many years. Copper is effective in protecting wood, especially against the action of fungi, and its use is relatively safe compared to other types of preservatives, eg. ex. organic. However, copper has a major drawback: it is not fixed to wood, and therefore has a tendency to leach outwards; But the combination of copper with chromium solved this problem. Chromium IV is known for its carcinogenic nature, therefore its use is prohibited in many applications, while chromium (III) is considered an essential nutrient for humans.
    [0017] Other types of non-metallic preservatives are also available, such as disodium octaborate and other borates (SBX), organic biocides / pesticides such as: triazoles, synthetic pyrethroids, chlorothalonylquats, didecyldimethylammonium chloride (DDAC) and isothiazolone and 4,5-dichloro -2-n-octyl-4-isothiazol-3-one (DCOIT); or combinations of metallic and non-metallic preservatives, such as the composition described in document US2007 / 0151476A1. Although the incorporation of carboxylic acids of 6 or more carbon atoms appears to improve the fixation of copper to the wood, somewhat reducing the leaching of copper, to a degree similar to the copper and chromium compositions mentioned above, this is not completely eliminated. problem.
    [0019] In view of these reasons, it is necessary to develop new wood preservative products that overcome the aforementioned problems, taking into account environmental considerations and minimizing the harmful effects for humans. In this context, the use of lignin, which is a natural polymer present in plants and trees, abundant and has bioprotective activity, in other words, a natural protector of the plant against the attack of microorganisms and pests, is outlined as a good option to develop a new biopreservative, effective and environmentally safe.
    [0021] The use of vegetable biomass as a basic raw material implies the change of an economy based on the exploitation of fossil and non-renewable fuels, with limited reserves, to a bio-economy based on the use of renewable organic natural resources, with balanced regeneration and extraction cycles.
    [0022] Lignin with CAS number 9005-53-2 is a complex macromolecule in relation to its structure and heterogeneity. For this reason it is not possible to describe a defined structure of lignin; however, numerous models have been proposed that represent its structure. But it is known that it is part of the cell wall of plants, acts as a cement between the cells and protects the cellulose fibers, giving them better mechanical properties, giving elasticity and resistance to the material. It is mainly concentrated in the middle lamella. It is an amorphous three-dimensional molecule made up of oxygenated phenylpropane units, linked by C-C bonds or ether-type bonds. The precursors of lignin, which can be formed from D-glucose, are p-hydroxyphenyl propane (H), Guaiacil (G) and the alcohol Syringuil (S). which, through complex reactions, give rise to coniferilic, synapilic and para-coumarilic alcohols, which is why lignin has a high molecular weight, which results from the union of various phenylpropyl acids and alcohols. The random coupling of these radicals gives rise to the three-dimensional amorphous structure, characteristic of lignin.
    [0024] The structural base of lignin is phenylpropane, having a variable number of hydroxylic and methoxylic groups bound to the benzene ring. Methoxylic groups (-OCH 3 ) are the most characteristic functional group of lignin and about 90% of methoxylic groups in wood are from lignin.
    [0026] The hydroxyl groups (OH) present in lignins represent about 10% of their weight (1.1 / unit of phenyl-propane) for coniferous trees. These groups are generally phenolic or alcoholic in nature (primary, secondary and tertiary alcohols).
    [0028] Other functional groups are present in lignin, among which the carboxylic groups (CO OH) stand out around 0.05 / unit of phenylpropane and carboxylic groups (CO), 0.1% to 0.2 / unit of phenyl-propane.
    [0030] Although the structure of lignin is complex and variable, it is readily available commercially. But it is known that there are differences between lignin in its natural state and lignin that is isolated by different methods. Due to its complex structure during its isolation from cell walls, lignin undergoes structural modifications, which makes it impossible to obtain lignin exactly as in plants, since once the lignin is isolated from its union with the cell wall it it will cause a breakdown of the lignin bonds with polysaccharides and a reduction in molecular weight.
    [0032] There are different methods of isolating lignin, but only two types of lignin are commercially available: sulfonated lignins and Kraft lignins. In the present invention the Kraft and Organosolv method were used.
    [0034] The process known as "Organosolv", is a process in which organic solvents are used (such as, for example, acetone, methanol, ethanol, butanol, ethylene glycol, formic acid and acetic acid), mixed with water as a cooking medium, sometimes being able to be in the presence of catalyst, acid or basic. It is a process that causes less environmental impact, since the waste recovery system is simpler and by distillation it is possible to recover organic solvents, which in conventional processes is not so simple. In this process the biomass reacts with organic solvents on the OH groups of the lignin, thus isolating the alcoholic lignin. The Organosolv process has not been very successful in its industrial implementation, due to the high working pressure required for extraction and also the high flammability, since most of the solvents used are very volatile.
    [0036] The Kraft process is the most important industrial process for the production of cellulosic pulps, since it represents approximately 90% of chemical pulp, which is characterized by being applicable to any type of wood and forest species. Another important factor is that inorganic process chemicals can be efficiently recovered and reused. Around 130 million tons of pulp are produced per year by the Kraft process worldwide. However, the volume of waste generated during the production of Kraft pulp is a concern for the environment, requiring new uses and products based on the waste generated in the Kraft process, such as isolated Kraft lignin.
    [0038] Therefore, for all its characteristics and due to its great productive potential, lignin would be a very suitable component for a preservative product for wood.
    [0040] SUMMARY OF THE INVENTION
    [0042] The authors of the present invention have now found that the modification of lignin by sodium borate or nitrate and subsequently with salts of chromium (II), copper (II), cadmium (II) or zinc (II), provides a protective effect against degrading agents of the wood and improves some properties of the same, such as hygroscopicity and fire resistance.
    [0044] Therefore, the present invention refers to a process for preparing a wood preservative composition, which comprises modifying lignin with Na 2 B 4 O 7 or NaNO 3 and subsequently with a salt of chromium (II), copper (II), cadmium (II) or zinc (II), for example metal nitrates (Cr (NO 3 ) 2 , Cu (NO 3 ) 2 , Cd (NO 3 ) 2 , Zn (NO 3 ) 2 ); to the preservative obtainable by this procedure; as well as a procedure to preserve wood; and to preserved wood according to the invention. The preservative of the invention prevents degradation by xylophagous agents and fungi, as well as improves some properties of the wood, such as hygroscopicity and fire resistance.
    [0046] DESCRIPTION OF THE FIGURES
    [0048] Figure 1 shows a possible construction of the cylinder used for impregnating the wood.
    [0050] Figure 2 shows a graph that reflects the behavior of the contact angle as a function of time for the wood samples treated with the different treatments in longitudinal tangential sections.
    [0052] Figure 3 shows a graph that reflects the effect of the sessile drop behavior as a function of time, for the wood samples of Pinus spp. treated with the different treatments in the tangential longitudinal section.
    [0054] Figure 4 shows a graph that reflects the effect of different lignin treatments on the results observed for the hardness of the samples.
    [0056] Figure 5 shows a graph that reflects the behavior of the wood samples treated with the different treatments for adhesion resistance.
    [0058] Figure 6 shows a graph that reflects the mass loss behavior in the wood samples treated with the different treatments for resistance to fire by direct exposure.
    [0060] Figure 7 shows a graph that reflects the behavior of the wood samples treated with the different treatments for fire resistance by exposure for 2 minutes.
    [0062] Figure 8 shows the site of the degradation field installation in a eucalyptus forest .
    [0063] Figure 9 shows a graph that reflects the behavior of the wood samples from Pinus spp. with the different treatments according to the invention, exposed to accelerated aging in a weathering chamber.
    [0064] Figure 10 shows a graph that reflects the retention of the woods treated with the different treatments present in the invention.
    [0066] DESCRIPTION OF THE INVENTION
    [0068] According to a first aspect, the present invention refers to a process for preparing a preservative composition for wood, which comprises the steps of:
    [0069] a) mixing lignin and a solution of Na 2 B 4 O 7 or N aN O 3 under stirring;
    [0070] b) adding, under stirring, a metal salt containing an M2 + ion, where M is an element selected from Groups 6, 11 or 12 of the Periodic Table of Elements; c) filtering the solid resulting in step c), which is a modified lignin;
    [0071] d) suspending the modified lignin in water to obtain the wood preservative composition.
    [0073] The lignin used can be any obtained from different processes (Kraft and Organosolv) and preferably any commercially available.
    [0075] The addition of Na 2 B 4 O 7 or NaNO 3 carried out in step a), mainly modifies the carboxyl and hydroxyl groups of lignin, allowing the interaction of those M 2+ ions that are added in step b) with the molecule of lignin. Group 6 of the Periodic Table of the Elements includes, among others, the elements chromium and molybdenum; Group 11 comprises copper, silver and gold; Group 12 comprises zinc and cadmium.
    [0076] Preferably M is selected from the group consisting of chromium, copper, zinc and cadmium, the cation of the metal salt being one of the group consisting of Cr (II), Cu (II), Zn (II) and Cd (II).
    [0077] Preferably, the anion of the metal salt is selected from the group consisting of NO 3 2- , for example metal nitrates (Cr (NO 3 ) 2 , Cu (NO 3 ) 2 , Cd (NO 3 ) 2 , Zn (NO 3 ) 2 ), or Zn (NO 3 ) 2 ) Preferably, in order to obtain a composition that is as homogeneous as possible, in step d) of the above procedure the water in which the solid is suspended contains a base, in order to dispose of a pH between 7 and 13, and later an acid is added to finally obtain a pH of around 7.
    [0078] Said base is preferably selected from the group consisting of NaOH and KOH, although other bases known to the person skilled in the art could be used, and the acid preferably, although not limited to, is selected from the group consisting of boric acid, acetic acid, acid sulfuric, and hydrochloric acid.
    [0080] The final concentration of the modified lignin in the preservative composition can vary between 0.1 to 30% by weight, with respect to the total weight of the preservative solution. According to particular embodiments, the final concentration can be, for example, greater than 0.5%, or greater than 1%, or greater than 3%, or greater than 5%, or greater than 7.5%, or greater. to 10%, and may be, for example, less than 23 % by weight, or less than 21%, or less than 19%, or less than 18%, or less than 16%, or less than 15%. All the indicated lower and upper values are combinable with each other. Preferably, the range will be between 5 and 18%.
    [0082] According to another aspect of the invention, it refers to a wood preservative composition based on modified lignin, obtainable by means of the previously detailed procedure. Likewise, it refers to the preservative composition for wood based on modified lignin, obtained by said process of the invention.
    [0084] Another aspect of the invention relates to a composition containing lignin (CAS 9005-53-2), modified with Na 2 B 4 O 7 or NaNO 3 and M2 + metal ions, as defined above. All defined, exemplified, or preferable embodiments listed above are applicable to this composition.
    [0086] According to a further aspect, the present invention is related to a method for preserving wood, which comprises impregnating the wood to be preserved with the preservative composition obtainable or obtainable according to the present invention.
    [0088] The impregnation can be carried out using any impregnation method known in the state of the art, for example, but not limited to, the Bethell process or dipping, methods commonly practiced in the wood industry, with a solution containing modified lignin of according to the present invention
    [0089] Another aspect of the present invention is a preserved wood obtainable by the preservation process of the invention, using the previously detailed modified lignin-containing preservative composition. The wood to be preserved can be any type of wood, from hardwoods to softwoods.
    [0091] Hard woods are those that come from slow-growing trees, so they are denser and better withstand inclement weather than soft woods because of nature, even if they have not received preservative treatment. These woods generally come from deciduous trees, but they can also be evergreen, which take decades, and even centuries, to reach a sufficient degree of maturity to be cut and used in the manufacture of furniture or beams of farmhouses or single-family homes. They are much more expensive than soft ones, because their slow growth causes their scarcity, but they are much more attractive to build furniture with. Examples of trees that are considered to provide hardwoods are, for example, beech, oak, walnut, maple, hornbeam, teak, lapacho, etc. Chestnut is often classified in hardwoods for its hardness as well. Although the preservation of hardwoods is perhaps not as necessary as it is for softwoods, given their high price, it is convenient to also submit them to preservative treatments, in order to further increase their useful life.
    [0093] Softwoods, meanwhile, include wood from trees belonging to the order of conifers and others of rapid growth. The great advantage they have compared to hard woods is their lightness and their much lower price. However, they do not have as long a life as the hard ones. Its handling is much simpler, although it has the disadvantage of producing a larger quantity of chips. Some examples of widely used softwoods are: pine, elm, fir, birch, poplar, cypress, balso, etc. Chestnut is often classified in softwoods for its flexibility as well.
    [0095] The present invention is especially useful for the preservation of soft woods, improving their durability and resistance, being able to maintain their affordable price, for example, pine or fir woods, widely used.
    [0097] Specifically, the preserved wood according to the present invention presents a loss of mass due to Trametes versicolour fungal attack , measured according to the ASTM D2017-94 standard, at least 75% lower than the loss of the same untreated wood, preferably at least 80% lower, more preferably at least 85% lower, and even more preferably at least 90% lower.
    [0099] Herein, when reference is made to an ASTM standard, reference is made to American Society for Testing and Materials. ASTM D-1413 (2007): standard test method for wood preservatives by laboratory soil-block cultures. Philadelphia, 2007.8p.
    [0101] - ASTM D - 2017 (1994): Standard Method Of Accelerated Laboratory Test Of Natural Decay Resistance Of Wood. Annual Book of ASTM Standards, San Diego, v. 410, 1994, 4p.
    [0102] - ASTM D3165-07 (2014), Standard Test Method for Strength Properties of Adhesives in Shear by Tension Loading of Single-Lap-Joint Laminated Assemblies, Annual Book of ASTM Standards, San Diego, PA, 2014.3p.
    [0104] Likewise, preserved wood according to the present invention has a Brinell hardness at least 40% higher than the same untreated wood, preferably at least 60% higher, more preferably at least 75% higher, and even more preferably at least a 90% higher.
    [0106] Furthermore, the preserved wood according to the present invention exhibits a loss of mass in the fire resistance test by direct exposure lower by at least four percentage points than the same untreated wood, preferably by at least 5 percentage points.
    [0108] Next, the present invention will be described in greater detail based on a series of examples; however, in no case should they be considered as limiting the scope of the invention, which is given by the appended claims.
    [0110] EXAMPLES
    [0112] Preparation of preservative compositions according to the invention
    [0114] Example 1: preparation of a preservative composition based on lignin modified with NaNO3 and Cu (NO 3) 2
    [0116] 5 g of lignin was added to 2 L of a solution containing 1.6998 g of NaNO 3 under constant and vigorous stirring. In a second stage, 1.546 g of Cu (NO 3) 2 were added to the suspension containing the lignin pre-modified with NaNO 3 . After 1h under constant stirring, the solution was filtered through a 0.45 micron polyamide filter. The resulting solid, which is a modified lignin according to the present invention, is dried in an oven at 50 ° C for 24 hours.
    [0118] For the preparation of preservative compositions according to the present invention, the copper-modified lignin obtained above was used; for this, said modified lignin was added, at different concentrations, which can vary from 0.1 to 30% by weight, to a 0.1% NaOH solution with stirring for 5 minutes; immediately afterwards an acid (3% sulfuric acid or 6.8% boric acid) was added until obtaining a pH of approximately 7 (approximately 100 milliliters),
    [0121] maintaining stirring for 5 minutes; finally the volume was made up to 1 liter.
    [0123] Example 2: Preparation of a preservative composition based on lignin modified with Na2B4O7 and Cu (NO3) 2
    [0125] 5 g of each lignin sample was added to 2 L of a 4.024 gram solution of Na 2 B 4 O 7 applying constant and vigorous stirring. Immediately after maintaining 2 h at room temperature, the pH was adjusted to 7 by adding 98% H 2 S O 4 acid , before adding the metal ions. 6.30 g of Cu (NO 3) 2 was added to the suspension containing the pre-modified lignin, and the conductivity and pH values were measured. After 1h under constant stirring, the solution was filtered through a 0.45 micron filter of polyamide. The resulting solid, which is a modified lignin according to the present invention, was oven dried at 50 ° C for 24h.
    [0126] For the preparation of preservative compositions according to the present invention, the copper-modified lignin obtained above was used; for this, said modified lignin was added, at different concentrations, which can vary from 0.1 to 30% by weight, to a 0.1% NaOH solution with stirring for 5 minutes; immediately afterwards an acid was added (3% sulfuric acid or 6.8% boric acid) until obtaining a pH of approximately 7 (approximately 100 milliliters), maintaining stirring for 5 minutes; finally the volume was made up to 1 liter.
    [0128] Example 3: Preparation of a preservative composition based on lignin modified with NaNO3 and Cd (NO3) 3
    [0130] 5 g of lignin was added to 2 L of a solution containing 1.6998 g of NaNO 3 under constant and vigorous stirring. In a second stage 0.987g of Cd (NO 3) 3 were added to the suspension containing the lignin pre-modified with NaNO 3 .
    [0132] After 1 h under constant stirring, the same procedures as in Example 1 were carried out. This modified lignin was used for the preparation of a preservative composition according to the invention.
    [0133] Use of the preservative compositions according to the invention in the treatment of wood
    [0134] Example 4: Treatment of wood with the preservative composition obtained in Examples 1, 2 and 3
    [0136] In this study, the efficacy of the use of the preservative composition of the present invention was verified, specifically the composition obtained in Examples 1 and 3 above. This efficiency was verified using 5 wood trees from Pinus spp and Eucalyptus spp, obtained from a homogeneous population; From all the trees the first torso with the diameter at chest height (DBH, approximately 1.30 meters) was removed, a piece from which the samples were taken for different analyzes, and placed in a climatic chamber at 20 ° C and a relative humidity of 65%, in order to stabilize the equilibrium moisture content.
    [0138] The wood was treated with the preservative composition of the present invention according to the modified ASTM D-1413-07 standard. The treatment was carried out in a treatment cylinder and a vacuum pump (see Figure 1) by a procedure analogous to the Bethel treatment for wooden posts. The samples were placed inside the cylinder, an initial vacuum of 600 µm Hg was applied for 30 min., Under vacuum the solution was released into the cylinder and then a pressure of 6 bar was applied for 60 min. A final vacuum of 30 min is carried out. to remove excess solution from the specimens. Once the treatment was finished, the treated samples were removed and immediately afterwards weighed to determine the absorption of the preservative composition, to determine the average of the retention capacity (kg / m3) in each treatment. Finally, the samples were placed in a climatic chamber at 20 ° C and a relative humidity of 65%, in order to stabilize the moisture content in equilibrium, to carry out the subsequent analyzes.
    [0140] Evaluation of the efficacy of the preservative compositions according to the invention
    [0141] The characterization of the wood treated with the different preservative compositions prepared according to the present invention was carried out (Table 1). This characterization is very important for determining the effectiveness of the compositions, as well as their possible uses. Antifungal activity was determined by fungal attack Trametes versicolour and Ganoderma applanatum : loss of mass, chemical modification, hygroscopicity, specular gloss and hardness.
    [0142] Table 1. The different treatments with modified lignin applied to wood.
    [0144] Treatment Pre-treatment lignin Type of preservative
    [0148] NT = untreated sample EOL Cu = Copper-modified Lignin Organosolv Emulsion, EOL Cd = Cadmium-modified Lignin Organosolv Emulsion, EOL Zn = Zinc-modified Organosolv Lignin Emulsion, EKL Cu = Copper-modified Kraft Lignin Emulsion, EKL Cd = Lignin Emulsion modified Kraft cadmium, EKL zn = Kraft Lignin Emulsion modified with zinc, EOL Organosolv Lignin Cucrb = Emulsion modified with copper, chromium and boron and EKL Cucrb = Emulsion Kraft Lignin modified copper, chromium and boron.
    [0150] Example 5: Loss of mass due to fungal attack.
    [0152] The resistance of each one of the samples treated with preservative of the present invention was determined in accordance with the ASTM D 2017-94 standard. The standard is used to evaluate the resistance of wood products or other organic materials subjected to decay by fungi that destroy wood, such as Trametes versicolour and Ganoderma applanatum.
    [0154] The results obtained are indicated in Table 2; The samples that exhibited the best result were treated with treatment III (EOLCd) where the Organosolv lignin modified with cadmium was used, with a lower percentage of weight loss when exposed to the Trametes versicolour fungus during a period of 48 weeks of exposure. These samples were classified according to ASTM D2017-94 as long lasting (very resistant). The samples without treatment showed a greater loss of mass, being classified according to the ASTMD-2017-94 Standard as moderately resistant (moderately resistant). All the treatments with compositions according to the present invention have had better results than the untreated samples, for which they are useful as a wood preservative, to increase the resistance to the fungus T. versicolour and G.applanatum.
    [0157] Table 2. Effect of different treatments with modified lignin on the loss of mass in samples exposed to fungal attack.
    [0159] Fungus treatment Loss of mass (%)
    [0161] I Trametes versicolor 35.80 (8.66) b II Trametes versicolor 0.99 (0.50) to III Trametes versicolor 0.80 (0.17) to IV Trametes versicolor 3.08 (2.25) to V Trametes versicolor 3.20 (2.91) to VI Trametes versicolor 4.73 (1.90) to VII Trametes versicolor 1.64 (0.24) to VIII Ganoderma applanatum 18.05 (7.7) to IX Ganoderma applanatum 17.38 (7.6) a The values in parentheses are the mean values of the standard deviation, in the same column, samples that share different letters are significantly different at the 5% level in the Tukey test.
    [0163] Example 6: Determination of hygroscopicity
    [0165] Figure 2 shows the results of the samples treated with the different preservative treatments of the present invention. It is possible to observe that in all the treatments there was an improvement in the hygroscopicity of the wood, becoming more and more hydrophobic, compared to the untreated wood. The efficiency of preservatives or chemical preservatives is mainly due to their hygroscopicity, because reducing the moisture content of the wood inhibits the growth of fungi. The treatment that showed the best results was the wood treated with treatment III (EOL cd ), showing average values of 86.56 ° in the angle of the sessile drop after 180 seconds of exposure, being a value higher than the average of the untreated wood (64.74 °), in the values after the exposure of the sessile drop (initial moment), as can be seen in Figure 3.
    [0167] Example 7: Determination of Brinell hardness
    [0169] The hardness (Brinell) was higher with preservative treatments of the present invention compared to untreated wood; Wood treated with IV treatment (EOL zn ) for Pinus species showed an increase of around 98% in Brinell hardness compared to untreated wood. The results show a reduction in the hardness of treatments III (EOL cd ) and VI (EKL cd ) for the Pinus species , compared to the other treatments performed, but the lower average hardness values for the different treatments showed an increase 41% compared to untreated wood, as can be seen in Figure 4. Hardness is known to have various influences such as wood density, but it is possible observe in this study that the treatment with metal-modified lignin influenced the variation of hardness in the samples of both species.
    [0171] For the Pinus sp. Species , the EKL Cd treatment presented the highest values for Brinell hardness. However, the wood samples of Eucalyptus sp. subjected to the same treatment presented the lowest hardness values. The results show that the treatments with EOL Cu and EOL Cd reduced the hardness of the wood of the Pinus sp.
    [0173] Example 8: Determination of bond strength
    [0175] In this study, the different treatments according to the invention studied in the adhesion resistance process of the wood were evaluated (Figure 5).
    [0177] The average values of the shear strength of the wood of Eucalyptus spp they were increased with the treatments according to the invention with the exception of treatment III (EOLCd), which presented a reduction at cut of 4.5% with respect to the untreated wood. This fact can be explained by the reduced hygroscopicity of the wood, which with treatment became more hydrophobic. This reduced the penetrability of the adhesive, but still presents results in accordance with the ASTM D-3165-07 standard, ABNT 790, which stipulates that preservative products for wood must guarantee durability and biological protection, without prejudice of adhesive adhesion.
    [0179] ABNT is an abbreviation for ASSOCIAQÁO BRASILEIRA DE NORM AS TÉCNICAS. NBR 16202: Eucalyptus poles preserved for distribution networks. Rio de Janeiro, 2013. 65 p.
    [0181] The results of the shear resistance of the woods treated according to the invention (Figure 5) in comparison with the untreated wood, revealed that the wood of Pinus spp had the worst behavior with respect to treatment.
    [0183] Example 9: Fire resistance for short periods
    [0185] This study evaluated the different treatments with the preservative of the present invention in the exposure of the wood in contact with direct fire for two minutes; then, in the absence of fire, it was observed how long the mass loss remained and the ignition, flame and ember times. All the treatments carried out with the preservatives of the present invention produced a decrease in the loss of mass with respect to the untreated wood for both species (Figure 6),
    [0188] with the exception of the EKL treatment, which presented the same value as the untreated Pinus spp.
    [0190] In Figure 7 it is possible to observe that treatment III (EOLCd) is the one that was maintained for the shortest time in flame and embers; In all other treatments, the samples presented longer times than the untreated sample. Figure 7 shows that the treatment with EOLCd presented the longest ignition time for Pinus spp., With 32.8 seconds, which represents an increase of 144% in relation to the untreated samples.
    [0192] It is also observed in Figure 7 that the burning time is shorter in the woods of the Eucalyptus species than in those of Pinus. In the Eucalyptus wood , only the EOLZn treatment had a longer burning time compared to the untreated wood. For Eucalyptus spp., None of the evaluated treatments presented a reduction in the burning time compared to the woods without treatment. This fact means that the treatment makes it difficult for the fire to penetrate the surface of the wood, reaching its interior; For this reason, there was a reduction in the loss of mass (Figure 6) of the samples due to exposure to fire.
    [0194] The results showed that the treatments have a very interesting behavior in contact with fire, which demonstrates the efficiency of the different preservative compositions of the present invention as fire retardants.
    [0196] Example 10: Color Test
    [0198] Aesthetics have gained importance in recent years and wood is an attractive material, depending on its design, color, and surface. It is also necessary to take into account the external appearance of the wood, as it can become one of the most important criteria when deciding to buy. In order to quantitatively evaluate the change in color of pine samples treated with different preservatives according to the present invention, the color of the wood was measured in the CIE L * a * b * system (Hunter, Richard Sewall. "Photoelectric Color-Difference Meter". JOSA. 38 (7): 661, 1948). The woods treated according to the present invention also show improvements in terms of the color obtained (Table 3). Treatments IV (EOLZn) and V (EKLcu) resulted in darker final products with a decrease in the mean values of (L *), which indicates the luminosity of the wood. In general, the darker color is more attractive and competitive, since it brings the appearance of the wood of the present invention closer to that of some noble woods. The coordinate (a *) in the woods treated according to the invention has a range of 7 to 9.00, compared to no
    [0201] 3.6 treated, that is, they show an intensification of the color in the direction of red with the different treatments carried out. The average values of the color variation (ED *) were found between 9.39 and 26.52, presenting a very significant variation. This is due to the color of the emulsion, black-brown, which produced the variation of the initial color of the samples visible to the human eye. The ink angle (H °) decreased in all the treatments of the invention.
    [0203] Table 3 . Effect of the different position on color parameters on the surface of the samples of different treatments studied.
    [0204] Treatment L * a * b * CH ° DE * I 82.41 (2.8) d 3.60 (0.8) a 21.60 (1.2) a 21.91 (1.23) ab 80 .57 (1.99) c -II 74.91 (1.68) c 8.27 (1.15) bc 24.78 (0.30) ab 26.14 (0.44) cd 71.58 ( 2.41) b 9.39 III 8.66 (1.15) bc 25.55 (2.45) abc 27.00 (2.75) d 71.39 (2.38) b 14.47 IV 56 .68 (8.76) a 7.21 (0.95) b 19.73 (3.19) bcd 21.03 (3.16) a 69.72 (2.84) ab 26.05 V 56, 45 (9.41) a 9.00 (0.54) c 22.07 (2.87) bcd 23.86 (2.67) abc 67.57 (2.84) a 13.03 VI 70.08 (2.60) bc 7.59 (1.24) bc 22.91 (0.99) cd 24.15 (1.28) bcd 71.76 (2.25) b 16.18 The values in parentheses are mean standard deviation values, in the same column samples sharing different letters are significantly different at the 5% level in the Tukey test.
    [0206] Example 11: Natural aging in degradation field
    [0208] Field testing is essential and represents a vital point in evaluating the potential for use of a new preservative. To evaluate the behavior of the samples treated with the preservative emulsions of the present invention, the wood in contact with the degradation field during 405 days of exposure (Figure 8) in a eucalyptus forest, the incidence of the attack has been visually evaluated of fungi and termites, determining the health index of the samples. A greater degradation of the wood samples of Pinus spp without treatment was observed at the end of 405 days of exposure, being classified as intensely attacked by fungi after 315 days of exposure, and destroyed after 405 days of exposure. Only 3 untreated samples in the whole experiment presented some attack by termites, both slightly attacked, being samples obtained at different times (225, 360 and 405 days) of exposure.
    [0210] The samples of Pinus spp. treated with preservative according to the present invention were slightly attacked by fungi after 315 days of exposure, but without any incidence of attack by termites, with the exception of the treatment with EOL zn , which was moderately attacked by fungi after 315 days of exposure .
    [0211] Eucalyptus spp samples without treatment were intensely attacked by fungi. As for the samples with the EOLcu and EOLzn treatments, they were slightly attacked, without any incidence of termite attack during the 405 days of exposure.
    [0213] Example 12: Accelerated weathering chamber.
    [0215] In this stage the samples of Pinus sp. treated with preservative according to the present invention, of three different compositions, specifically the emulsions of Kraft lignin and Organosolv modified with Chromium, Copper and Boron (EKLCucrb and EOLCucrb). All experiments were compared with untreated wood.
    [0217] In Figure 9 it is possible to observe the degradation of the Pinus sp. Samples, exposed to accelerated aging in a weathering chamber during a period of 1680 hours of exposure, where the untreated samples presented cracks throughout the exposure. All the treatments presented darker coloration than the untreated wood. The untreated wood presented a greater loss, of 70.6%, than the wood treated with EKLCucrb, EK_Cucrb, which demonstrates the efficiency of the treatment over 1680 hours of direct exposure to ultraviolet rays. The other treatments showed lower mass loss results than the untreated wood.
    [0219] Example 13: Retention of the preservative according to the present invention
    [0220] The volumetric analysis was used to calculate the retention of the preservatives according to the present invention in the wood samples ( Pinus and Eucalyptus), by quantitative method. With the results of atomic absorption spectrophotometry (EAA), the percentages of active ingredient (metal) in the preservatives of the present invention, which were used to treat wood, have been calculated. They are as follows: EOLCu 0.24% Cu; EOLZn, 0.55% Zn, EOLCd, 0.15% Cd, EKLCd, 0.28% Cd, KLCu, 0.47% Cu, and finally KLZn, 1.12% Zn. Figure 10 depicts the retention of the preservatives of the present invention. It is observed that the samples with the highest retentions are those treated with Zn and were those with the highest concentration of metal. According to the NBR 16202 standard (ABNT, 2013), retention is a quantitative parameter, it is considered the most important factor to evaluate the quality of a preservative or preservative treatment and refers to the amount of toxic product retained in a given volume express wood
    [0223] in kg / m3. In the species Pinus sp. treated with EOLZn, a mean retention of 5.68 kg / m3 of emulsion was achieved (Figure 10). For the Eucalyptus sp. treated with EOLZn, a mean retention of 5.2 kg / m3 was achieved. The recommended retention for eucalyptus posts is approximately 5 kg / m3 NBR 16202 (ABNT, 2013).
    1
    权利要求:
    Claims (15)
    [1]
    1) Procedure to prepare a preservative composition for wood, which comprises the steps of:
    a) mixing lignin and a solution of Na 2 B 4 O 7 or N aN O 3 under stirring;
    b) adding, under stirring, a metal salt containing an M2 + ion, where M is an element selected from Groups 6, 11 or 12 of the Periodic Table of Elements;
    c) filtering the solid resulting in step c), which is a modified lignin;
    d) suspending the modified lignin in water to obtain the wood preservative composition.
    [2]
    2) Process according to claim 1, where M is selected from the group consisting of chromium, copper, zinc and cadmium.
    [3]
    3) Process according to any of claims 1 or 2, where the anion of the metal salt is NO 3 2-.
    [4]
    4) Process according to claim 1, where in step d) the water in which the solid is suspended contains a base in order to have a pH between 7 and 13, and subsequently an acid is added to obtain a pH of around 7.
    [5]
    5) Process according to claim 4, wherein the base is selected from the group consisting of NaOH and KOH.
    [6]
    6) Process according to claim 4 or 5, wherein the acid is selected from the group consisting of sulfuric acid, boric acid, acetic acid and hydrochloric acid.
    [7]
    7) Process according to any one of claims 1 to 6, wherein the amount of modified lignin is between 0.1 and 30% by weight with respect to the total weight of the preservative composition.
    2
    [8]
    8) Process according to any one of claims 1 to 7, where the metal salt is selected from the group consisting of Cr (NO 3 ) 2 , Cu (NO 3 ) 2 , Cd (NO 3) 2 and Zn (NO3) 2 ).
    [9]
    9) Preservative composition for wood based on modified lignin, obtainable by the process of any one of claims 1 to 8.
    [10]
    10) Process to preserve wood, which comprises impregnating the wood to be preserved with the preservative composition of claim 9.
    [11]
    11) Preserved wood obtainable by the method of claim 10.
    [12]
    12) Preserved wood according to claim 11, which presents a loss of mass due to Trametes versicolour fungal attack , measured in accordance with the ASTM D2017-94 standard, at least 75% lower than the loss of the same untreated wood.
    [13]
    13) Preserved wood according to claim 11, which has a Brinell hardness at least 40% higher than the same untreated wood.
    [14]
    14) Preserved wood according to claim 11, which presents a loss of mass in the fire resistance test by direct exposure lower by at least four percentage points than the same untreated wood.
    [15]
    15) Preserved wood according to any of claims 11 to 14, for exterior use.
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    同族专利:
    公开号 | 公开日
    EP3809850A1|2021-04-28|
    CA3104354A1|2019-12-26|
    BR112020026258A2|2021-03-30|
    US20210251222A1|2021-08-19|
    ES2800104B2|2021-05-21|
    CL2020003317A1|2021-06-11|
    WO2019243569A1|2019-12-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5246739A|1992-01-24|1993-09-21|Lignotech Usa, Inc.|Method for the treatment of wood with metal-lignin salts|
    EP1034903A1|1997-11-26|2000-09-13|Showa Denko Kabushiki Kaisha|Method for the treatment of wood with metallic treatment and wood treated by the method|
    WO2015105751A1|2014-01-07|2015-07-16|Liquid Lignin Company, Llc|Wood preservatives and methods for treating wood|
    SE465815B|1985-04-04|1991-11-04|Knut Lundquist|PROCEDURE FOR IMPROVING WOOD WITH ALKALILIGNIN|
    SI21885B|2004-09-17|2009-10-31|Košmerl Stojan|Wood protection agent|
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    ES201830613A|ES2800104B2|2018-06-21|2018-06-21|PRESERVATIVE COMPOSITION FOR WOOD BASED ON MODIFIED LIGNIN|ES201830613A| ES2800104B2|2018-06-21|2018-06-21|PRESERVATIVE COMPOSITION FOR WOOD BASED ON MODIFIED LIGNIN|
    EP19739884.5A| EP3809850A1|2018-06-21|2019-06-21|Preservative composition for wood based on modified lignin|
    BR112020026258-7A| BR112020026258A2|2018-06-21|2019-06-21|PRESERVING COMPOSITION FOR MODIFIED LIGNIN-BASED WOOD|
    US17/253,318| US20210251222A1|2018-06-21|2019-06-21|Preservative composition for wood based on modified lignin|
    PCT/EP2019/066459| WO2019243569A1|2018-06-21|2019-06-21|Preservative composition for wood based on modified lignin|
    CA3104354A| CA3104354A1|2018-06-21|2019-06-21|Preservative composition for wood based on modified lignin|
    CL2020003317A| CL2020003317A1|2018-06-21|2020-12-21|Composition of preservative for wood based on modified lignin|
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