• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    A method is described for achieving permanent binding of certain flame retardants to wood and/or wood products by an enzymatic chemical treatment. For this, immobilized oxidative enzymes are used by conventional methods, which are able to act on some compounds that are used as flame retardants, in particular halogenated organic compounds. After enzymatic activation of the flame retardants and subsequent separation of the immobilized enzyme from the solution with the activated retardants, the contact between the activated flame retardants and the wood to be treated, allows to generate stable chemical bonds between the flame retardants and the wood. This provides a permanent union of flame retardants to wood and/or wood products, which prevents their release and leaching during the commissioning of treated wood, which eliminates the main problem of the application of this type of retardants of flame. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2666709A1
    申请号:ES201600924
    申请日:2016-11-03
    公开日:2018-05-07
    发明作者:Diego MOLDES MOREIRA；Alberto DOMÍNGUEZ REPRESAS；Abdelmageed Mohamed OTHMAN MOSTAFA；María Ángeles SANROMÁN BRAGA
    申请人:Universidade de Vigo；
    IPC主号:
    专利说明:

    Procedure for stable binding of flame retardants to wood products by enzymatic catalysis SECTOR OF THE TECHNIQUE
    The invention is directed to the sector of treatment of materials, specifically to wood and products derived from it, with the aim of improving its properties. More specifically, the property that is improved is the resistance of the material against combustion, so that the invention is also related to flame retardant treatments. BACKGROUND OF THE INVENTION
    Wood is a natural and renewable material with a complex structure. Cellulose, hemicellulose and lignin are its main components; in smaller quantities there are other types of compounds such as fats, extractants, metals, etc. Cellulose and especially hemicellulose are the polymers that provide wood with low fire resistance. On the contrary, lignin does offer some resistance to being carbonized. Although the wood offers a certain initial resistance to fire, due to its low thermal conductivity and the presence of lignin, this capacity depends on the various characteristics of the type of wood considered. Factors such as density, permeability, morphology, moisture content or chemical composition of wood significantly affect fire resistance properties.
    Wood, for use as a construction, transport or decoration material, needs to meet fire resistance requirements. It is usually necessary in such cases to use compounds that increase that resistance, they are called flame retardants. Flame retardants are chemical compounds that reduce the likelihood of a fire occurring or delay its spread once it has started. There are several methods to apply these compounds: by spraying, by brush, by immersion or impregnation under vacuum-pressure.
    From a chemical point of view, flame retardants can be classified into five main categories:
    one. Inorganic compounds, which in turn can be divided into active compounds and passive compounds. The former act by releasing water when heated and therefore decreasing the heat of the surface of the burning material. Examples of active compounds would be aluminum trihydroxide and magnesium dioxide. Passive compounds work by preventing or hindering contact between combustible substances released by the material and the flame, either by reaction with those substances or by the formation of a layer that physically limits their release. Passive retarders are zinc borate or antimony trioxide.
    2. Additives containing silicon, such as silicon dioxide nanoparticles or natural clays.
    3. Phosphorus organic compounds, such as triphenyl phosphate or ammonium polyphosphate. They act normally by encouraging the generation of a carbon layer on the surface of the material, which limits the release of flammable gases during combustion.
    Four. Nitrogen rich compounds such as melamine and its derivatives. These compounds are capable of reducing the concentration of flammable gases produced in combustion, but also releasing inert gases that inhibit the chemical reactions that occur during combustion.
    5. Halogenated organic compounds, whether brominated, gold or fluorinated. They act directly on the combustion reaction by stopping the reactions that lead to flame formation.
    The halogenated compounds most commonly used as flame retardants are polybrominated biphenyls, polybrominated diphenyleters and tetrabromobisphenol A. Initially, polybrominated biphenyls were used to a large extent, but concerns about their environmental impact caused them to be gradually replaced by the brominated poly diphenylether. In turn, these have also been replaced by tetrabromobisphenol A, in an attempt to reduce environmental risk. All these brominated compounds seem to have a high persistence in the environment and tend to accumulate in the fatty tissues of the animals, which can cause damage to health. These compounds are present, as flame retardants, in a multitude of materials, such as computer plastics, televisions, car seats and textile fibers.
    The use of a certain treatment of wood protection against fire must take into account, not only the result of the tests once such treatment has been applied, but also the durability of the treatment over time. The washing of flame retardants in wood exposed to humidity or weather conditions will be all the greater the greater its solubility. Inorganic salts, very soluble in water, can be a problem for these uses. The use of flame retardants rich in nitrogen or phosphorus can accelerate microbial growth on wood, and its degradation. Some treatments can give unwanted colors, worsen the subsequent application of paints or adhesives, generate corrosion or even weaken the structure of the wood.
    It is important to note that the use as an additive of a flame retardant is not the same as the use as a reagent. For example, tetrabromobisphenol A is used as a reagent by bonding through a covalent bond to the plastic material that is intended to improve its resistance to fire, while polybrominated diphenylether would simply be trapped in its structure. The reactive compounds are less likely to leach or volatilize, while the additives are more easily released.
    Therefore, in the case of wood and wood derivatives, the ideal would be to find a flame retardant that could covalently bind to such materials, so that it was maintained during use in service, without giving it undesirable properties such as color , promotion of microbial growth, structural weakness, etc.
    A flame retardant with these characteristics would also avoid environmental and health problems arising from their release over time. This problem is one of the main drawbacks of these compounds, so that the stable binding of flame retardants to wood would avoid this type of inconvenience.
    Some oxidases enzymes, such as peroxidases, lacases, tyrosinases, etc., have the ability to bind some phenolic compounds to lignocellulosic materials. Thus, the modification of cellulose in paper pulps or even wood modification has been described, with the aim of modifying its properties, especially to improve hydrophobicity. These enzymes are capable of performing, using oxygen from the air, a radical coupling of phenolic compounds to lignocellulosic fibers, similar to what happens in nature in the polymerization of lignin in the cell walls of plants. In addition, these enzymes can be used in aqueous media that contain high percentages of some organic solvents, so very water-soluble substrates could be used.
    Among the oxidases, the ones that arouse the most interest, although not exclusively, because of their greater ease of industrial application are lacases, which are capable of acting before some phenolic compounds and aromatic amines. The reactivity of the laccases depends on the particularities of the enzyme (redox potential, producing organism) and its substrate. Thus, the phenolic compounds will react with the laccases, depending on their qUlmlca structure, and generate their corresponding phenoxy radicals, which may react in various ways. One of these possible forms is the union of certain materials, such as wood. In this way the lacquers have the ability to promote the stable binding of some of their substrates to certain materials.
    What is intended is to use these enzymes to make a permanent bond between the wood and a flame retardant, which must be phenolic in nature. This limits the scope of this application to halogenated organic retardants. The advantages of this treatment would be:
    • A longer duration of protection against fire by not losing the retardant by leaching or volatilization, since the link between the flame retardant and the wood material is covalent in nature, therefore stable.
    • A safer product from the sanitary point of view, for the same reason as explained in the previous point, since the washing and / or volatility of the compounds is limited. In this way the direct contact of the flame retardants with living beings is eliminated, since the flame retardants are not free, but covalently bound to the treated wood.
    • A range of conditions (T, pH) of application adjustable by the choice of the enzyme, but always in conditions mild enough not to significantly damage the wood or wood material to be treated.
    • The application of the treatment in conditions and with conventional materials. EXPLANATION OF THE INVENTION
    The present invention consists of a process by which halogenated flame retardant compounds are joined, which contain phenolic and / or amino groups in their chemical structure, to wood or wood-derived products, by the action of oxidases enzymes such as Catechol oxidases, tyrosinases or lacases. The enzyme used promotes stable bonding between the flame retardant and the wood, so that the flame retardant remains attached to the treated material after the procedure and does not volatilize or leach.
    The compounds used as flame retardants according to this procedure, have significant environmental disadvantages due to certain biological and health effects. The hazards of materials conventionally treated with these compounds are those derived from their volatilization and leaching to the environment. The proposed procedure avoids these processes of release of flame retardants to the environment, thus eliminating the problem of biological and health effects, thanks to the promotion of covalent bonding of said flame retardants to treated wood materials.
    The procedure consists of the following main stages: a) a preconditioning of the material comprising cleaning and / or washing, machining (debarking, incision, cutting to measure) and drying actions that will vary according to the type of wood; b) an enzymatic chemical treatment of the wood material with a solution of a compound or a mixture of halogenated organic flame retardant compounds of the phenolic type activated by an enzyme of the oxidase type; c) a drying of the treated wood material and, d) a washing to remove the by-products generated in the previous treatment and / or the flame retardant compounds not attached to the wood
    The wood or wood products to be treated should be conditioned so that the proposed enzymatic chemical treatment is as effective as possible. The conditioning consists in the realization of various stages of machining of the materials to be treated to give them their final surface dimension and texture, such as barking, possible incision if the permeability of the wood is very low, cut to size of the pieces, sanding and drying, because the humidity of the wood should not be high (preferably not more than 20%) to favor the penetration of the treatment solution. Mechanical treatments subsequent to enzymatic chemical treatment should be minimized as much as possible, since they could erode the treated material and affect its result.
    After conditioning the wood materials, the chemical-enzymatic treatment is carried out, which consists of the enzymatic reaction between an enzyme of the oxidase type and a solution of flame retardant compounds, preferably halogenated organic compounds of the phenolic type or a mixture of the same. This reaction activates flame retardants so that they bind to wood stably, if it is present. This treatment initially consists in the preparation of the solution of flame retardant compounds and the enzyme oxidase to be used, and subsequent impregnation of the conditioned wood. Said preparation and impregnation will vary according to the enzyme addition mode:
    1) Enzyme in solution: in this case the flame retardant and enzyme solutions can be added separately or previously mixed to the wood material to be treated, although this last type of application is recommended. The aqueous medium, with the enzyme and the flame retardant compound, must be brought into contact with the wood, so that the "flame retardant-wood" bond is initiated, so that there is free liquid on the surface of the wood so that the oxidized flame retardant can reach a point of attachment in the wood.
    2) immobilized enzyme: in this second case, the enzyme must be previously immobilized to a solid support, either by adsorption or covalent bonding, or be confined by encapsulation or the like. In this treatment modality, said enzyme does not contact the wood directly, but there is a preactivation step of the flame retardant in which the selected flame retardant compound and immobilized enzyme are contacted. Following this contact between enzyme and flame retardant solution, the resulting solution, which includes the flame retardant activated by the enzyme, is brought into contact with the wood or wood product. This method of using the enzyme in an immobilized state allows the enzyme to be reused easily.
    In any case, regardless of the above modalities, the addition of the activated flame retardant solution to the wood to be treated is compatible with any of the conventional methods and equipment used in the treatment of wood, such as surface treatments. (spraying, brushing, brief immersion) or in depth (prolonged immersion, vacuum-pressure impregnation). The treatment ends, in all cases, allowing the activated flame retardants to act for a recommended time of about 2 hours on air. Anyway, this time can vary between 1 minute and 20 hours depending on the type and amount of enzyme, the type of wood and the mode of application
    In a preferred embodiment, the concentration of the active compounds will vary depending on the wood to be treated, the enzyme used, the expected result and the compound or compounds used as flame retardants. For guidance, the enzymatic activity to be used should be of the order of 0.1 to 100 U1g of dry wood for the enzyme in solution, while in the case of immobilized enzyme the concentration could be lower, between 0.01 and 100 U / g of wood dry, considering the particularities of the treatment. The concentration of the flame retardant will be between 0.1 and 10 mM.
    In a preferred embodiment, some compounds that improve the treatment such as:
    a) organic surfactants or solvents to favor the dissolution of the retarder
    of flame; organic solvents preferably in a proportion not
    greater than 40% by volume.
    b) acidic, basic or regulatory solutions, to maintain the pH of the solution
    within the appropriate range for the correct functioning of the enzyme, being
    preferably the reaction solvent an aqueous medium with pH between 4 and
    10, preferably buffered with citrate / phosphate buffer.
    In a preferred embodiment, those compounds that have two characteristics: 1) that have in their chemical structure groups in which the oxidases enzymes can act and activate in such a way that they are able to be used as flame retardant compounds are initially capable of being used as flame retardant compounds can produce its stable bonding to wood.
    2) that possess some halogen element, fundamentally chlorine (CI) or bromine (Br) in their chemical structure These compounds are fundamentally the so-called phenolic and halogenated organic compounds (the halogenated element is denoted by "X" in the
    5 following structures of said chemical compounds), such as:a) Structures based on Tetrabromo bisphenol A
    x x
    OH
    x x
    b) Halogenated phenols with a single phenolic group and a single aromatic ring x x x x x
    x X X X X CH3 OH OH OH
    c) Halogenated catechols X X X X X
    X
    X
    X
    OH
    d) Trihalogenated phenol X
    x x
    OH
    e) Halogenated Methoxy Phenols
    x
    OH OH OH
    x x
    OH
    x
    x
    OH
    f) Diphenyl polyhalogenated ethers
    X
    X
    X X
    In a preferred embodiment, the type of enzyme can be used various oxidases such as phenoloxidases (tyrosinases), catechol oxidases or lacases, which can come from various microbial sources, or be produced either by organisms naturally producing these enzymes, or by modified organisms. Optimum operating conditions will vary depending on the type of enzyme and flame retardant compound to be used.
    After chemical-enzymatic treatment, either with immobilized enzyme or with enzyme in solution (with prior mixing with the flame retardant, or not), the treated wood material is dried to a value close to or below 18% humidity ; This drying can be done at room temperature or at higher temperatures, preferably not exceeding 95 ° C, by natural or artificial drying.
    Preferably, the wood must be subjected, finally, to a wash to remove the unbound compounds in a covalent way, if the environmental regulations require that there is no release of this compound during the use in service of the wood. This washing can be carried out with aqueous solutions, organic solvents or mixtures thereof, in order to eliminate flame retardants not covalently bonded to wood. Performing this washing eliminates future leaching of the same during the wood put into service. It should be taken into account that the wash waters may contain flame retardants, so that they have to be managed properly.
    The specified procedure for joining flame retardant compounds can be applied to woods of various types and origins (angiosperms, gymnosperms, tropical, mid-latitudes, etc.). In addition it is also applicable to all types of products derived from them or their major components (cellulose and lignin), such as wooden boards (of particles, fibers, plywood, laminates, etc.), paper pulp (chemical or mechanical), plastic and wood composites, cork, cardboard.
    The application of the procedure in each particular case may require slight modifications in the reaction conditions, considering the characteristics of each material. In the case of plastic and wood composites, as well as in fiber or particle boards, it is recommended, although not limited, to carry out the treatment before the process of manufacturing said composites or boards.
    Therefore, the described procedure has the following advantages over the more conventional procedures:
    • Stable union of flame retardants and wood, so that leaching and / or volatilization is avoided, thus eliminating environmental and human health risks.
    • Treatment durability, due to the absence of flame retardant leaks from the treated wood material.
    • Adaptability of application to conventional wood treatment systems.
    • Soft treatment conditions: non-abrasive chemical components with the material to be treated, mild temperatures (recommended not exceeding 70CC), aqueous medium, non-extreme pH (between 4 and 9; preferably neutral pH).
    • Possible enzyme reuse if immobilized enzyme is used. BRIEF DESCRIPTION OF THE DRAWINGS
    The description is complemented by a set of drawings or figures that illustrate the potential results of the treatment:
    Figure 1. Results of the temporal evolution of the contact angles of water droplets on the surface of beech wood samples, resulting from two types of experiments: treatment with Tetrabromocatecol (TBC) and enzyme immobilized in stage 1 and on the other "control treatment" part (TBC but without immobilized enzyme).
    Figure 2. Photographs of the evolution of a drop of water over time for samples of treated beech wood (TBC and immobilized enzyme in stage 1) And control samples (TBC without enzyme in stage 1). PREFERRED EMBODIMENT OF THE INVENTION
    A preferred way of carrying out the process for stably linking flame retardants to wood products includes the following steps:
    1) conditioning of the material to be treated: barking, cleaning, machining of the pieces to give them the desired size, shape and texture and drying.
    2) preparation of the solutions for the treatment of the conditioned wood: dissolution of the enzyme and flame retardant solution, the latter with an organic solvent concentration (for example acetone) of 20% by volume.
    As an enzyme, various oxidases such as phenoloxidases (tyrosinases), catechol oxidases or lacases can be used, produced either by naturally occurring organisms of these enzymes, or by modified organisms, although lacases (which are shown below) they can be from various microbial sources, each with its specific activity on the phenolic substrate used and optimal operating conditions). The trametes vil / osa and Myceliophthora thermophila fungi lays stand out for their greater commercial availability.
    To ensure the good dissolution of the substrate used, acetone can be added to the aqueous medium, up to a maximum of 40% to ensure enzymatic viability. The buffer used will be citrate / phosphate with a pH value between 4 and 9, since other organic acids can inhibit the enzyme. The reaction temperature may be between 20 and 70 oC, the optimum value will depend on the specific type of enzyme. In the example detailed below, in which immersion of wood samples in the treatment solution occurs, the dose of laccase enzyme in the aqueous solution will be between 0.1 and 50 U / mL, and that of retardant of flame between 0.1 and 5 mM. If an in-depth treatment is intended, whereby the solution has to penetrate significantly into the wood (from 3 mm), so that the treatment is not considered superficial, the dose of laccase should refer to the amount of wood to be treated, and should be 1 to 100 U / g of dry wood to be treated.
    In this case, a unit of laccase activity is defined as that amount of enzyme that is capable of oxidizing 1 I-lmol of 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid (ABTS) per minute. Amount can be determined by UV-Vis spectrophotometry by measuring the oxidation of the substrate under certain conditions (pH 7 set by 0.1 M phosphate buffer, 23 ° C and using the ABTS E436 molar absorptivity coefficient = 29300 M · 1 cm -1).
    3) impregnation of the wood with the mixture solution. For this, any of the conventional methodologies can be used, each of which requires also conventional conditions and application times; For example, brushing requires two or three application coats allowing drying at room temperature between each of the applications. The doses of active components specified above must be taken into account.
    4) drying of treated wood material to levels of 18% humidity or lower. Drying can be done by natural or artificial methods at room temperature or at high temperatures, but it is recommended not to exceed 95 ° C.
    5) washing the material with acetone solution in water (20% acetone by volume) and then with water.
    Examples With the intention of showing the present invention in an illustrative way but in no way limiting, the specific conditions used to carry out the treatment of beech wood sheets (Fagus sylvafica) of 5x1 cm, with the Myceliophfhora fhermophila house, are shown for the binding of tetrabromobisphenol A and tetrabromocatecol, in two modalities, with the enzyme in solution and immobilized.
    Example 1: treatment with enzyme in solution Beech wood sheets are previously washed with acetone in a Soxhlet according to TAPPI T-264, to eliminate possible impurities and agents that may interfere. Wood samples were placed inside the Soxhlet in a cellulose cartridge and the extraction was refluxed for 8 hours. The sheets were then washed with water and their washing was completed by immersing them in distilled water at 100 ° C for 1 hour.
    The washed sheets were immersed in an aqueous medium containing one of the two flame retardants selected, tetrabromobisphenol A or tetrabromocatecol, and commercial enzyme laccase of Myceliophfhora fhermophila. The concentration of phenolic flame retardant in the reaction medium was 1 mM, and the enzyme laccase was added at a rate of 25 U / mL. This aqueous solution to treat the wood was previously adjusted to pH 8.0 with a citric / phosphate buffer (50 mM final concentration) and containing acetone (25% volume ratio). The contact between the wood and the solution took place at 50 oC for 2 hours. As a control, two types of treatments were performed under identical conditions; in one of them no retarder was added
    5 of some flame, while in the other the enzyme lacasa was not added.
    Once the reaction has elapsed, the wood sheets are subjected to a new wash similar to the initial one, that is, a wash with acetone in Soxhlet and another with hot distilled water. This eliminates the flame retardant that has not been
    10 stably attached to the wood.
    The wood sheets, once dried, were subjected to a technique of elementary surface analysis by X-ray photoelectronic spectroscopy (XPS). This technique allows to detect the elements present on the surface of the wood and
    15 its relative proportion. Therefore it serves to detect, or not, on the surface of the wood the brominated flame retardants that were intended to be joined. The measurement has been made in three points of each sheet to correct the heterogeneity of the wood. The results obtained can be seen in the following table:
    Treated wood sheet: Point% of C% ofO% of Br
    Without phenolic compound and with laccase one65.6230.47n.d.
    2 65.5529.30n.d.
    3 64.2829.61n.d.
    With tetrabromocatecol and without laccase one64.1032.99n.d.
    2 65.1633.28n.d.
    3 65.6731, 90n.d.
    With tetrabromobisphenol A and without laccase one63.8933.98n.d.
    2 64.1933.99n.d.
    3 64.9532.76n.d.
    With tetrabromocatecol and with lacasa one65.4530.880.21
    2 63.9331, 250.55
    3 63.9731, 740.46
    With tetrabromobisphenol A and with laccase one66.0230.130.40
    2 66.3929.300.57
    3 64.5331.450.38
    Therefore, in this example, it is evident that when the wood is brought into contact with the flame retardants (but without enzyme), or the wood with enzyme (but without flame retardants) there is no union between the flame retardant and wood, since the bromine element is not detected by XPS. While when the laccase and a flame retardant are present at the same time, in both cases tested, the flame retardants are attached to the wood sheet, which is observed thanks to the detection of bromine in the wood even after of doing an intense process of washing the treated wood.
    Example 2: immobilized enzyme treatment.Beech sheets were used and washed and conditionedSo in the previous example.
    The enzymatic chemical treatment in this case was carried out in two different stages:
    Step 1: A 20 mL reaction mixture was prepared with phosphate buffer pH 7.0 (0.1 M), 5mM tetrabromocatechol (TBC), 40% (v / v) acetone and 12U of the covalently immobilized laccase in the commercial solid support Immobead 150P. The reaction mixture was incubated for 2 hours at 50 ° C with stirring (75rpm). The liquid mixture was subsequently separated from the commercial support with immobilized enzyme.
    Stage 2: the wood samples were impregnated with the liquid resulting from the reaction of the previous stage, in which there is no enzyme. The impregnation time was 20 hours at 50 ° C and with stirring (75rpm). Subsequently, the wood samples were allowed to dry at room temperature for 1 h, washed in a bath with distilled water at 80 ° C for 2 hours and with stirring (75 rpm). After this washing, the wood samples were washed with distilled water at room temperature and dried at 60 ° C for 1 hour.
    To analyze the effectiveness of the treatment, the hydrophobicity of the treated samples was measured and compared with the control samples, which were treated in the same way but without the addition of immobilized enzyme in step 1. The hydrophobic effect of the halogenated compounds is known, as the brominated compounds used in the examples provided, to the materials to which they are applied. Thus, in this case the hydrophobicity of the wood is directly related to the binding of the brominated compounds thereto. Hydrophobicity was measured by measuring the contact angle of water droplets with the surface of the samples.
    It can be clearly seen in Figure 1, as with the passage of time after the addition of water, the contact angle in the treated samples is reduced by a smaller amount than in the control samples, indicating the union of the TBC in the wood and that this compound is bound in such a way that it remains in the wood although it
    10 Perform an aggressive wash. This effect is also clearly visible in Figure 2, which shows the increase in hydrophobicity, due to the presence of bromine, of the samples treated in stage 1 with TBC and immobilized laccase.
    权利要求:
    Claims (14)
    [1]
    1. Procedure for stable binding of flame retardants to wood products
    by enzymatic catalysis, characterized by comprising the following stages: a) a preconditioning of the material comprising cleaning and / or washing, machining (debarking, incision, cutting to measure) and drying actions that will vary according to the type of wood; b) an enzymatic chemical treatment of the wood material with a solution activated by an oxidase type enzyme, this solution containing a phenolic and halogenated organic flame retardant compound, or a mixture of several of these flame retardant compounds; c) drying of treated wood material and; d) a wash to remove the by-products generated in the previous treatment and / or the flame retardant compounds not attached to the wood.
    [2]
    2. Procedure for the stable binding of flame retardants to wood products by enzymatic catalysis, according to claim 1, characterized in that the chemical-enzymatic treatment according to step b) consists in the prior preparation of the solution of flame retardant compound and the enzyme oxidase to be used, and subsequent impregnation of the conditioned wood, which varies according to the method of addition of the enzyme:
    a) enzyme in solution, in this case the flame retardant solutions and
    enzyme can be added separately or previously mixed to the material
    logger to be treated;
    b) immobilized enzyme, the enzyme must be previously immobilized in a
    solid support, then the retarder solution of
    flame, or mixture of retarders, with the enzyme immobilized in order to pre-activate it, and
    another stage in which the activated flame retardant solution is used to
    treat the wood;
    in both cases, the impregnation of the activated flame retardant solution to the wood material cannot exceed 2 hours before its application to the wood material to be treated.
    [3]
    3. Process for the stable binding of flame retardants to wood products by enzymatic catalysis, according to claim 2, characterized in that the immobilization of the enzyme to a solid support, can be by adsorption or covalent bonding, or be confined by encapsulation or the like.
    [4]
    Four. Procedure for the stable binding of flame retardants to wood products by enzymatic catalysis, according to claims 1 and 2, characterized in that the enzyme oxidase to be used according to step b) is selected from phenoloxidases (tyrosinases), catechol oxidases or laccase, which can proceed from various sources
    10 microbials, either produced either by organisms naturally producing these enzymes, or by modified organisms.
    [5]
    5. Procedure for the stable binding of flame retardants to wood products by enzymatic catalysis, according to claims 1 and 2, characterized in that the
    Phenolic halogenated organic flame retardant is a molecule selected from the following formulas, in which "X" represents an element of the group of halogens such as Fluorine (F), Chlorine (CI), Bromine (Br) and / or mud (1):
    a) Structures based on Tetrabromo bisphenol A
    X XCH3
    I
    HO
     C OH
    I
    CH3 20 X X
    b) Halogenated phenols with a single phenolic group and a single aromatic ring
    X X
    X X X X X
    X
    X XX X
    OH OH
    e) Halogenated catechols
    x X
    xx
    OH OH OH
    d) Trihalogenated phenol
    x x
    e) Halogenated Methoxy Phenols
    x
    xn
    H, CO l / OH
    x
    X
    OH
    f) Diphenyl polyhalogenated ethersX HOX XXXor
    X
    x
    X X Xx xX O
    X X
    [6]
    6. Procedure for stable binding of flame retardants to wood products by enzymatic catalysis, according to claims 1 to 5, characterized in that the chemical-enzymatic treatment is applied by spraying, brushing or immersion operations or applied by means of application systems vacuum-pressure impregnation.
    [7]
    7. Process for the stable binding of flame retardants to wood products by enzymatic catalysis, according to claims 1 to 6, characterized in that the solution used for the enzymatic chemical treatment comprises a flame retardant concentration between 0.1 mM and 10 mM.
    [8]
    8. Procedure for the stable binding of flame retardants to wood products by enzymatic catalysis, according to claims 1 to 7, characterized in that the amount of enzyme used in the case of the enzyme mode in solution is between 0.1 to 100 U / g of dry wood , and in the case of immobilized enzyme modality it comprises a concentration between 0.01 to 100 U / g of dry wood.
    [9]
    9. Process for the stable binding of flame retardants to wood products by enzymatic catalysis, according to claims 1 to 8, wherein the reaction solvent medium is an aqueous medium with pH between 4 and 10, preferably buffered with citrate / phosphate buffer, and finally If the retarder is dissolved, an organic solvent can be added in a proportion not exceeding 40% by volume.
    [10]
    10. Procedure for the stable binding of flame retardants to wood products by enzymatic catalysis, according to claims 1 to 9, characterized in that the reaction temperature of the enzymatic treatment stage b) is between 20 and 70oe.
    [11 ]
    eleven . Process for the stable bonding of flame retardants to wood products by enzymatic catalysis, according to claims 1 to 10, wherein the impregnation time of the flame retardant solution activated with the wood to be treated in step b) is comprised between 1 minute and 20 hours, depending on the type and amount of enzyme, type of wood and mode of application.
    [12]
    12. Process for the stable binding of flame retardants to wood products by enzymatic catalysis, according to claim 1, wherein the stage of drying stage c) is carried out by conventional methods (natural, artificial or mixed) until humidity levels of 18% are reached. or lower
    [13]
    13. Process for the stable binding of flame retardants to wood products by enzymatic catalysis, according to claim 1, wherein the washing or extraction of step a and d) is carried out with a solvent or with water, or with
    5 mixture of both components.
    [14]
    14. Use of the method according to previous claims, characterized in that it can be used to treat wood of various types and origins, as well as all types of derivatives thereof or their major components (cellulose and lignin)
    10 such as wooden boards, paper pulps, plastic and wood composites, cork and cardboard.
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    Q) or ...
    .....
    "OR
    0.
    OR
    "5
    ·· 0
    Ol
    , «C: 20
    --- TBC + immobilized lacquers ··· 0 ·· TBC
    OR
    O 50 100 150 200 250
    Time (s)
    Figure 1
    25
     Figure 2
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