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    • 专利摘要:
    Mixture of non-polymeric organic components with flame retardant capacity method of preparation and use. The object of the present invention is a mixture with flame retardant capacity, free of pyrophosphates, characterized in that it comprises a mixture of non-polymeric organic components, where at least one first compound of the mixture acts as a hydrogen bond donor; and at least one second compound in the mixture acts as a hydrogen bond acceptor. The method of preparing said flame retardant mixture and its use as a flame retardant agent in extinguishing forest fires is also an object of the present invention. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2837489A1
    申请号:ES201931175
    申请日:2019-12-31
    公开日:2021-06-30
    发明作者:Tayari Abdessamad Grirrane；Gomez Hermenegildo Garcia；Escrig Francisco Antonio Alandi；Lleo Juan Llobell；Mondria Regina Garcia
    申请人:Primalchit Solutions S L；Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    [0002] MIX OF NON-POLYMERIC ORGANIC COMPONENTS WITH CAPACITY
    [0004] TECHNICAL SECTOR
    [0005] The present invention falls within the flame retardant (or combustion retardant) compounds and mixtures that can be used in open spaces for the control and extinction of large fires, mainly forest masses. The invention also relates to their method of preparation, as well as to the use of said mixtures in fire fighting.
    [0007] BACKGROUND OF THE INVENTION
    [0008] The flame retardants currently used in fire fighting are inorganic compounds, mainly phosphorus and nitrogen. In particular, there is a combustion retardant formulation on the market (FIRE-TROL) that is the most widely used in the extinction of forest fires worldwide. Although this formulation has shown its efficiency, the fundamental component of the formulation are pyrophosphates which, due to their non-biodegradable nature, end up concentrating in aquifers and produce eutrophication effects as a consequence of their activity that favors the growth of algae and plants, particularly those high concentrations that can be reached in water as a consequence of fire fighting tasks. Unlike this formulation, the present invention describes mixtures of harmless or very low toxicity compounds that, being biodegradable, act as flame retardants.
    [0010] There are also numerous organic compounds for which their ability to retard combustion or to extinguish combustion has been determined. The flame retardant effect is understood to be the ability of some compounds or mixtures to inhibit the combustion of a combustible material by coating its surface, either by extinguishing the flame or by making the progression of the fire front slower than in its absence.
    [0011] Among the non-polymeric organic compounds used in fire extinguishing, a type of general use are those that have halogens in their composition.
    [0013] Thus, for example, the application CA2052887 refers to a composition with a combustion retarding capacity that comprises at least one compound selected from isomers of dichloropentafluoropropane.
    [0015] Likewise, the application WO2015104004 refers to a composition with the ability to extinguish combustion that comprises a derivative of carboxylic acid and a pyrotechnic agent.
    [0017] The vast majority of non-halogenated organic compounds are flammable and have no flame retardant activity. Some types of organic compounds used in fire extinguishing are halogenated compounds that can generate highly toxic gases in their transformation, as well as having very adverse effects on the environment. Thus, for example, chlorinated compounds generate phosgene which is a highly toxic compound in a certain percentage.
    [0019] In the commercialization of flame retardants, the brominated variety is the most used. These brominated organic compounds are very effective in plastics, textiles, electronics, clothing and furniture, but they have the disadvantage of being highly neurotoxic compounds, which is why they are not used as fire retardants in forest fires.
    [0021] The present invention arises from the unexpected and unpredictable result of the flame retardant ability of mixtures of two or more flammable organic compounds. This unexpected activity derives from self-assembly and the formation of sufficiently strong hydrogen bonding between the components of the mixture. This strong interaction makes the combustion process endergonic, allowing the flame to go out, being the basis of the object of the present invention.
    [0023] DESCRIPTION OF THE INVENTION
    [0024] A first object of the invention is a mixture or composite free of pyrophosphates and with Flame retardant capacity, not based on the use of polymeric materials, and which is suitable for use in extinguishing fires (preferably forest fires), characterized by comprising a mixture of non-polymeric organic components, of low toxicity and biodegradability , where:
    [0025] to. at least one of the components of the mixture acts as a hydrogen bond donor, being preferably selected from a group consisting of dicyandiamide, urea, malonic acid, glycerol, guanidine, 1,1-dimethylurea, oxalic acid, ethylene glycol and derivatives, trifluoroacetamide, 1-methylurea, imidazole, 1,3-dimethylurea, lactic acid, resorcinol, 2-imidazoline, arginine, benzoic acid, benzyl alcohol, propyleneurea, thiourea, 4-hydroxybenzoic acid, succinic acid, acetamide, benzamide, levulinyl acid gallic acid, ammonium formate, tartaric acid, malonic acid and derivatives, adipic acid, oleic acid, linoleic acid, stearic acid, trimyristin, citric acid and isocitric acid, as well as any of their combinations;
    [0026] b. and at least one of the components of the mixture acts as a hydrogen bond acceptor, being preferably selected from a group consisting of lidocaine or an ester derivative, proline, histidine, nicotinic acid, (phenylmethyl) triphenylphosphonium chloride, alanine , methyl triphenylphosphonium bromide, glycine, ethanolamine, betaine, ammonium formate and ammonium oxalate, as well as any of their combinations.
    [0028] Preferably, the molar ratio of the hydrogen bonding acceptor and donor compound can vary from 1: 5 to 5: 1.
    [0030] Surprisingly and that cannot be deduced by an expert in the field, it has been found that the mixture of two or more non-polymeric organic compounds that individually can be flammable (such as those described above), gives rise to a mixture with properties Combustion retardants due to the formation of strong hydrogen bonds that increase their thermodynamic stability, to the point that their flammability disappears, acting for this reason as combustion retardants.
    [0032] This union or self-assembly of the components of the mixture occurs spontaneously, giving rise to a supramolecular aggregate that can be characterized as an entity different from that of its individual components, based on their properties. The origin of self-assembly is the establishment of a strong intermolecular interaction that maintains the union of the components of the mixture. In the present invention, the interaction that is established as the origin of the self-assembly and that is, therefore, responsible for the flame retardant effect, is the hydrogen bridge interaction.
    [0034] These interactions between hydrogen bonding donor and hydrogen bonding acceptor decrease the entropy difference of the phase transition and increase the stability of the aggregate with respect to that of its individual components. The strength of hydrogen bonds is related to the phase transition temperature, thermodynamic stability, and other properties of the mixture. The present invention reveals that these forces can become strong enough to disfavor the enthalpy of combustion of the aggregate relative to that of its individual components.
    [0036] Along with the flame retardant activity of the mixture, other criteria met by the components of the mixture are:
    [0037] • presenting minimal negative effects for vegetation and ecosystems at concentrations that can be reached if used in the extinction of forest fires;
    [0038] • biodegradability, so that they do not persist indefinitely in the environment;
    [0039] • solubility in water and / or short persistence in aqueous medium. This is a key aspect, as it is a universal solvent in fire fighting. Since the self-assembly origin of the flame retardant effect is the hydrogen bonding interaction, the components of the mixture are soluble in water. Furthermore, self-assembly is not observed in this medium, since the interaction of each component with water prevails. However, when the water evaporates, due to its low boiling point, the components of the mixture are recognized and, at that moment, cause the desired retarding effect. That is why in an aqueous medium it cannot be considered that the self-assembly mixture is present, forming as the water evaporates.
    [0041] Other desirable properties are wide availability and low cost, stability, and easy handling.
    [0042] Within the strong interactions that are capable of altering the enthalpy of combustion, there is a great diversity of possible combinations of the starting components. This great diversity of options is a great advantage, since it allows to control the physical and phase properties of the self-assembly mixtures. Among these properties is the ability to dissolve solutes of a very different nature.
    [0044] Thus, in particular embodiments of the invention, the mixture may comprise at least one additional additive that can preferably be selected from a group consisting of:
    [0045] to. water, preferably in a percentage comprised between 50% and 95%; b. at least one inorganic or organic compound with acid or base chemical properties, preferably in a percentage equal to or less than 30% by weight with respect to the total mixture. In preferred embodiments of the invention, the acid additive will be selected from a group consisting of hydrochloric acid, sulfuric acid, sulfonic acid, carbonic acid, and carboxylic acid, as well as any of their combinations. As the basic additive, preferably an alkali, alkaline earth metal carbonate or bicarbonate will be employed, preferably selected from a group consisting of sodium, potassium, magnesium and calcium, as well as ammonium carbonate. These additives can be pure or dissolved in aqueous medium and make it possible to regulate the pH value of the self-assembly mixture and of the corresponding aqueous solutions around almost neutral values and, preferably, in the range between 5 and 9. The value of Final pH may also depend on the nature of the soil where the retarding agent is to be used;
    [0046] c. at least one solid compound on which the mixture is impregnated. Preferably, said solid compound can be selected from a group consisting of clays (preferably selected from montmorillonite, sepiolite and kaolin) and agricultural waste (preferably straws from agricultural crops such as rice, wheat, barley and tigernut, among others), as well as any of its combinations (for example, like adobe). In preferred embodiments of the invention, the percentage of the retardant mixture that is impregnating the solid compound may vary between 5% and 40% by weight, and more preferably between 5% and 10% by weight;
    [0047] d. at least one coloring substance or a pigment, suitable for visualizing the area where the flame retardant mixture is to be applied. Pigments can be natural, preferably metal oxides and more preferably iron (red) oxides or biodegradable natural organic colorants such as those obtained from insects, mollusks, plants and fruits. The percentage of these colorants will preferably be less than 5% by weight and preferably less than 1%.
    [0049] Thus, as indicated, in particular embodiments of the invention the mixtures may be used pure. In other embodiments of the invention, the mixtures may be used in aqueous solution of the desired concentration (preferably between 5% and 10% by weight). Finally, the mixtures may also be used supported on fireproof solids or not. The water used to dissolve the mixtures with a retarding effect can be fresh or sea water.
    [0051] One of the general characteristics of the mixtures described here, due to their flame retardant effect, is that, since the individual compounds can be solid at room temperature, their mixture produces a notable decrease in the melting point, sometimes higher than 100 oC of decrease, being able in many cases to become liquid at room temperature (approximately 25 ° C). This effect is due to the strong interaction that is established between the components of the mixture, which determines that the crystal lattice of the individual components is not the most stable when the mixture occurs.
    [0053] Additionally, the object of the invention is the method of preparing mixtures of hydrogen donor and acceptor compounds. In particular, this method may comprise preparing the mixture simply by intimately mixing its components, either by co-grinding the components (when at least one is solid) or by evaporating solutions of the compounds. In some cases, a change in physical state is observed, resulting in the mixture being a viscous liquid. This change in physical state reflects the strong interaction between both compounds, which spontaneously undergo self-assembly. Any other way of preparing the mixtures, such as melting the components and pouring one component over the other with stirring or the aqueous dissolution of the components together or separately and their subsequent mixing is also suitable for carrying out the preparation of self-assembly mixture with retarding properties of calls.
    [0055] In those embodiments in which the mixture is used to impregnate solids that act as a support for the mixture, said impregnation may be suitably carried out by dissolving the mixture or its components in aqueous medium and then adding the desired amount of the solid. The suspension is then stirred and the water slowly evaporated by heating, by means of forced air passage, by means of vacuum or a combination of these procedures. Alternatively to evaporation, it is possible to recover the solid, once impregnated, by filtration or centrifugation. Other suitable forms of impregnation may include painting or spraying with aerosols, among others.
    [0057] In the case of impregnating a solid material with the self-assembling mixtures with flame retardant properties, this solid material can have some other additional functionality. Thus, when the flame retardant self-assembly mixture impregnates the rice straw, it may contain seeds of shrubs characteristic of the forest area affected by the fire. In this way, in addition to the fire retardant effect, the combination can help to repopulate the affected forest area. Other functions of the impregnation result can be to avoid the dragging of the soil damaged by heavy rains or to contain nutrients or desirable phytosanitary compounds.
    [0059] Finally, the use of claimed self-assembly mixtures as flame retardant agents in extinguishing forest fires is also an object of the invention, particularly those mixtures that also meet the criteria of benignity for the environment, for vegetation and for natural ecosystems. Furthermore, widely available and low cost combinations of compounds are preferable.
    [0061] DETAILED DESCRIPTION OF THE INVENTION
    [0062] Among the combinations of organic hydrogen bond donor and acceptor molecules, those with the most effective fire retardant activity are those with the highest endothermic peak in thermogravimetric profiles. The value of this endothermic peak shows greater stability in self-assembly and greater resistance to combustion. In this sense, among the most used for the generation of these mixtures of organic molecules that undergo self-assembly and that are free of pyrophosphates are certain aminoamides and, more preferably, lidocaine (melting point 69 ° C), which is an affordable, biodegradable and non-toxic compound . In combination with a hydrogen donor species (DH), which must meet the same characteristics of biorenovability and lack of toxicity, such as urea (melting point 133 ° C), dicyandiamide (melting point 209 ° C), acids preferably renewable carboxylics (oxalic, succinic, citric and lactic, among others), amino acids, natural polyols such as glycerol and carbohydrates. With all these compounds, lidocaine is capable of forming non-toxic and bio-renewable self-assembly mixtures, with low melting points (between 0 ° C to 50 ° C) in some cases, which makes it possible to handle it as liquid mixtures at temperature. ambient (between 10 ° C and 35 ° C).
    [0064] In principle, organic compounds undergo endothermic combustion. Lidocaine and urea are two cases of that general rule. Thus, during the thermogravimetric analysis of lidocaine, two endothermic signals are observed, the first centered at 75 ° C and the second centered at 250 ° C, which could be due, respectively, to loss of moisture and oxidative degradation.
    [0066] On the other hand, thermogravimetric analysis of urea exhibits a two-step decomposition that results from the sequential decomposition of the reactions of NH2CONH2 (NH 2 CONH 2 - »■ NH3 HNCO and HNCO H20 -» ■ NH3 C02) that occur, respectively, in the temperature range between 150 ° C and 270 ° C. In addition, five endothermic signals are observed centered respectively at 140 ° C, 220 ° C, 240 ° C, 386 ° C, and 407 ° C.
    [0068] In a particular embodiment of the invention, the mixture can be a combination of solid lidocaine and solid urea in a weight ratio of 1 to 1, in the presence of an equivalent of hydrochloric acid (37% aqueous solution). This mixture is liquid at room temperature (25 ° C) and has a pH value between 7 and 9. The impregnation with this mixture of a combustible object such as wood or paper produces an unexpected effect on it as a flame retardant.
    [0070] Therefore, it has been shown that the combination of lidocaine and urea in the indicated proportion does not present the calorimetric behavior of the components. individual, but gives off less heat of combustion. These differences in the thermodynamics of the combustion reaction are due to the donor-receptor self-assembly, which establishes a strong interaction between both components.
    [0072] Thus, in a preferred embodiment of the invention, the hydrogen bond acceptor compound is lidocaine or an ester derivative and the donor compound is dicyanamide or urea. Even more preferably, the molar ratio between them can vary between 1: 1 and 1.2.
    [0074] In another preferred embodiment of the invention, the hydrogen bridging compound is glycine and the acceptor compound is urea or dicyandiamide, preferably in a molar ratio that can vary between 1: 1 and 1: 2.
    [0076] In another preferred embodiment of the invention, the hydrogen bonding compound is ammonium formate and the hydrogen bonding acceptor is selected from glycine, urea, and dicyandiamide. More preferably, the molar ratio of these components can vary between 1: 1 and 1: 2.
    [0078] BRIEF DESCRIPTION OF THE FIGURES
    [0080] Figures 1 and 2 show examples of composite structures that give rise to self-assembling mixtures with flame retardant effect that are representative, but not limiting, of the present invention.
    [0082] Figure 1 shows a group of hydrogen-accepting organic molecules that can be used in the preparation of self-assembling mixtures with flame retardant properties that are the object of the present invention.
    [0084] Figure 2 shows a group of organic hydrogen donor molecules that can be used in the preparation of self-assembly mixtures with flame retardant properties that are the object of the present invention.
    [0086] EXAMPLES
    [0087] Next, non-limiting examples of the present invention will be described.
    [0088] Example 1
    [0089] Formation of self-assembly mixtures between lidocaine (LIC) and urea. In a 100 ml flask, 30 mmol (7.02 g) of lidocaine (LIC), 30 mmol (1.80 g) of urea and 30 mmol (1.09 g) of hydrochloric acid are introduced at room temperature. The resulting mixture is heated at 80 ° C for 12 h. After this time, the liquid mixture 1LIC / 1Urea / 1HCl is obtained whose approximate pH value is in the range between 8 and 9. This mixture with fire retardant effect can be used directly, it can be diluted in fresh or sea water at a concentration of around 10% or less or serves to impregnate solid supports.
    [0091] This mixture, when impregnated on a strip of cardboard 2 cm wide by 10 long and allowed to dry, causes this cardboard not to burn, even when subjected to the prolonged action of a torch flame. In comparison, the same cardboard burns completely when the flame is approached, ignites the flame in the cardboard, and the cardboard is allowed to burn completely in the absence of the flame that started the fire.
    [0093] Example 2
    [0094] Formation of self-assembly mixtures between lidocaine and dicyandiamide (DCD). The procedure is as in Example 1, replacing the urea mass with 30 mmol (2.52 g) of dicyandiamide (DCD), using the same amounts of lidocaine and hydrochloric acid. The resulting mixture is heated at 80 ° C for 10 hours. After this time, the liquid mixture 1LIC / 1DCD / 1HCl is obtained whose pH value is in the range between 7 and 8. This mixture with fire retardant effect can be used directly, it can be diluted or it is used to impregnate solid supports.
    [0096] When a cardboard strip is impregnated with this mixture and allowed to dry, the cardboard becomes resistant to combustion even when subjected to a flame from a torch. In comparison, a strip of the same cardboard burns completely when a flame is lit on it.
    [0098] Example 3
    [0099] Formation of aqueous mixtures between lidocaine, urea and sodium bicarbonate. The procedure is carried out according to the procedure and quantities indicated in Example 1, heating the mixture at 80 ° C for 10 h. After that time, a solution of 2.52 g of sodium bicarbonate is added little by little to this mixture of LIC and urea. (30 mmol) in 50 ml of water with a pH value of 10 and stirred for another 2 h at 80 ° C. The final aqueous solution 1LIC / 1urea / 1HCl / 1NaHCO3 obtained with a fire retardant effect can be used directly, it can be diluted in fresh or salt water at a concentration of approximately 10% or it can be used to impregnate solid supports.
    [0101] When a cardboard strip is impregnated with this mixture and allowed to dry completely, the cardboard becomes resistant to combustion, not igniting the flame of a torch. In comparison, the same cardboard strip burns completely when a flame is lit in it by a blowtorch.
    [0103] Example 4
    [0104] Formation of aqueous solutions of lidocaine, dicyandiamide and sodium bicarbonate. Proceed as in Example 2 placing at room temperature, in a 100 ml flask, 30 mmol (7.02 g) of lidocaine (LIC), 30 mmol (2.52 g) of dicyandiamide (DCD) and 30 mmol (1.09 g) of acid hydrochloric. The resulting mixture is heated at 80 ° C for 10 hours. After that time, a solution of 2.52 g of sodium bicarbonate (30 mmol) in 50 ml of water is added little by little to the self-assembly mixture and the solution is stirred for 2 h at 80 ° C. Other bases that can also be used are potassium, magnesium and calcium bicarbonate, in the corresponding weights to maintain the molar ratio. The final aqueous mixture 1LIC / 1DCD / 1HCl / 1NaHCO3 obtained with a fire retardant effect has an approximate pH value of 7. This mixture can be used directly, it can be diluted or it can be used to impregnate solid substrates.
    [0106] As in the previous examples, a cardboard combustion test in strips or wood chips comparing a sample impregnated with the mixture 1LIC / 1DCD / 1HCl / 1NaHCO3 after allowing it to dry demonstrates its flame retardant effect.
    [0108] Example 5
    [0109] Impregnation of aqueous suspensions of lidocaine and dicyandiamide on clays. 30 mmol (7.02 g) of lidocaine (LIC), 30 mmol (2.52 g) of dicyandiamide (DCD) and 30 mmol (1.09 g) of hydrochloric acid are introduced into a 100 ml flask at room temperature. The resulting solution is heated at 80 ° C for 10 h. After that time, a solution of 2.52 g of sodium bicarbonate (30 mmol) in 50 ml of water is added to this solution little by little and with constant stirring, maintaining stirring after completion of the addition for 2 hours at 80 ° C. 2 g of montmorillonite are added to the aqueous solution consisting of 1LIC / 1DCD / 1HCl / 1NaHCO3 and the mixture is stirred for 2 h at 80 ° C. After this time, the water is completely evaporated by heating to 80 ° C. This solid can be used directly or it can be pressed and ground in order to obtain particles of suitable dimensions, preferably between 100 and 500 µm, for use.
    [0111] Example 6
    [0112] Impregnation of mixtures of lidocaine and dicyandiamide on straws. 30 mmol (7.02 g) of lidocaine (LIC), 30 mmol (2.52 g) of dicyandiamide (DCD) and 30 mmol (1.09 g) of hydrochloric acid are introduced into a 100 ml flask. The resulting mixture is heated at 80 ° C for 10 hours. After this time, a solution of 2.52 g of sodium bicarbonate (30 mmol), or the appropriate amount of a bicarbonate of another metal, in 50 ml of water is added little by little to the previous solution and stirred for 2 hours at 80 ° C. On the final aqueous mixture consisting of 1LIC / 1DCD / 1HCl / 1NaHCO3, 1 g of rice straw is added and it is stirred for 2 hours at 80 ° C. The rice straw must be previously milled to obtain particles of dimensions less than 1 mm. After this time, the water is completely evaporated by heating to 80 ° C. The resulting solid can be used directly or can be suitably modified, by pressing, grinding and sieving, for use.
    [0114] Example 7
    [0115] Impregnation of mixtures with flame retardant properties on clay and straw. In a 100 ml flask, 30 mmol (7.02 g) of lidocaine (LIC), 30 mmol (2.52 g) of dicyandiamide (DCD) and 30 mmol (1.09 g) of hydrochloric acid are introduced at room temperature. The resulting mixture is heated at 80 ° C for 10 hours. After this time, a solution of 2.52 g of sodium bicarbonate (30 mmol) in 50 ml of water is added little by little, containing the self-assembly mixture and stirred for 2 hours at 80 ° C.
    [0117] 2 g of montmorillonite and 1 g of rice straw are added to the final aqueous mixture of 1LIC / 1DCD / 1HCl / 1NaHCO3 obtained and stirred for 2 hours at 80 ° C. Mix Montmorillonite and straw may have previously been modified, forming an adobe that is ground into millimeter-sized particles.
    [0119] Example 8
    [0120] Formation of self-assembling mixtures of lidocaine and urea, supported on montmorillonite. The procedure is as in Example 5, replacing the amount of dicyandiamide with 30 mmol (1.80 g) of urea. As an alternative to urea, any other of the compound compounds indicated in Figure 2 can be used, which act as hydrogen donors in the amount equivalent to 30 mmol. The resulting solid can be used directly or can be suitably modified for use.
    [0122] Example 9
    [0123] Impregnation of self-assembly mixtures of lidocaine and urea on straw. The procedure is as in Example 6, replacing the amount of dicyandiamide with 30 mmol (1.80 g) of urea. As an alternative to urea, any other of the compound compounds indicated in Figure 2 can be used, which act as hydrogen donors in the amount equivalent to 30 mmol. The resulting solid can be used directly or can be suitably modified for use.
    [0125] Example 10
    [0126] Impregnation of mixtures of lidocaine and urea or other donor on adobe. The procedure is as indicated in Example 8, replacing the amount of dicyandiamide with 30 mmol (1.80 g) of urea. As an alternative to urea, any other of the compound compounds indicated in Figure 2 can be used, which act as hydrogen donors in the amount equivalent to 30 mmol. It is convenient that the adobe be formed by mixing clay and straw and that this adobe is ground into particles of suitable dimensions prior to impregnation with the mixture of lidocaine and urea. The resulting solid can be used directly or can be suitably modified for use.
    [0128] Example 11
    [0129] Formation of self-assembly mixtures of betaine and urea with subsequent impregnation on montmorillonite In a 100 ml flask, 15 mmol (2.30 g) of betaine hydrochloride (BETCl) and 30 mmol are introduced at room temperature (1.80 g) of urea. The resulting mixture is heated at 80 ° C for 5 hours. After that time, a solution of 2.52 g of sodium bicarbonate (30 mmol) in 40 ml of water is added little by little into the flask containing the self-assembly mixture and stirred for 1 hour at 80 ° C. This aqueous solution can be used as a flame retardant agent and the water can be evaporated to obtain the pure mixture.
    [0131] Alternatively, to this aqueous solution containing 1BETCl / 2Urea / 2NaHCO3, add 2 g of montmorillonite and stir for 1 hour at 80 ° C. Montmorillonite can be ground and sieved prior to impregnation or the particulate of the material can be modified after impregnation.
    [0133] Example 12
    [0134] Impregnation of self-assembly mixtures based on betaine and urea on straw. Proceed as in Example 11 to obtain the flame retardant mixture in the indicated amounts. On the final aqueous mixture 1BETCl / 2Urea / 2NaHCO3 1 g of rice straw previously milled is added to a particle size of around 1 millimeter. Shrub seeds can be added to this straw impregnated with the retardant in a percentage of 20% by weight to favor the recovery of the flora in the area damaged by fire.
    [0136] Example 13
    [0137] Impregnation of nanoparticles of montmorillonite adobe and rice straw with a self-assembling mixture of betaine and urea neutralized with sodium bicarbonate. The procedure is as indicated in Example 11 to prepare a self-assembling mixture of betaine chloride and urea in a 1: 2 molar ratio, together with sodium bicarbonate as a pH regulating buffer. To this mixture in solution, 3 g of adobe previously ground and sieved to sizes of 100-200 mesh are added, proceeding to stir for 2 hours at 80 ° C and, after that time, evaporate the water. The adobe is obtained by mixing 2 g of montmorillonite with 1 g of ground rice straw in 50 ml of water, stirring for 2 h at 80 ° C and, after that time, evaporating the water. The adobe thus obtained is ground and sieved to the desired particle size.
    [0139] Example 14
    [0140] Formation of self-assembling mixtures of betaine and dicyandiamide neutralized with sodium bicarbonate and their subsequent use to impregnate montmoriNonite. 20 mmol (3.07 g) of betaine hydrochloride (BETCl) and 20 mmol (1.68 g) of dicyandiamide (DCD) are introduced into a 100 ml flask at room temperature. The resulting mixture is heated at 80 ° C for 5 hours in order to allow the spontaneous self-assembly of both molecules. After this time, a solution of 1.68 g of sodium bicarbonate (20 mmol) in 40 ml of water is slowly added, the solution being stirred for 1 hour at 80 ° C. 2 g of montmorillonite are added to the final aqueous mixture 1BETCl / 1DCD / 1NaHCO3 and the mixture is stirred for 1 hour at 80 ° C. The water is evaporated at 80 ° C in order to obtain the impregnated montmorillonite. This material can be pressed, ground and sieved for proper handling.
    [0142] Example 15
    [0143] Impregnation of self-assembly mixture of betaine and dicyandiamide on rice straw. The self-assembly mixture of betaine hydrochloride and dicyandiamide, neutralized with sodium bicarbonate, is prepared as indicated in Example 14. Similarly, the impregnation is carried out following the procedure indicated in Example 14, substituting the clay for 1 g of rice straw in the form of shavings.
    [0145] Example 16
    [0146] Impregnation of the self-assembly mixture of betaine hydrochloride and dicyandiamide in adobe. The procedure is as indicated in Example 14, replacing the 2 g of montmorillonite with 3 g of ground adobe and sieved between a particle size of 100 to 200 mesh. This sticky material can then be pressed and ground for proper handling.
    [0148] Example 17
    [0149] Formation of self-assembly mixtures between betaine hydrochloride and dicyandiamide neutralized by ammonium bicarbonate. 20 mmol (3.07 g) of betaine hydrochloride (BETCl) and 20 mmol (1.68 g) of dicyandiamide (DCD) are introduced into a 100 ml flask at room temperature. The resulting mixture is heated at 80 ° C for 3 hours. After this time, a solution of 1.58 g of ammonium bicarbonate (20 mmol) in 30 ml of water is added little by little to the self-assembly mixture and the solution is stirred for 1 hour at 80 ° C. Mix Final aqueous 1BETCl / 1DCD / 1 (NH4) HCO3 obtained, with fire retardant effect, can be used directly, can be diluted in fresh or sea water at a concentration of 10% or less. Alternatively, this self-assembling mixture can be used to impregnate solid supports such as those indicated in previous examples.
    [0151] Example 18
    [0152] Impregnation of the self-assembling mixture of betaine hydrochloride and neutralized dicyandiamide with ammonium bicarbonate in clays. The procedure is as in Example 17 and the aqueous solution of betaine hydrochloride and dicyandiamide neutralized with ammonium bicarbonate is used to impregnate 2 g of montmorillonite. The process is carried out by mechanical stirring for 1 h and slow evaporation of the water at 80 ° C. A similar procedure can be carried out to impregnate other types of natural clays, such as sepiolites, kaolin, halloysite and vermiculite, among others.
    [0154] Example 19
    [0155] Impregnation of the self-assembling mixture of betaine hydrochloride and neutralized dicyandiamide with ammonium bicarbonate in rice straw. The procedure is as in Example 18, replacing the montmorillonite with 1 g of rice straw. Alternatively, straws from other crops, such as tigernut straw or another type of agricultural waste suitably treated in the form of shavings, sawdust or other types of particles, can be used as a support for the retarder.
    [0157] Example 20
    [0158] Impregnation of the self-assembling mixture of betaine hydrochloride and neutralized dicyandiamide with ammonium bicarbonate in adobe. The procedure is as in Example 18, replacing the montmorillonite with 3 g of adobe in the form of particles. The adobe is prepared by any procedure such as that indicated in Example 7, mixing 2 g of montmorillonite or other micronized clay with 1 g of rice straw or of another crop and proceeding to mix it in aqueous suspension, drying it by evaporation of the water, to its grinding into particles and their sieving.
    [0160] Example 21
    [0161] Formation of self-assembly mixtures between glycine hydrochloride and dicyandiamide, neutralized by potassium bicarbonate. In a 100 ml flask, 20 mmol (2.23 g) of glycine hydrochloride (GLI) and 20 mmol (1.68 g) of dicyandiamide (DCD) are introduced at room temperature. The resulting mixture is heated at 80 ° C for 3 hours. After this time, another solution of 2 g of potassium bicarbonate (20 mmol) in 30 ml of water is slowly added to the solution formed and the mixture is stirred for 1 hour at 80 ° C. The final aqueous solution formed by 1GLI / 1DCD / 1HCl / 1KHCO3 can be concentrated by evaporation of the water at 80 ° C or it can be used diluted to a concentration between 5 and 20% by weight in water.
    [0163] Example 22
    [0164] Impregnation of the self-assembling mixture of glycine hydrochloride and dicyandiamide in montmorillonite or silicates. The procedure is as in Example 21, adding to the self-assembling mixture of glycine hydrochloride and dicyanamide 2 g of montmorillonite or another natural or synthetic clay or silicate. The suspension is stirred for 1 hour at 80 ° C. After this time, the water evaporates at 80 ° C, maintaining the mechanical agitation of the suspension, obtaining a sticky residue from the clay coated with the self-assembly mixture.
    [0166] Example 23
    [0167] Impregnation of the self-assembly mixture of glycine hydrochloride and dicyandiamide in straw of agricultural crops. The procedure is as in Example 22, replacing the montmorillonite with 1 g of rice straw or of another agricultural crop or with shavings or sawdust from biomass residues.
    [0169] Example 24
    [0170] Impregnation of the self-assembly mixture of glycine hydrochloride and dicyandiamide in adobe. The procedure is as in Example 22, substituting 3 g of adobe for the montmorillonite prepared as indicated in Example 7.
    [0172] Example 25
    [0173] Formation of self-assembly mixtures between lidocaine and glycerol. At room temperature, 20 mmol (4.69 g) of lidocaine (LIC), 20 mmol (1.46 ml) of glycerol (GLC, average molecular weight 10,000) and 30 mmol (0.73 g) of hydrochloric acid are placed in a 100 ml flask. . The resulting mixture is heated at 80 ° C for 6 hours. After this time, the solution is neutralized by slowly adding 2 g of potassium bicarbonate (20 mmol) in 40 ml of water. The solution is stirred for 2 hours at 80 ° C. The final aqueous mixture 1LIC / 1GLC / 1HCl / 1KHCO3 can be used directly, it can be diluted to a percentage between 5 and 20% by weight or it can be concentrated by evaporation of the water at 80 ° C under mechanical stirring.
    [0175] Example 26
    [0176] Impregnation of the self-assembling mixture of lidocaine and glycerol in montmorillonite or silicates. Proceed as indicated in Example 25. Once the neutralized aqueous solution of 1LIC / 1GLC / 1HCl / 1KHCO3 is obtained, 2 g of montmorillonite or other natural clay or natural or synthetic silicate are added to this solution and the suspension is mechanically stirred for 2 hours at 80 ° C. Subsequently, the water is completely evaporated by heating to 80 ° C under constant mechanical stirring.
    [0178] Example 27
    [0179] Impregnation of the self-assembly mixture of lidocaine and glycerol in rice straw. The procedure is as in Example 26, replacing the montmorillonite with 1 g of rice straw or another crop or sawdust or shavings from biomass and the suspension is stirred at 80 ° C under constant mechanical stirring until complete evaporation of the water.
    [0181] Example 28
    [0182] Impregnation of the self-assembly mixture of lidocaine and glycerol in adobe. Proceed as in Example 26, replacing the montmorillonite with 3 g of adobe. The adobe can be prepared as indicated in Example 7.
    [0184] Example 29
    [0185] Obtaining colored solids with fire retardant properties by impregnating adobe with a self-assembling mixture of lycodaine and glycerol. The procedure is as in Example 28, but 0.016 g of commercial PureMarin® dye is added to the 1LIC / 1GLC / 1HCl / 1KHCO3 self-assembly solution and the solution is homogenized for 3 hours at 80 ° C before adding the 3 g of adobe.
    [0187] Example 30
    [0188] Colored sample with fire retardant effect obtained by impregnation of adobe with the self-assembly mixture between (phenylmethyl) triphenylphosphonium chloride and glycerol. 20 mmol (7.77 g) of (phenylmethyl) triphenylphosphonium chloride (BfCl) and 20 mmol (1.46 ml) of glycerol (GLC) are introduced into a 100 ml flask. The resulting mixture is heated at 80 ° C for 5 hours. After this time, a solution of 2 g of potassium bicarbonate (20 mmol) in 60 ml of water is slowly added and the solution is stirred for 1 hour at 80 ° C. On the final aqueous solution 1BfCl / 1GLC / 1KHCO3 3 g of adobe prepared as indicated in example 7 and 0.016 g of commercial PureMarin® dye are added and the suspension is stirred mechanically at 80 ° C for sufficient time to achieve complete evaporation of water.
    [0190] Example 31
    [0191] Colored sample with fire retardant effect obtained by impregnating adobe with the self-assembly mixture between glycine and glycerol. In a 100 ml flask, 20 mmol (1.5 g) of glycine (Gli) and 20 mmol (1.46 ml) of glycerol (GLC, average molecular weight 10,000) are introduced at room temperature. The resulting mixture is heated at 80 ° C for 5 hours. After this time, a solution of 2 g of potassium bicarbonate (20 mmol) in 60 ml of water is slowly added and the solution is stirred for 1 hour at 80 ° C. On the aqueous mixture constituted by 1Gli / 1GLC / 1KHCO3 3 g of adobe prepared as indicated in example 7 and 0.016 g of commercial PureMarin® dye are added. The suspension is mechanically stirred at 80 ° C until the water has completely evaporated, obtaining a sticky residue with flame retardant properties.
    [0193] Example 32
    [0194] Formation of self-assembly mixtures between ammonium formate and urea. 60 mmol (3.78 g) of ammonium formate (FDA) and 60 mmol (3.60 g) of urea are introduced into a 50 ml flask at room temperature. The resulting mixture is heated at 80 ° C for 12 h. After this time, the viscous 1FDA / 1Urea mixture is obtained, which on cooling becomes solid at room temperature. This mixture with a fire retardant effect can be diluted in water between 5 and 50% by weight or it can be used to impregnate solid substrates such as clays, natural or synthetic silicates, biomass residues, among others. In addition, a colorant can be added that allows the position of the mixture to be geographically located.
    [0195] Example 33
    [0196] Formation of self-assembly mixtures between ammonium formate and dicyandiamide. In a 50 ml flask, 60 mmol (3.78 g) of ammonium formate (FDA) and 60 mmol (5.04 g) of dicyandiamide (DCD) are introduced at room temperature. The resulting mixture is heated at 80 ° C for 12 h. After this time and cooling to room temperature, the solid mixture 1FDA / 1DCD is obtained. This mixture with a fire retardant effect can be diluted for use in water between 5 and 50% by weight or it can be used to impregnate solid supports such as those indicated in example 32.
    [0198] Example 34
    [0199] Formation of self-assembling mixtures between ammonium formate and glycine. In a 50 ml flask, 60 mmol (3.78 g) of ammonium formate (FDA) and 60 mmol (4.50 g) of glycine (GLI) are introduced at room temperature. The resulting mixture is heated at 80 ° C for 12 h. After this time, the viscous mixture 1FDA / 1GLI is obtained, which on cooling becomes solid at room temperature. This mixture with a fire retardant effect can be diluted for use in water between 5 and 50% by weight or it can be used to impregnate solid substrates such as those indicated in example 32.
    [0201] Example 35
    [0202] Formation of self-assembly mixtures between glycine and urea. 30 mmol (2.25 g) of glycine (GLI), 60 mmol (3.60 g) of urea and 30 mmol (1.09 g) of hydrochloric acid (37%) are introduced into a 50 ml flask. The resulting mixture is heated at 80 ° C for 6 h. After this time, the viscous mixture 1LIC / 2urea / 1HCl is obtained which, by eliminating the water under reduced pressure of 40 mm Hg, becomes solid again at room temperature (25 ° C). This mixture with a fire retardant effect can be diluted in water in a percentage between 5 and 50% by weight or it can serve to impregnate solid substrates such as any of those indicated in previous examples.
    [0204] Example 36
    [0205] Formation of self-assembly mixtures between glycine and dicyandiamide. 30 mmol (2.25 g) of glycine (GLI), 30 mmol (2.52 g) of dicyandiamide (DCD) and 60 mmol (2.18 g) of hydrochloric acid are placed in a 50 ml flask at room temperature. The resulting mixture is heated at 80 ° C for 7 hours. After that time, the viscous mixture 1LIC / 1DCD / 2HCI with an approximate pH between 1 and 3 is obtained. This mixture with a fire retardant effect can be diluted in water for use between 5 and 50% by weight or it can be used to impregnate solid substrates as indicated in example 32.
    权利要求:
    Claims (16)
    [1]
    1. Mixture with flame retardant capacity, free of pyrophosphates, characterized in that it comprises a mixture of non-polymeric organic components:
    to. at least one first compound of the mixture acts as a hydrogen bond donor; Y
    b. at least one second compound in the mixture acts as a hydrogen bond acceptor.
    [2]
    2. Mixture according to claim 1, wherein the molar ratio of the hydrogen bond donor compound and the hydrogen bond acceptor compound ranges from 1: 5 to 5: 1.
    [3]
    3. Mixture according to claim 1 or 2, wherein the hydrogen bonding compound is selected from a group consisting of dicyandiamide, urea, malonic acid, glycerol, guanidine, 1,1-dimethylurea, oxalic acid, ethylene glycol and derivatives, trifluoroacetamide, 1-methylurea, imidazole, 1,3-dimethylurea, lactic acid, resorcinol, 2-imidazoline, arginine, benzoic acid, benzyl alcohol, propyleneurea, thiourea, 4-hydroxybenzoic acid, succinic acid, acetamide, benzamide, acid levulinilic acid, gallic acid, ammonium formate, tartaric acid, malonic acid and derivatives, adipic acid, oleic acid, linoleic acid, stearic acid, trimyristin, citric acid and isocytric acid, as well as any of their combinations.
    [4]
    4. Mixture according to any one of the preceding claims, wherein the hydrogen bond acceptor compound is selected from a group consisting of lidocaine or a derivative of the ester type, proline, histidine, nicotinic acid, (phenylmethyl) triphenylphosphonium chloride. , alanine, methyl triphenylphosphonium bromide, glycine, ethanolamine, betaine, ammonium formate and ammonium oxalate, as well as any of their combinations
    [5]
    5. Mixture according to any one of the preceding claims, wherein said mixture additionally comprises water, in a percentage comprised between 50% and 95% of the total weight of the mixture.
    [6]
    6. Mixture according to any one of the preceding claims, wherein said mixture additionally comprises at least one inorganic or organic compound with acid or base chemical properties, in a percentage equal to or less than 30% by weight relative to the total weight of the mixture.
    [7]
    7. Mixture according to claim 6, wherein the compound with acid chemical properties is selected from a group consisting of hydrochloric acid, sulfuric acid, sulfonic acid, carbonic acid and carboxylic acid, as well as any of their combinations.
    [8]
    8. Mixture according to claim 6, wherein the compound with basic chemical properties is selected from a group consisting of a carbonate or bicarbonate of an alkali metal, ammonia, amine or metal hydroxides.
    [9]
    9. Mixture according to any one of the preceding claims, wherein said mixture additionally comprises at least one solid compound on which the mixture is impregnated.
    [10]
    10. Mixture according to claim 9, wherein said solid compound is selected from a group consisting of clays and at least one agricultural waste, as well as any of their combinations.
    [11]
    11. Mixture according to claim 9 or 10, wherein the mixture is impregnating the solid compound in a percentage comprised between 5 and 40% by weight.
    [12]
    12. Mixture according to any one of the preceding claims, wherein said mixture additionally comprises at least one coloring substance or a pigment.
    [13]
    13. Method of preparing a mixture according to any one of claims 1 to 12, characterized in that it comprises intimately mixing at least one first compound of the mixture that acts as a hydrogen bond donor and at least one second compound of the mixture acts as a hydrogen bond acceptor.
    [14]
    14. Method according to claim 13, characterized in that it additionally comprises the impregnation of at least one solid.
    [15]
    15. Use of a mixture according to any one of claims 1 to 12, as a flame retardant agent in extinguishing forest fires.
    [16]
    16. Use according to claim 15, where the mixture is used in aqueous solution or supported in at least one fireproof or flammable solid.
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    同族专利:
    公开号 | 公开日
    WO2021136859A1|2021-07-08|
    ES2837489B2|2022-02-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN101716408A|2008-10-09|2010-06-02|王悦之|Forest fire-fighting agent|
    KR20120051449A|2010-11-12|2012-05-22|아해|Flame retardant paint composition having high reflectivity for sun light|
    EP2742978A1|2011-08-16|2014-06-18|Xi'an J&R Fire Fighting Equipment Co., Ltd.|Fire-extinguishing composition comprising organic acid compound|
    CN103274626A|2013-05-27|2013-09-04|许盛英|Red mud flame retardant foaming agent|
    CN104368114A|2013-08-14|2015-02-25|左桂兰|Instant efficient fire extinguishing agent|
    EP3384966A1|2015-12-01|2018-10-10|Xi'an Westpeace Fire Technology Co., Ltd|Fire-extinguishing composition|
    CN103463790A|2013-08-19|2013-12-25|扬州江亚消防药剂有限公司|Seawater-resistant insoluble aqueous film-forming foam extinguishing agent and preparation method thereof|
    CN103788407B|2014-01-16|2016-03-16|上海工程技术大学|The preparation method of the pillared phyllosilicate flame retardant of a kind of porous|
    CN105013125A|2015-06-10|2015-11-04|厦门安港消防科技有限公司|Foam extinguishing agent|
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