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    • 专利摘要:
    Flame retardant composition, based on ammonium polyphosphate with a polymer content between 50-70% by weight and P2 O5 (phosphoric anhydride) between 30- 40% by weight, so that the composition incorporates: as a corrosion inhibitor urea in a percentage between 3-10% by weight in aqueous solution between 40% - 60% by weight, in combination with sodium polyphosphates with a length chain between 2 and 6, supplemented with Zn derivatives (except phosphates) and with triazoles; as inorganic thickener modified sepiolite in a percentage between 1-4% by weight; as organic thickener granulated xanthan gum in a percentage between 0.5-1.5% by weight; as pigmentary inorganic dyes derived from the iron oxide family in a percentage between 0.5-2.0% by weight, and as fugitive dyes derived from the cochineal red family in a percentage between 0.2-0, 8% by weight. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2812305A1
    申请号:ES202031325
    申请日:2020-12-31
    公开日:2021-03-16
    发明作者:Vallespín José Alberto Enfedaque
    申请人:Barricade Brs S L；
    IPC主号:
    专利说明:

    [0004] OBJECT OF THE INVENTION
    [0006] The following invention refers to a flame retardant composition, having as its object its use by aerial means and with a long-term effect, that is, once the water necessary for its application has evaporated.
    [0008] Furthermore, since sodium polyphosphate is used as a humectant, it is possible to substantially reduce the content of urea as an anticorrosive additive, avoiding corrosion problems in the storage tanks of the composition made of aluminum alloys. Likewise, by incorporating the ferric oxide composition, in a percentage equal to or less than 1% by weight of the composition, in the presence of a fugitive dye based on carminic acid, it has a high covering power on the vegetation. On the other hand, the addition of a micronized modified sepiolite as a suspension stabilizer presents clear advantages over other conventional clays such as powdered sepiolite and attapulgite. Likewise, the incorporation into the composition of xanthan gum, previously granulated to a size greater than 100 microns, given its excellent results in terms of dispersion, facilitates the preparation of the concentrate, and also avoids the formation of dust in the manufacturing process.
    [0010] Ultimately, the composition provides novel anti-corrosion additives, a food-grade fugitive pigment with zero environmental impact, as a whole, complying with all the requirements for long-term retardants.
    [0012] BACKGROUND OF THE INVENTION
    [0014] Forest fires have always been modelers of the terrestrial vegetation cover. Since the beginning of the industrial era and with the progressive abandonment of forests, the amount of fuel in them has increased considerably. If we also unite factors such as the consequences of climate change and the notable increase in urban-forest interface areas, the accident rate of forest fires is a major concern.
    [0015] Among the many tools used in the fight against forest fires, there are retardant additives, which can be applied directly or indirectly on the fire front, either by aerial or terrestrial means that intervene in the extinction of the fire. forest.
    [0017] It is possible to distinguish between long-term and short-term retardants. Basically the former have their extinguishing or flame retardant effect, although the water that has been needed for their application evaporates, through a carbonization effect of the cellulosic material of the plant instead of the emission of flammable gases and consequent inflammation and flame. The latter are only effective as long as there is water present and therefore their extinguishing capacity is based on the endothermic effect of water evaporation. These long-term retardant compositions must be diluted with water before application. This dilution is typically 1 part concentrate to 4 parts water by volume.
    [0019] The present novelty focuses on long-term retardants, from now on retardants, used in particular in the fight by aerial means against forest fires. The use of retardants began in the 1950s with the help of the TVA ( Tennessee Valley Authority) with the application of liquid fertilizers, mainly ammonium polyphosphate, with the addition of clays as suspension fertilizers.
    [0021] Later, the problem of corrosion in aircraft was raised and the formulations were optimized with anticorrosive additives, basically to prevent corrosion in the aluminum alloy AL2024T3 used in fixed-wing aircraft, such as sodium ferrocyanide (US3960735A), as phosphates. zinc (WO 2008/155187) or as iron pyrophosphates (US6802994). The fireproofing of the wood is carried out in an industrial way in the current state of the art, applying the P / N synergy (phosphorus / nitrogen) for an optimal result (US3887511A). The use of nitrogenous agents, such as urea, complementary to phosphates and polyphosphates, is already mentioned in the literature for an application in forest fires as anticorrosive for aluminum alloys at high doses higher than 10% and that must be incorporated together with the corresponding triazole to the ammonium polyphosphate manufacturing process. This represents a difficulty since the production of the latter is carried out in large fertilizer plants and a modification for this process would not be economically viable (US3809653).
    [0022] The pigments used to make the discharge visible were also optimized and subsequently, photosensitive pigments of the Rhodamine (EP 0693304 A1) or azoic type began to be formulated, so that in the short term the color mark of the discharge would disappear on the forest surface. . At the same time, other organic thickening agents were incorporated to improve both the stability of the concentrated liquid and to increase the viscosity of the application mixture, improving adherence to the vegetable (US 4822524). To achieve a good wetting of the pigments and a good wettability of the vegetable substrates, surfactants widely used in the paint sector are used, of an anionic organic type such as lauryl sulfonates or benzene sulfonates and their sodium salts, or inorganic such as polyphosphates. alkaline.
    [0024] Long-term retardants have technical specifications of minimum requirements to be met by public administrations and / or users of aerial means in the fight against forest fires. The reference specifications to contrast the novelties described below are:
    [0026] • Efficacy: test methodology of the INIA (Instituto Nacional de Investigaciones Agrarias, ES), which rates the extinguishing efficacy in values from 0 to 4, with 0 being the best. Long-term rated retarders are required to have a value of 0-1 at the manufacturer's recommended dilution ratio with water.
    [0027] • Corrosion: CEREN (Center d'Essais et de Reserche, FR) test methodology to evaluate corrosion in steel, aluminum and brass specimens, which requires the following for its acceptance and use in extinguishing media, including aerial media Corrosion values: For concentrated product 1,450 x 10-6 cm / h and for diluted product 0.580 x 10-6 cm / h.
    [0028] • Adhesion / wettability: this characteristic indicates how the retarder adheres by providing enough retarding agent to prevent inflammation. The minimum level of deposited product expressed in P205 must be 5%.
    [0029] • Stability: this characteristic evaluates the effectiveness of organic and inorganic thickening agents in terms of keeping pigments in suspension for the longest period of time possible. It is measured according to the syneresis presented by the suspension, that is, the separation into two phases the product presents in a state of rest. A syneresis of less than 5% is considered correct.
    [0030] • Visibility: the coloration and its visibility are evaluated after 24 hours of application on or shrub material and at a distance of 15 m, with a dose of 2 l / m on one o
    [0031] surface of 1 m. The application must be visible to the human eye, qualifying as very good, good, acceptable and not acceptable.
    [0033] DETAILED DESCRIPTION OF THE INVENTION
    [0035] In the present specification a flame retardant composition is described, based on ammonium polyphosphate with a content of between 80-90% by weight, preferably 85% by weight, so that the composition incorporates:
    [0036] - as a corrosion inhibitor: a) urea, in a percentage between 3-10% by weight and in the form of an aqueous solution; b) sodium polyphosphates with a chain length between 2 and 6; c) Zn derivatives (except phosphates) and, d) triazole derivatives;
    [0037] - as an inorganic thickener paligorskite-sepiolite modified in a percentage between 1.5-2.5% by weight;
    [0038] - as organic thickener granulated xanthan gum in a percentage between 0.4-0.8% by weight;
    [0039] - as inorganic pigment dyes derived from the family of iron oxides in a percentage between 0.5-1.5% by weight, and;
    [0040] - as fugitive dyes derived from the family of natural cochineal reds, CAS 1260-17-9, of formula C 22 H 20 0 13 , in a percentage between 0.2-0.6% by weight.
    [0042] Ultimately, the composition provides novel anti-corrosion additives, a food-grade fugitive pigment with zero environmental impact, as a whole, complying with all the requirements for long-term retardants.
    [0044] In a practical embodiment of the invention the addition of ammonium polyphosphate is between 80-90% by weight, preferably 85% by total weight of the composition. In a particular embodiment of the present invention, the ammonium polyphosphate consists of 50-70% by weight of polymer and between 30-50% by weight of phosphoric anhydride (P 2 0 5 ), with respect to the total polyphosphate ammonium in the composition. In a preferred embodiment, the ammonium polyphosphate has a P 2 0 5 comprised between 36% and 38% by weight and a polymerization index greater than 60%. Thus, ammonium polyphosphate has a polymer content of between 50-70% by total weight of the composition and a content of phosphoric anhydride (P 2 0 5 ) of between 34-40% by total weight of the composition. In particular modes of the invention, the polymer content is between 50-70%, between 55-70%, or between 60-70%. by total weight of the composition, and the content of phosphoric anhydride (P205) is between 20-40%, between 25-40%, between 30-40% or between 34-40% by total weight of the composition. In particular modes of the invention, the polymer content is 50%, 55%, 60%, 65%, or 70% by total weight of the composition, and the content of phosphoric anhydride (P205) is 20 %, 25%, 30%, 35% or 40% by total weight of the composition.
    [0046] Corrosion inhibitors: The addition of urea is 4.5% by weight, and it is previously dissolved 40-60% in water, preferably 50%, before incorporating it into the mixture. The sodium polyphosphate is Na2H2P207 (disodium pyrophosphate), CAS 7722-88-5, with an addition of 0.5% to 2% by weight, and more preferably 1% by weight. The Zn derivative as a complementary corrosion inhibitor is Zn sulfate with a percentage between 0.4% and 0.6% by weight, and more preferably 0.5% by weight. Among the group of triazoles as a complementary corrosion inhibitor is benzotriazole added in a percentage between 0.4% and 0.6% by weight, and more preferably 0.5% by weight.
    [0048] Thickeners: As inorganic thickener, paligorskite-sepiolite is incorporated in a percentage between 1.5% and 2.5% by weight, and more preferably, 2% by weight. As organic thickener, 80 mesh granulated xanthan gum is incorporated in a percentage between 0.4% and 0.8% by weight, and more preferably 0.6% by weight. The granulated xanthan gum is micro-encapsulated in a rotary drum with 1% PVA (polyvinyl alcohol) and 1% water.
    [0050] Colorants: As inorganic pigment colorants, the composition incorporates ferric oxide in a percentage between 0.5% and 1.5% by weight, and more preferably, 1% by weight. As fugitive colorants it incorporates cochineal red in a percentage of 0.2% to 0.6% by weight, and more preferably, 0.4% by weight.
    [0052] We can emphasize that corrosion on aircraft has always been a matter of concern, particularly because of the aluminum alloy that makes up the fuselage and other important parts of the aircraft. Ammonium polyphosphate is highly corrosive and needs to incorporate anti-corrosion additives for its use. There have been many corrosion inhibitors used in the past, but due to toxicity, environmental impact, etc. their employment has been restricted. Therefore, in the last decade, all research has focused on finding environmentally friendly anticorrosive additives, having found, for example, that certain iron and / or zinc compounds are effective anticorrosive. It is in this sense to incorporate a combination of environmentally friendly additives and formulated in such a way that its content is optimized with respect to previous knowledge.
    [0054] In any development on retardants, it is always necessary to comply with minimum values of their benefits, to be qualified as such, and therefore all the novelties incorporated into the formulation must meet these minimum requirements, not only for the purpose of the invention, as they are novelty in corrosion and coloration, but in all its other characteristics
    [0056] Thus, surprisingly, and on the basis of optimizing the effectiveness of the retardant with the incorporation of nitrogenous agents such as urea in the manufacturing process of the concentrate (see formulations in table 1), it has been found that its combination with anticorrosive pigments salts, oxides and / or Zinc hydroxides claimed in ES2310963B1, with the exception of Zinc phosphates (ES 200701696), derivatives of triazoles typically used to prevent corrosion in copper alloys, using sodium polyphosphate as a novel humectant in this application, it allows to substantially reduce the content of Urea necessary for acceptable corrosion and below the limits expressed in the state of the art (US3809653) in aluminum alloys, according to the CEREN methodology.
    [0058] In addition, not only has the extinguishing capacity in terms of dilution necessary to pass the efficacy test defined by the INIA (National Institute of Agrarian Research) been maintained, but it has also presented a satisfactory covering power on the vegetation (visibility) with a dosage of ferric oxide equal to or less than 1%, in the presence of a novel fugitive dye in this application and of food quality with zero environmental impact. The coloration of the retardant is important for the identification of discharges by aerial means. Ferric oxide red is commonly used as an opaque pigment, but recently there has been progress towards fugitive pigmentation, that is, not permanent. For this, synthetic organic pigments are formulated in conjunction with an opaque pigment in reduced content, such as ferric oxide, resulting in these photosensitive pigments of a questionable environmental impact in relation to their PBT. Therefore, finding a new fugitive natural pigment with zero environmental impact is also a novel objective.
    [0059] In the same way, it has been verified that the clays modified and processed according to document ES201130128A, based on highly micronized paligorskite-sepiolite or attapulgite, and initially designed to be compatible with organic polymeric matrices, and with a particle size of 95% less than 45 microns, remarkably improve on conventional clays to achieve the desired parameters regarding the stability of the concentrate in this application, as well as with regard to the ability to adhere to vertical surfaces. Likewise, it has been formulated with xanthan gum, previously granulated to a size greater than 100 microns, due to its excellent results in terms of its dispersion in the preparation of the concentrate, avoiding the formation of dust in the manufacturing process and avoiding the formation of lumps. in the process of dispersing it in the concentrated retardant.
    [0061] The dispersions were prepared using a Cowles type stirrer with a 5 cm diameter plate and a tangential speed of 15 m / s in a 1000 cm3 beaker. The order of incorporation of the additives is that expressed in the order of the formulation, resulting in the duration of the operation of 20 minutes per operation. The temperature was kept between 20-25 ° C. The tests with diluted product have always been carried out with a dilution ratio of 1: 4 parts of concentrate: parts of water by volume.
    [0063] Additionally, the invention relates to the following aspects:
    [0065] 1. A flame retardant composition based on ammonium polyphosphate, characterized in that the composition comprises:
    [0066] a) a corrosion inhibitor consisting of:
    [0067] • an aqueous solution of urea, in a percentage between 3-10% by total weight of the composition;
    [0068] • sodium polyphosphates with a chain length between 2 and 6;
    [0069] • Zn derivatives (except phosphates); Y
    [0070] • triazole derivatives.
    [0071] b) an inorganic thickener in a percentage between 1.5-2.5% by total weight of the composition, where the inorganic thickener is micronized modified paligorskite-sepiolite or micronized modified attapulgite;
    [0072] c) an organic thickener in a percentage between 0.4-0.8% by total weight of the composition;
    [0073] d) inorganic pigment dyes in a percentage between 0.5-1.5% by total weight of the composition, where the inorganic pigment dyes are derived from the family of iron oxides; Y
    [0074] e) fugitive dyes in a percentage between 0.2-0.6% by total weight of the composition, where the fugitive dyes are derived from the cochineal red family.
    [0076] The flame retardant composition according to aspect 1, characterized in that the ammonium polyphosphate consists of 50-70% by weight of polymer and between 30-50% by weight of phosphoric anhydride (P205), with respect to the total ammonium polyphosphate in composition.
    [0078] The flame retardant composition according to any one of aspects 1 or 2, characterized in that the ammonium polyphosphate contains P205 in a percentage comprised between 36% and 38% by weight and a polymerization index greater than 60%.
    [0080] The flame retardant composition according to any one of aspects 1 to 3, characterized in that the ammonium polyphosphate is between 80-90% by total weight of the composition, preferably 85% by total weight of the composition.
    [0082] The flame retardant composition according to any one of aspects 1 to 4, characterized in that the aqueous urea solution is 4.5% by total weight of the composition.
    [0084] The flame retardant composition according to any one of aspects 1 to 5, characterized in that the aqueous solution of urea is urea dissolved in water at 40-60%, preferably urea dissolved in water at 50%.
    [0086] The flame retardant composition according to any one of aspects 1 to 6, characterized in that the sodium polyphosphate is Na2H2P207 (disodium pyrophosphate), CAS 7722-88-5, with a percentage of 0.5% to 2% in total weight of the composition, and more preferably 1% by total weight of the composition.
    [0088] The flame retardant composition according to any one of aspects 1 to 7, characterized in that the Zn derivative is Zn sulfate with a percentage between 0.4% and 0.6% by total weight of the composition, and more preferably 0.5% by total weight of the composition.
    [0090] The flame retardant composition according to any one of aspects 1 to 8, characterized in that among the group of triazoles is benzotriazole added in a percentage between 0.4% and 0.6% in total weight of the composition, and more preferably 0.5% by total weight of the composition.
    [0092] The flame retardant composition according to any one of aspects 1 to 9, characterized in that the inorganic thickener is micronized modified paligorskite-sepiolite in a percentage between 1.5% and 2.5% by total weight of the composition, preferably the 2% by total weight of the composition.
    [0094] The flame retardant composition according to any one of aspects 1 to 10, characterized in that the organic thickener is xanthan gum in a percentage between 0.4% and 0.8% by total weight of the composition, preferably 0.6 % by total weight of the composition.
    [0096] The flame retardant composition according to aspect 11, characterized in that the xanthan gum is xanthan gum granulated to 80 mesh.
    [0098] The flame retardant composition according to aspect 12, characterized in that the granulated xanthan gum is micro-encapsulated in a rotary drum with 1% PVA (polyvinyl alcohol) and 1% water.
    [0100] The flame retardant composition according to any one of aspects 1 to 13, characterized in that the pigmentary inorganic colorant comprises ferric oxide in a percentage between 0.5% and 1.5% by total weight of the composition, and more preferably, 1% by total weight of the composition.
    [0102] The flame retardant composition according to any one of aspects 1 to 14, characterized in that the fugitive dye incorporates carmine red CAS 1260-17-9, in a percentage of 0.2% to 0.6% by weight in total weight of the composition, and more preferably 0.4% by weight by total weight of the composition.
    [0103] 16. A flame retardant composition based on ammonium polyphosphate, characterized in that the composition comprises an inorganic thickener in a percentage between 1.5-2.5% by total weight of the composition, where the inorganic thickener is micronized modified paligorskitasepiolite or attapulgite modified micronized.
    [0105] 17. The flame retardant composition according to aspect 16, characterized in that the composition also comprises pigment inorganic colorants in a percentage between 0.5-1.5% by total weight of the composition, where the pigment inorganic colorants are derived from iron oxide family; preferably ferric oxide in a percentage between 0.5% and 1.5% by total weight of the composition, and more preferably, 1% by total weight of the composition.
    [0107] 18. The flame retardant composition according to aspect 17, characterized in that the composition further comprises a corrosion inhibitor comprising urea.
    [0109] 19. The flame retardant composition according to any one of aspects 16 to 18, characterized in that the ammonium polyphosphate consists of 50-70% by weight of polymer and between 30-50% by weight of phosphorous oxide (P205) , with respect to the total ammonium polyphosphate in the composition.
    [0111] 20. The flame retardant composition according to any one of aspects 16 to 19, characterized in that the ammonium polyphosphate contains P205 in a percentage comprised between 36% and 38% by weight and a polymerization index greater than 60%.
    [0113] 21. The flame retardant composition according to any one of aspects 16 to 20, characterized in that the ammonium polyphosphate is between 80-90% by total weight of the composition, preferably 85% by total weight of the composition.
    [0115] All the terms and embodiments described in any section of this document are equally applicable to any aspect of the invention.
    [0117] EXAMPLES
    [0119] The following invention is described by means of the following examples, which are to be construed as merely illustrative and not limiting of the scope of the invention.
    [0120] Example 1.- Formulations of the invention
    [0122] A table 1 with different formulations is attached with this report in order to assess those that really meet the desired objective, so that a series of examples are analyzed below:
    [0124] Table 1: Formulations of the invention
    [0126]
    [0129] ammonium polyphosphate additive 1;
    [0130] additive 2 water;
    [0131] additive 3 urea;
    [0132] additive 4 sepiolite powder;
    [0133] additive 5 micronized modified sepiolite;
    [0134] additive 6 attapulgite powder;
    [0135] Additive 7 granulated xanthan gum;
    [0136] 8 additive sodium pyrophosphate powder;
    [0137] pigmented ferric oxide additive 9;
    [0138] additive 10 carmine red powder;
    [0139] - 11 benzotriazole additive;
    [0140] - additive 12 Zn sulfate.
    [0142] Base formulation (0)
    [0143] Formulation (0) (table 1), considered as the basis for the novel development of the invention, which contains ammonium polyphosphate as its main element and includes known additives, such as zinc sulfate, benzotriazole, xanthan gum, pigmentary ferric oxide, sepiolite in powder and water, provides results at the threshold or below the minimum requirements demanded in terms of effectiveness, corrosion, adhesion and stability, although the novel incorporation of the fugitive pigment of natural food-grade cochineal red represents an environmental advantage compared to other photosensitive pigments used in this application and complying with what is required in terms of required visibility. Likewise, formulation (0) is prepared using a xanthan gum with a particle size greater than 100 microns and previously granulated. The incorporation of the additive in this form means a better dispersion in the manufacturing process, avoiding the formation of lumps and significantly reducing manufacturing times.
    [0145] Formulations (1), (2) and (3)
    [0146] Formulations (1), (2) and (3) (table 1) all incorporate 1% sodium pyrophosphate versus 0% of formulation (0) and three types of clays are compared: sepiolite powder formulation (1 ), micronized modified sepiolite formulation (2) and formulation attapulgite (3) .A substantial improvement in terms of corrosion is observed in all of them, reaching in the case of micronized modified sepiolite of formulation (2) to enter the limits of the acceptability according to CEREN, a correct adhesion / wetting capacity and improved by 50% compared to the previous one, as well as a correct stability but at the threshold of acceptability. This example illustrates how: a) the incorporation of a surfactant, sodium pyrophosphate, to improve wetting, has had a favorable impact on reducing corrosion and notably improving stability and: b) the clay with which the specification is reached is sepiolite modified micronized object of the invention referred to in formulation (2) and that, in comparison with the sepiolite powder of formulation (1) and attapulgite of formulation (2), usually used and in the same percentage (2%), it is obtained a significant reduction in the corrosion rate (40%) reaching values lower than those required by CEREN. Thus, it also meets the minimum efficacy parameters required according to INIA at a dilution ratio with water of 1: 4 by volume. Likewise, the wetting and adhesion values on vertical surfaces improve in 30%. Likewise, the stability also improves by 70%.
    [0148] Formulations (4), (5) v (6)
    [0149] The formulations (4), (5) and (6) intend to study the impact in terms of corrosion, efficacy, stability and coloration that can occur when reducing the pigmentary ferric oxide content from 1% to 0.6%, which which is especially relevant in the case of retardants with fugitive coloration, the origin of sepiolite varying in the formulations as in formulations (1), (2), v (3). The results indicate that the optimal formulation continues to be the one containing the modified sepiolite, meeting all the INIA requirements, stability and coloration except for CEREN corrosion.
    [0151] Formulations (7), (8) v (9)
    [0152] Formulations (7), (8) and (9) incorporate water and urea into the formulation, returning to the initial dose of 1% ferric oxide. The differences between them remain the three types of clays, powdered sepiolite formulation (7), micronized modified sepiolite formulation (8) and attapulgite formulation (9). Again, in the formulation containing the modified sepiolite of formulation (8), compared to formulation (2), an improvement of 23% in terms of corrosion is observed, resulting very favorably within the requirements of CEREN. Regarding the efficacy according to INIA, it presents a 50% improvement in terms of weight loss compared to formulation (2) and it places formulation (8) with a maximum efficacy classification. The values in stability and adhesion / wetting remain within specification. This example makes it clear that the incorporation of urea in aqueous solution notably improves corrosion and retardant efficiency.
    [0154] Formulations (10), (11) v (12)
    [0155] Formulations (10), (11) v (12) intend to study again the reduction of pigmentary ferric oxide from 1% to 0.6% in successful formulations (7), (8) v (9), which include urea, in order to see if this reduction does not interfere with compliance with the minimum requirements for corrosion and the other parameters. Indeed, as can be seen from the results tables, formulation (11), which is the one containing the micronized modified sepiolite, is the one that meets all the technical requirements for corrosion, efficacy, stability and coloration. Therefore, ferric oxide can be reduced to 0.6% in these formulations.
    [0157] Example 2.- Corrosion results in Aluminum
    [0158] Table 2: Corrosion results of the product by total immersion
    [0160]
    [0163] Annex to example 2: Determination of corrosion by total immersion in Aluminum
    [0165] The metal specimen necessary to carry out the test is an Aluminum 2024-T3 alloy.
    [0167] The rectangular metal specimens have the following dimensions: 2.5 x 10.2 x 0.3 cm. They should have a 0.5 cm diameter hole centered 1.3 cm from one end.
    [0169] Preparation of the specimens. It is necessary to gently clean all the faces of the specimens to remove traces of grease, oxidized deposits or impurities with a 2.5 x 7.5 cm scouring pad (medium grain) always in the lamination direction. Each piece of scourer used must be used for only one type of alloy. First, the test tubes must be immersed in the specific cleaning solution according to the table in a plastic beaker. The specimens must not touch each other.
    [0170]
    [0173] After the time of immersion in the cleaning solution, they are removed and rubbed with a scouring pad. Clean plates are rinsed with distilled water and the surface is dried. The sheets are dried suspended in an oven at 50 ° C. Do not use the same stove that will be used for the immersion tests. The vapors generated can modify the corrosion phenomena. The sheets must be handled with tweezers and gloves. When they are dry, they are removed from the stove and allowed to warm up for approximately 15 minutes. They are weighed on a precision balance (0.1 mg) before immersion in the product to be tested.
    [0175] Corrosion is studied in total or partial immersion in the product to be tested. For a total immersion the volume of liquid introduced must be 800 ml. For a partial immersion 400 ml is sufficient. A fiberglass reinforced strip is glued across the open canister from side to side through the opening of the bottle and halfway down each side. A nylon thread is prepared to tie to the hole of the test tube and to be able to leave it in suspension. The cylinder is immersed in the test solution in each bottle. It is tied with an adhesive tape to one side of the boat so that it is suspended in the desired position. The test tubes for total immersion tests are placed so that they are completely covered by the solution, but without touching the bottom of the bottle. Specimens for partial immersion tests are positioned so that the bottom 5 cm of the specimen is immersed in the retarder. A small pencil mark on the edge of the cylinder indicates the proper level of immersion. These cans are covered. Each vial must be properly labeled with the name of the product, the batch number of the test product, the identification of the test tube immersed in the product, and the date of immersion. The vials are placed in the incubators at the appropriate temperature (21 ° C or 49 ° C), and allowed to stand undisturbed for the 90-day exposure period.
    [0177] End of trial. After the end of the test exposure, the vials are removed from the incubators. An inspection of the jars and contents is carried out and notes are taken of any broken flasks, evaporated test solution or test tubes that are destroyed or parts are missing. The test tubes are removed from the flasks. Each cylinder is rinsed with a vigorous stream of cold tap water to remove loose residual test solution. The specimens are allowed to air dry while still suspended from the fishing line. When the test tubes are dry (usually overnight), the fishing line is removed. Once dry, corrosion products are removed from the specimens by scraping with the flat edge of a stainless steel spatula. In some cases, the inhibitor film must be gently chipped to clean the test tube. Once the product remains and the corrosion products have been removed, it is necessary to clean the specimens in the chemical solutions. Each batch of test tubes (no more than six) is cleaned together with a control tube. The aluminum, steel and brass cylinders are immersed in the cleaning solution, resting against the sides of the container in a plastic beaker of about 600 mL, in such a way that the cylinders should not touch each other. After immersion as specified in the table, clean with a new scourer. The clean specimens are rinsed with distilled water and dried with a lint-free absorbent paper and suspended in the oven as in the initial cleaning. If persistent residue remains, the specimens can be cleaned a second time, using the control tube to determine the weight lost during cleaning. After drying, the specimens are cooled and weighed.
    [0179] Control specimens. Control tubes reserved for this purpose are not exposed to any of the test solutions. They are cleaned and rethought prior to use along with the set of exposed specimens, and then weighed again to determine the specimen weight loss.
    [0181] Corrosion rate calculations. The corrosion rate is calculated for each specimen using the initial and final weights, surface area, alloy density, and exposure time in the formula.
    [0185] Where:
    [0186] - Weighti = initial weight of the specimen (mg)
    [0187] - Pesf = final weight of the specimen (mg)
    [0188] - Pesoc, i = initial weight of the control specimen (mg)
    [0189] - Pesoc, f = initial weight of the specimen (mg)
    [0190] - Area = exposed surface of the specimen (in2)
    [0191] - Time = exposure time (h)
    [0192] - Density = density of the alloy (g / cm3)
    [0193] 2.77 g / cm3 for 2024-T3 Aluminum
    [0194] 7.86 g / cm3 for 4130 steel
    [0195] 8.53 g / cm3 for brass
    [0197] Three replicates will be made for each trial. Manufacturers may request that additional replicas be made. The results of all tests (except those that are rejected by visual inspection of any test failure) with the same alloy, temperature and immersion conditions will be averaged to determine the final corrosion rate.
    [0199] Example 3.- Adhesion and stability results
    [0201] Table 3: Adhesion results on vertical surfaces and concentrate stability (syneresis). Dilution ratio 1: 4 by volume (25% by weight). Concentration of P205 in concentrate 30%.
    [0206] Formulas 2, 5, 8, 11 obtain the best results in dilute adherence and concentrate stability.
    [0207] Annex I to example 3: Methodology to evaluate the adhesion capacity on vertical plant surfaces of a long-term retardant (Document proposed to the CTN 23 SC 5 GT Retardantes de UNE).
    [0209] Object: To evaluate the adhesion capacity on a vegetable support of a retardant mixture under the conditions of application.
    [0211] Procedure: To do this, define a pine wood support conditioned at 40 ° C for 4 h. Said support with dimensions of 10 cm x 15 cm x 3 mm thickness (commercially available as 3mm thick plywood) consists of three 1-0.5 / 1-2 / 1-0.5 pine wood sheets mm thick per layer and glued together. For the purpose of the test, the impregnation of the outer layers is considered for the effect of adherence and effectiveness. A mark is drawn on this support 10 cm from the lower edge. The weight of the support (P0) is taken and stored in a desiccator at room temperature (20-25 ° C). On the other hand, the retardant mixture is prepared, according to the dilution instructions recommended by the manufacturer, in a 600 cm3 beaker with a mixture volume of 500 cm3. The mixture with water is stirred with a magnetic rod or with a non-intense mechanical stirrer (approx. 200 rpm) for 5 min. at room temperature (20-25 ° C).
    [0213] Immediately after stirring, the support is submerged vertically up to the 10 cm mark for 5 seconds, immediately withdrawing it and allowing it to drain vertically for another 10 seconds. The wet impregnated support (P1) is weighed. The vertical adhesion (VA) is calculated as the weight deposited in gr / cm2.
    [0214] AV = (P1-P0) / 100
    [0215] As a blank, the same test is carried out with distilled water, PA0 of the support and PA1 after immersion.
    [0216] AAV = (PA1-PA0) / 100
    [0218] Interpretation of the result:
    [0219] 1- Fireproofing criteria. It is known that a concentration of P (as P205) higher than 5% will imply the non-flammability of the cellulosic material. By calculating the weight of retardant deposited and its concentration in P205, this concentration can be obtained on the wood support. On the other hand, 100% of the outer sheet (1mm) is considered impregnable for calculation purposes.
    [0220] P205 concentration (%) = AV x 0.20 x Rd x C
    [0221] Being:
    [0222] Rd:% concentrate in dilution mixture by weight.
    [0223] C:% of P205 in the concentrated retardant according to the manufacturer's declaration.
    [0224] 2- Wetting criteria. It will be understood that the retarder improves adhesion vertically than water if the weight retained in the case of the retarder is at least 50% higher.
    [0226] Retention ratio compared to water (RR in%)
    [0227] RR = (AV - AAV) x 100 / AAV
    [0229] Annex II to example 3: Stability, determination of syneresis at 30 days.
    [0231] After manual stirring, the product is poured and a cylindrical cylinder is made up to 100 cc. It is left to rest at a temperature between 20-25 ° C for 30 days. The decanted ml (clear liquid on the surface) are measured and related to the 100 ml of the test tube, resulting in the value directly as% of the total.
    [0233] Example 4.- Efficacy results
    [0235] Table 4: Efficacy tests on thermobalance
    [0240] Annex to example 4: fire performance test.
    [0242] The test is carried out on a combustion table with gravimetric monitoring. Saying The experimental device is made up of a fuel support tray, made up of two borosilicate plates 1.5 cm thick, 70 cm wide and 120 cm long, resting on aluminum profiles. The set rests on a scale with a sensitivity of 1 g that allows a continuous record, throughout the test, of the variation in the weight of the fuel on the table, as a result of its combustion.
    [0244] The forest fuel used is made up of needles from the litter of a Pinus pinea (stone pine) forest. In the laboratory, decomposing needles, twigs and various existing residues are removed, in order to keep only the needles intact. The choice of this fuel is determined by its homogeneity, its easy availability and the ease of handling to obtain the desired special arrangement, as well as its energy and fire behavior adaptation to the general characteristics of the test. The needles are conditioned in a chamber (Temperature = 23 ° C and Relative Humidity = 50%) until reaching a moisture content of around 9-10%. The humidity determination is carried out by drying in an oven (100 ° C), until constant weight, of three samples taken from the fuel immediately before carrying out the test. The amount of o
    [0245] The fuel used in each test is 700 g / m of dry matter, homogeneously arranged along the burning table. The one corresponding to the first 80 cm of the table "untreated area" is arranged directly on the table of the experimental device and the one corresponding to the last 40 cm "treated area" is arranged in a separate tray on which the solution is applied with the product to be tested, or the water, in the case of the control tests. This application is carried out with an extinguishing backpack, the main characteristics of which are:
    [0246] • Capacity: 18 l
    [0247] or
    [0248] • Residual volume: 200 cm
    [0249] • Tank dimensions: 49 cm x 65 cm
    [0250] • Double-stroke manual NOZZLE, with suction filter and double-effect nozzle: jet-spray.
    [0251] • Scope:
    [0252] • Jet> 8m
    [0253] • Spraying> 3 m
    [0254] or
    [0255] • Flow: 120 cm (complete round trip)
    [0256] • Dimensions of the lance: 1070 - 670 mm
    [0257] Concentration and dose: A concentration of 1: 4 in volume (recommended or by the applicant companies) is considered, applying the solution, in fresh water, at a rate of 1 l / m. However, the applicant company may require testing at other concentrations.
    [0259] Once the application is made, two types of test conditions or treatments are carried out:
    [0260] • The treated fuel is left to rest for 15 minutes, in the laboratory, at room temperature, and then it is kept in an oven at 42 ± 2 ° C for 30 minutes.
    [0261] • The treated fuel is left to rest for 15 minutes, in the laboratory, at room temperature, and then it is kept in an oven at 42 ± 2 ° C for 90 minutes.
    [0263] Development of the test: Once the time defined for each of the treatments has elapsed, the untreated fuel and the treated fuel are placed with the solution of the product to be tested, in their corresponding zone of
    [0264] For each of the conditions, at least two repetitions are performed. During the course of each of the tests, photographs are taken that allow different aspects of it to be visualized.
    [0265] As has been pointed out, the experimental device designed to carry out the described efficiency tests allows a continuous recording of the loss of weight of the fuel throughout the combustion, both in the untreated fuel zone and in the zone in which treatment has been carried out. The recorded data allow the weight variation curve to be traced over the duration of the test, in which the successive phases of combustion are differentiated:
    [0266] 1. Establishment of the stationary combustion regime.
    [0267] 2. Stationary combustion regime established in the untreated fuel zone, which is represented by a straight line.
    [0268] 3. Combustion in the area of the treated fuel represented by the consequent decrease in the slope of the line, by virtue of the effectiveness of the product.
    [0270] For each product object of the test, the weight-time curves, means of the repetitions carried out for each of the treatments are presented in the reports. In the same graph, the curve corresponding to the "control" tests is presented, in which the fuel treatment has been carried out only with water, under identical conditions in terms of doses and treatments. Comparison of the slope of the curves allows to visualize the effectiveness of the product versus that of water and the difference between the types of treatment.
    [0272] On the other hand, and according to the percentage of weight consumed with respect to that initially arranged, in the "treated area", the classification presented in Table 1 has been proposed. Obviously, for the same test conditions, a greater weight of waste translates into greater product efficiency.
    [0276] Retardant efficacy rating
    [0278] Consequently, for each of the test conditions, the efficacy of the product is estimated through the comparison of the mean curve of variation of the weight with the time, and that obtained in control tests in which the corresponding treatment has been carried out only with water. Likewise, for each test condition, the resulting classification and that corresponding to the control tests are presented, according to the proposed scale. In the preparation of this test, the results of visual observations of the coloration of the product are recorded. ( National Institute for Food and Agricultural Research, INIA).
    权利要求:
    Claims (13)
    [1]
    1. Flame retardant composition, based on ammonium polyphosphate with a polymer content between 50-70% by weight and phosphoric anhydride between 34-40% by weight, characterized in that the composition incorporates:
    - as a corrosion inhibitor: a) urea, in a percentage between 3-10% by weight and in the form of an aqueous solution; b) sodium polyphosphates with a chain length between 2 and 6; c) Zn derivatives (except phosphates) and, d) triazole derivatives;
    - as inorganic thickener micronized modified paligorskite-sepiolite in a percentage between 1.5-2.5% by weight;
    - as organic thickener granulated xanthan gum in a percentage between 0.4-0.8% by weight;
    - as inorganic pigment dyes derived from the family of iron oxides in a percentage between 0.5-1.5% by weight, and;
    - as fugitive dyes derived from the cochineal red family in a percentage between 0.2-0.6% by weight.
    [2]
    2. Flame retardant composition , according to claim 1, characterized in that the addition of ammonium polyphosphate is between 80-90% by weight, preferably 85% by weight.
    [3]
    3. Flame retardant composition, according to claim 1, characterized in that the ammonium polyphosphate has a P205 comprised between 36% and 38% by weight and a polymerization index greater than 60%.
    [4]
    4. Flame retardant composition , according to claim 1, characterized in that the addition of urea is 4.5% by weight.
    [5]
    5. Flame retardant composition, according to claim 1, characterized in that the urea is previously dissolved 40-60% in water, preferably 50%, before incorporating it into the mixture.
    [6]
    6. Flame retardant composition, according to claim 1, characterized in that the sodium polyphosphate is Na2H2P207 (disodium pyrophosphate), CAS 7722-88-5, with an addition of 0.5% to 2% by weight, and more preferably, 1% by weight.
    [7]
    7. Flame retardant composition, according to claim 1, characterized in that the Zn derivative as a complementary corrosion inhibitor is Zn sulfate with a percentage between 0.4% and 0.6% by weight, and more preferably, 0.5% by weight.
    [8]
    8. Flame retardant composition, according to claim 1, characterized in that among the group of triazoles as a complementary corrosion inhibitor is benzotriazole added in a percentage between 0.4% and 0.6% by weight, and more preferably , 0.5% by weight.
    [9]
    Flame retardant composition, according to claim 1, characterized in that as inorganic thickener, micronized modified paligorskite-sepiolite is incorporated in a percentage between 1.5% and 2.5% by weight, and more preferably, 2% by weight. .
    [10]
    Flame retardant composition, according to claim 1, characterized in that as organic thickener xanthan gum granulated at 80 mesh is incorporated in a percentage between 0.4% and 0.8% by weight, and more preferably, 0.6% in weigh.
    [11]
    11. Flame retardant composition, according to claim 11, characterized in that the granulated xanthan gum is micro-encapsulated in a rotating drum with 1% PVA (polyvinyl alcohol) and 1% water.
    [12]
    12. Flame retardant composition, according to claim 1, characterized in that as pigmentary inorganic colorants it incorporates ferric oxide in a percentage between 0.5% and 1.5%, and more preferably, 1%.
    [13]
    13. Flame retardant composition, according to claim 1, characterized in that as fugitive colorants it incorporates carmine red CAS 1260-17-9, in a percentage of 0.2% to 0.6% by weight, and more preferably, 0, 4% by weight.
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    同族专利:
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    ES2812305B2|2021-05-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2002044305A2|2000-11-28|2002-06-06|Astaris Llc|Fire retardant compositions with reduced aluminum corrosivity|
    WO2003057317A1|2001-12-26|2003-07-17|Astaris Llc|Ammonium polyphosphate solutions containing multi-functional phosphonate corrosion inhibitors|
    WO2014121398A1|2013-02-06|2014-08-14|X'aan Innovations Inc.|Ammonium polyphosphate based fire-retardant compositions|
    WO2015189810A1|2014-06-13|2015-12-17|Csir|Liquid flame retardant composition|
    EP3546029A1|2018-03-26|2019-10-02|Kidde Technologies, Inc.|Colorant for solid fire suppression agent|
    WO2020163788A1|2019-02-08|2020-08-13|Perimeter Solutions Lp|Liquid concentrate fire retardant compositions containing mixtures of ammonium phosphates|
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