EP2923739A1 - Aqueous compositions for extinguishing fire - Google Patents

Abstract

Suggested are aqueous preparations containing (a) polymer condensates obtainable by treating microorganisms with aqueous alkali bases and subsequently reacting the intermediates thus obtained with triglycerides and optionally polybasic carboxylic acids and / or polyols having 2 to 12 carbon atoms and 2 to 6 hydroxyl groups, and (b) at least one additive selected from the group formed by (b1) surfactants based on renewable raw materials, (b2) fluorine compounds, and (b3) Silicone compounds.

Description

FIELD OF THE INVENTION

The invention is in the field of fire-extinguishing agents and relates to aqueous preparations with high environmental compatibility, which are particularly suitable for firefighting.

STATE OF THE ART

Extinguishing agents have the task to extinguish burning substances. For fire fighting they can be used by fire brigades as well as in automatic fire extinguishing systems or hand fire extinguishers. Each extinguishing agent has a main extinguishing effect specific to the preparation as well as one or more secondary extinguishing effects. The wrong choice of extinguishing agent can have fatal consequences. Burning metals such as sodium or magnesium, for example, can not be quenched with water, but only with the removal of oxygen, for example by carbon dioxide. Other chemicals can also react with the components of the extinguishing agent, causing toxic and corrosive vapors or explosions.

The most important additives for extinguishing water include the wetting agents, which serve to lower the surface tension; the preparations are then also referred to as mains water. The task of the wetting agent is to improve the penetration of the fire-fighting water into the fire or in some cases also to make possible. Thus, it is also possible to reach deep or hidden embers, as they occur, for example, in the humus soil in the forest or in chip bunkers. However, even in less complicated cases, the use of surfactants has proven to be advantageous because the water penetrates specifically into the burning material and not mainly flows due to the surface tension. In this way, the water requirement can be reduced and subsequently also reduce extinguishing water damage.

In principle, all surface-active substances are suitable as wetting agents, of which those which reduce the surface tension very clearly are of course preferred. For the application in the net water, they themselves need no foam properties. However, if extinguishing foams are to be produced, foamy surfactants are advantageous. In this case, a concentrate is foamed, for example, by compressed air, the foam settles on the fire and suffocates it.

Numerous examples of extinguishing water preparations are known from the prior art, which contain a wide variety of surfactants, with which the surface tension can be lowered and optionally also a foam can be produced. For this purpose have In addition to conventional surfactants such as the alkyl ether sulfates especially fluorine and silicone compounds proved to be particularly efficient. The problem, however, is that due to the large quantities of extinguishing water, which are usually used in firefighting, regularly comes to contamination of the groundwater, in which the water seeps with the surfactants. In particular, surfactants which are derivatized by fluorine groups are suspected of accumulating in the soil and can then possibly even detected in drinking water. The ecological concern of these substances is contrary to their high performance. The industry tries to compensate for this by developing new fluorosurfactants for this purpose, as for example in the international patent applications WO2008 003 444 A1 . WO2008 003 445 A1 . WO2008 003 446 A1 and WO2008 003 447 A1 (Merck) is expressed. The fabrics may have better ecological compatibility, but price and availability make their use only of limited attractiveness.

The object of the present invention has therefore been to provide new formulations, especially aqueous concentrates, which overcome the problems described above. Specifically sought were surfactant preparations, on the one hand ensure a strong reduction of the surface tension, but on the other hand, compared to products of the prior art have a significantly improved environmental compatibility in terms of biodegradability and water hazard class. Of course, the task also included that highly effective fire-extinguishing agents can be produced with the concentrates.

DESCRIPTION OF THE INVENTION

1. (a) Polymerkondensate, dadurch erhältlich, das man Mikroorganismen mit wässrigen Alkalibasen behandelt und die so erhaltenen Zwischenprodukte anschließend mit Triglyceriden sowie gegebenenfalls mehrwertigen Carbonsäuren und/oder Polyolen mit 2 bis 12 Kohlenstoffatomen und 2 bis 6 Hydroxylgruppen umsetzt, und
2. (b) mindestens einen Zusatzstoff ausgewählt aus der Gruppe die gebildet wird von
   • (b1) Tensiden auf Basis von nachwachsenden Rohstoffen und
   • (b2) Fluorverbindungen, und
   • (b3) Silikonverbindungen.

The invention relates to aqueous preparations containing

1. (a) polymer condensates obtainable by treating microorganisms with aqueous alkali bases and subsequently reacting the intermediates thus obtained with triglycerides and optionally polybasic carboxylic acids and / or polyols having 2 to 12 carbon atoms and 2 to 6 hydroxyl groups, and
2. (b) at least one additive selected from the group formed by
   • (b1) surfactants based on renewable raw materials and
   • (b2) fluorine compounds, and
   • (b3) Silicone compounds.

Surprisingly, it has been found that by partial replacement of conventional surfactants by polymer condensates, as they can be obtained in the context of the invention, fire extinguishing agents - both network water or extinguishing foams - are obtained, which reduces the surface tension of the water synergistically and thereby have a significantly improved biodegradability, so that they partially - namely depending on the amount of polymer condensates - can be classified in the water hazard class 1. Such preparations are new and highly interesting, since they can also be used in such places for firefighting, where contamination of the soil and groundwater must be absolutely prevented.

POLYMER CONDENSATES

The polymer condensates which constitute group (a) of the present invention are known in the art. Extensive and provided with many examples they are in the European patent EP0671973B1 (OLSCHEWSKI ), which is fully incorporated by reference into the disclosure for the preparation of the materials.

The polymer condensates of the present invention are obtained on the basis of available in large quantities microorganisms such as digested sludge, activated sludge or yeast, especially baker's yeast or brewer's yeast. Unlike in the prior art otherwise described, these microorganisms do not serve as biocatalysts that do not participate in the actual chemical reaction, but themselves represent the starting material. For the fact is that, for example, the yeast preferred in the context of the invention nothing more than complex mixtures of essentially proteins and polysaccharides which have numerous functional groups for subsequent reaction steps.

The molecular weight of these starting materials is in the range above 2 mDa, which means that there is no solubility in water or oil. In the first reaction step, therefore, an alkaline digestion, i. the microorganisms are mixed with aqueous highly concentrated alkali metal hydroxide, for example a 30% strength by weight sodium hydroxide solution, so that a pH in the range of at least 10, preferably from 12 to 14, and below the boiling point, preferably at 70 to 80 ° C stirred for about 2 to 5 hours. In this digestion, the high-molecular chains are broken and obtained fragments, which have compared to the starting materials only about one-tenth of the molecular weight. Preferably, the fragments have a molecular weight in the range of about 20 to about 250 kDa, more preferably about 50 to about 220 kDa, and most preferably about 150 to about 200 kDa. It is understood that individual fragments may also have significantly higher or lower molecular weights. Therefore, the above data are understood in particular as averages based on about 90 wt .-% of the total fraction.

In the second process step, which can be carried out separately or as a "one-pot process", substances are added to the digested microorganisms which can react with the functional groups in the molecules. These are triglycerides, polybasic carboxylic acids and / or polyols having 2 to 12 carbon atoms and 2 to 6 hydroxyl groups. The reactions take place base-catalyzed; i.e. As a rule, no further addition of alkali metal hydroxide is required since the solution is still sufficiently basic.

The addition of triglycerides leads to saponification under alkaline conditions. Fatty acids are released which can enter into ester or amide bonds with hydroxyl or amino groups in the protein or poly sugars. What remains are mainly partial glycerides, which are themselves surface-active and have excellent emulsifier properties. Fatty acids that do not react are present as soaps after the reaction and are therefore also surface-active.

Suitable triglycerides generally have 6 to 22 and preferably 12 to 18 carbon atoms and may be saturated or have 1, 2 or 3 double bonds. Typical examples are vegetable oils such as palm oil, palm kernel oil, coconut oil, sunflower oil, soybean oil, olive oil, rapeseed oil, safflower oil, linseed oil or (see) animal raw materials such as fish oil or beef tallow. The starting materials may have iodine numbers in the range of 1 to 120. Preferably, mixtures of saturated and unsaturated triglycerides are used, such as (hardened) palm oil and sunflower oil or (hardened) beef tallow and rapeseed oil or partially hydrogenated coconut oil.

The addition of polyvalent carboxylic acids can lead to the formation of bridged species via the acid functions. Suitable polybasic carboxylic acids are oxalic acid, adipic acid, malonic acid, maleic acid and in particular hydroxy acids such as citric and tartaric acids.

• Glycerin;
• Alkylenglykole, wie beispielsweise Ethylenglykol, Diethylenglykol, Propylenglykol, Butylenglykol, Hexylenglykol sowie Polyethylenglykole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton;
• technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;
• Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trimethylolbutan, Pentaerythrit und Dipentaerythrit;
• Niedrigalkylglucoside, insbesondere solche mit 1 bis 8 Kohlenstoffen im Alkylrest, wie beispielsweise Methyl- und Butylglucosid;
• Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Sorbit oder Mannit,
• Zucker mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Glucose oder Saccharose;
• Aminozucker, wie beispielsweise Glucamin;
• Dialkoholamine, wie Diethanolamin oder 2-Amino-1,3-propandiol.

The polyols are able to react with acid groups in the polymeric fragments or to scavenge excess released fatty acids. They may also contain other functional groups, in particular amino groups, or themselves be modified with nitrogen. Typical examples are

• glycerol;
• Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of 100 to 1,000 daltons;
• technical oligoglycerine blends having an inherent degree of condensation of from 1.5 to 10 such as technical grade diglycerin blends having a diglycerol content of from 40 to 50 weight percent;
• Methylol compounds, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
• Niedrigalkylglucoside, in particular those having 1 to 8 carbons in the alkyl radical, such as methyl and Butylglucosid;
• Sugar alcohols containing 5 to 12 carbon atoms, such as sorbitol or mannitol,
• Sugars having 5 to 12 carbon atoms, such as glucose or sucrose;
• Amino sugars such as glucamine;
• Dialcoholamines, such as diethanolamine or 2-amino-1,3-propanediol.

The molar ratio of the reactive groups in the sum of biomass and triglyceride on the one hand and polybasic carboxylic acids and polyols on the other hand is preferably 10: 1 to 1: 2 and especially about 3: 1 to about 1: 1. By selecting the derivatizing agents and their amount, the HLB value of the reaction products can be adjusted to a great extent so that more lipophilic preparations (HLB values 6 to 10) or hydrophilic mixtures (HLB values 11 to 18) are obtained as required , Regarding the selection rules is again on the disclosure in the aforementioned patent EP 0671973B1 directed.

The preferred polymer condensates are obtained on the basis of microorganisms, which are further reacted after alkaline digestion with triglycerides and citric acid become. Particularly preferred are those in which the microorganisms in turn represent yeasts, especially bakers yeast.

TENSIDES BASED ON RENEWABLE RAW MATERIALS

As component (b1) it is possible to contain anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants. Typical examples of anionic surfactants are soaps, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, alkyl ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, Sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat based vegetable products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, optionally partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products). , Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds such as dimethyl distearyl ammonium chloride, and ester quats, especially quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. Typical examples of particularly suitable milds, i. particularly skin-compatible surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefinsulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

Particularly preferred is the use of high-foaming anionic surfactants of the alkyl ether sulfates type, especially those having 12 to 18 carbon atoms and 1 to 6 carbon atoms. One typical example was the product Texapon.RTM ^® N should note (BASF Personal Care and Nutrition GmbH), which also carries the INCI name Sodium Laureth Sulfate-1.

Among the nonionic surfactants is the group of alkylpolyglycosides, especially alkylpolyglucosides with degrees of oligomerization in the range of about 1.5. These have a rather unusual for nonionic surfactants foaming power and are also classified in the water hazard class 1. These substances are for example available under the name glucopon ^® APG 100 from BASF Personal Care & Nutrition GmbH.

Among the amphoteric surfactants are as preferred representatives, the Betaine to mention specifically the cocamidopropyl that can be obtained, for example, under the name Dehyton ^® K from BASF Personal Care & Nutrition GmbH.

A specific embodiment of the present invention therefore relates to preparations which contain, in addition to component (a), surfactants of group (b1) which are alkyl ether sulfates, alkyl polyglycosides and / or betaines, the mixing ratio being about 10: 1 to 1: 1 5) can be-in each case based on the individual surfactants of group b1 or their sum.

FLUOR CONNECTIONS

Basically, all fluorine-containing halons are considered as group (b2), since these substances have a extinguishing effect via the so-called "homogeneous inhibition" - a chain termination reaction during combustion. However, the selection of these substances is limited to the fact that they must be approved and can be incorporated stably in an aqueous environment.

For this reason, the preferred fluorine compounds perfluorinated hydrocarbons, in particular having 6 to 18 carbon atoms, which optionally further solubility enhancing functional groups such as -CO, -COOH, -SO ₃ H or -SO ₄ H carry. Also suitable are fluorinated protein derivatives, such as protein hydrolysates.

das unter Bezeichnung Novec^® von 3M erhältlich ist. Es handelt sich um eine farblose, fast geruchlose Flüssigkeit, die chemisch gesehen ein perfluoriertes Ethyl-Isopropylketon) darstellt. Die Löschwirkung des in stationären Feuerlöschanlageneingesetzten Novec 1230 beruht, wie bei auch bei anderen Halonen, auf homogener Inhibition. Das Molekül besitzt keine elektrische Leitfähigkeit. Es hat mit einem Treibhauspotenzial (CO₂-Äquivalent) von 1 den geringsten Wert aller aktuell zugelassenen chemischen Löschmittel und zerfällt innerhalb weniger Tage unter Sonneneinstrahlung.
Ebenfalls geeignet sind beispielsweise die speziellen Fluorverbindungen, die in den eingangs genannten Merck-Schriften WO 2008 003 444 A1 , WO 2008 003 445 A1 , WO 2008 003 446 A1 und WO 2008 003 447 A1 beschrieben werden.Particularly preferred fluorosurfactants include 1,1,1,2,2,5,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone (FK 5-1-12)

which is available under the name Novec ^® 3M. It is a colorless, almost odorless liquid, which is chemically a perfluorinated ethyl isopropyl ketone). The extinguishing effect of the Novec 1230 used in stationary fire extinguishing systems is based on homogeneous inhibition, as with other halons. The molecule has no electrical conductivity. With a global warming potential (CO ₂ equivalent) of 1, it has the lowest value of all currently approved chemical extinguishing agents and decomposes into sunlight within a few days.
Also suitable are, for example, the special fluorine compounds described in the Merck publications mentioned above WO 2008 003 444 A1 . WO 2008 003 445 A1 . WO 2008 003 446 A1 and WO 2008 003 447 A1 to be discribed.

SILICON COMPOUNDS

Suitable silicone surfactants include modified silicone oils such as dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which are preferably liquid at room temperature. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates.

PREPARATIONS

• (a) etwa 10 bis etwa 40 Gew.-% Polymerkondensate,
• (b1) 0 bis etwa 30 Gew.-%, vorzugsweise etwa 1 bis etwa 20 Gew.-% und insbesondere etwa 5 bis etwa 20 Gew.-% Tenside auf Basis von nachwachsenden Rohstoffen,
• (b2) 0 bis etwa 30 Gew.-%, vorzugsweise etwa 1 bis etwa 20 Gew.-% und insbesondere etwa 5 bis etwa 20 Gew.-% Fluorverbindungen,
• (b3) 0 bis etwa 30 Gew.-%, vorzugsweise etwa 1 bis etwa 20 Gew.-% und insbesondere etwa 5 bis etwa 20 Gew.-% Silikonverbindungen,
• (c) 0 bis etwa 5 Gew.-%, vorzugsweise etwa 0,5 bis etwa 2 Gew.-% Frostschutzmittel, und
• (d) 0 bis etwa 2 Gew.-%, vorzugsweise 0,1 bis 1 Gew.-% Verdickungsmittel

mit den Maßgaben enthalten, dass die Komponenten der Gruppe (b) in Mengen von zusammen mindestens 1 Gew.-% zugegen sind und sich alle Mengenangaben mit Wasser und gegebenenfalls weiteren üblichen Zusatzstoffen zu 100 Gew.-% ergänzen.In a preferred embodiment of the invention, the preparations are characterized in that they

• (a) about 10 to about 40% by weight of polymer condensates,
• (b1) 0 to about 30% by weight, preferably about 1 to about 20% by weight and in particular about 5 to about 20% by weight of surfactants based on renewable raw materials,
• (b2) 0 to about 30% by weight, preferably about 1 to about 20% by weight and in particular about 5 to about 20% by weight of fluorine compounds,
• (b3) 0 to about 30% by weight, preferably about 1 to about 20% by weight and in particular about 5 to about 20% by weight of silicone compounds,
• (c) 0% to about 5%, preferably from about 0.5% to about 2%, by weight of antifreeze, and
• (d) 0 to about 2% by weight, preferably 0.1 to 1% by weight of thickener

containing the provisos that the components of group (b) are present in amounts of at least 1 wt .-% together and all quantities with water and optionally other customary additives to 100 wt .-% complement.

Particularly preferred are. Concentrates having a non-aqueous content of from about 40 to about 60 weight percent, and more preferably from about 45 to about 55 weight percent.

The concentrates are added to the extinguishing water or the extinguishing foam usually in such amounts that a surfactant content of about 0.1 to about 15 wt .-%, preferably about 0.5 to about 10 wt .-% and in particular about 1 to about 8 wt .-% sets.

ANTIFREEZE

Suitable antifreeze according to the invention are in the first place glycols such as ethylene and propylene glycol in question.

THICKENER

Suitable thickening agents are, for example, Aerosil types (hydrophilic silicic acids), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, and also higher molecular weight Polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (eg Carbopole® and Pemulen types from Goodrich, Synthalene® from Sigma, Keltrol grades from Kelco, sepiolite types from Seppic, salcare types from Allied Colloids), polyacrylamides, polymers, Polyvinyl alcohol and polyvinylpyrrolidone. As a particularly effective bentonites, such as Bentone ^® Gel VS-5PC (Rheox) have been found, which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate. Also suitable are surfactants, such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols, for example pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or alkyl oligoglucosides and also electrolytes, such as common salt and ammonium chloride.

OTHER ADDITIVES

Gelling agents. If a high adhesion and a higher viscosity of the extinguishing water is required, gelling agents can be added. These additives are usually based on superabsorbents and can be kept as powder or emulsion. Gelling agents are to achieve good results, for example, in so-called "DSD fires" (fires of stored packaging waste) and enable the creation of an airtight barrier layer in bulk solids, which is significantly more stable than a foam carpet, lasts longer and delivers significantly less water to the firing material. The water consumption is considerably lower in certain fire scenarios. If extinguishing gel is used, less water can be used for one bar setting. In the outdoor area without the risk of water damage, this is especially useful if the much cheaper water is not available in sufficient quantity or the type of development hinders its use in a sufficient amount. Extinguishing gel is attractive in almost all cases, where water can be transported only with difficulty and with high costs, because one must use for example helicopters. If the transport costs are significantly higher than the additional costs for the gel agent, it can be reasonable and reasonable to give the water a higher extinguishing effect in view of water hazard class 1.

Retardants are additives to extinguishing water, which are mainly used for firefighting vegetation fires with aircraft. For example, they should reduce evaporation, increase the boiling point and, through their color, make it easier to identify the places where extinguishing agents have already been applied. Many of these funds are based, at least in large part, on salts from the fertilizer industry. Some of these salts react with the surface of the organic material when exposed to heat, thereby reducing the flammability of the surface.

Salts are also common in portable fire extinguishers. They increase the boiling point of the water and thus the extinguishing power.

INDUSTRIAL APPLICABILITY

Another object of the invention relates to a method for combating fires, in which the preparations according to the invention are diluted with water and either directed in the form of a jet of water or as a water dust against the fire or foams and covers the fire with it. The water jet, the sprayed water or the water mist can be directed to the burning object from jet pipes, spray heads, sprinklers and similar devices.

Preferably, concentrates are used which have a non-aqueous content of about 40 to about 60 wt .-% and in particular about 45 to about 55 wt .-%. The concentrates are added to the extinguishing water or the extinguishing foam usually in such amounts that a surfactant content of about 0.1 to about 15 wt .-%, preferably about 0.5 to about 10 wt .-% and in particular about 1 to about 8 wt .-% sets.

In concentrations above 2 wt .-%, the concentrates are particularly suitable for the production of high foaming. Foaming numbers of more than 1000 are adjustable. At concentrations from about 6% by weight, it is also possible to produce medium and heavy foams which have foaming numbers of from 2 to 30 and in particular from 5 to 10. The production of these foams can be obtained by means of known components, especially those which mix in air after the liquid jet pump system.

For extinguishing liquid fires in containers of all kinds, the foam is expediently produced with pressure foam tubes, foam pumps or compressed air foam devices, then introduced into the liquid supply line, so that the foam can rise through the liquid to the burning surface. It has proved to be particularly advantageous if a branching of the product line takes place within the container in the sense that is possible for every 50 m ^2, a foam outlet opening is available. These openings are preferably close to the outer periphery of the container, since it has been shown that the foam thus produced is very resistant to erosion. A foam made with the concentrate of the invention stifles the fire very quickly. The subsequent foam blanket then closes gas-tight at the glowing or strongly heated wall surfaces. For the production of covering thin layers, it is sufficient if the foam is applied to relatively limited partial areas. Depending on the nature of the flammable liquid, this foam can be readily spread into extinguishable thin films which can not be delimited with the naked eye and which are capable of accelerating the extinguishment of the fire and of preventing reignition.

Depending on the choice of method of use and depending on the purpose of the use, the preparations according to the invention are suitable for fires of various kinds. For example, extinguishing waters which contain the preparations according to the invention as wetting agents are better, faster and more economical than products of the prior art fight. As a heavy foam fire extinguishing agents can also be used to combat conflagration, especially in environmentally sensitive areas.

In principle, embers of any kind can be extinguished by means of the fire-extinguishing agent according to the invention, unless the burning object gives rise to fire and explosion effects when it encounters water. Surprisingly, it has been found that the extinguishing agent according to the invention even in the form of high foaming even then could be used successfully if the fire itself burning oxygen carriers, react with water de chemicals and metals are involved. The amount of water present, when properly applied, did not give rise to explosions beyond the foam-filled space. The most effective as extinguishing decomposition products of the substances mentioned were kept in the immediate vicinity of the fire, so that fires of this type could be limited, the cooling effect of the source of fire to giving foam amount had a favorable effect.

Above all, however, fires of flammable liquids, especially fires of mineral oils in tanks, on the ground and on the water, moreover, under the same conditions, alcohol fires and those of butanol, isobutanol, amyl alcohol, etc. erasable. In this case, the concentrate used in the process according to the invention is used as a heavy foam. This foam can be passed in the stream or from elbows flowing on the fire surface; but it can also be introduced without much disturbing devices with the product lines under observation of certain procedural rules from the bottom in liquid container. As a result, in combating all liquid fires in tanks, the advantage is exploited that the application of the extinguishing agent provides directly to the fire zone, so that the fire itself does not affect the extinguishing agent, so that complicated and expensive piping devices are no longer required.

Compared to fires of gases that are under pressure, the extinguishing agent is also advantageously used as a heavy foam. It then appears cooling and anti-catalytic. Compared to electric fires, the use of the extinguishing agent is possible as a surface-active water mist, as a heavy foam and as a lightweight foam. In accordance with previous experience with extinguishing water dust, heavy foam and high-expansion foam, measures must be taken which result in the fact that the current of the electrical energy coming into contact with it does not cause any damage via the conductive extinguishing agent.

Another object of the invention relates to the use of polymer condensates which are obtainable by treating microorganisms with aqueous alkali bases and then reacting the resulting intermediates with triglycerides and optionally polybasic carboxylic acids and / or polyols having 2 to 12 carbon atoms and 2 to 6 hydroxyl groups , as a fire extinguishing agent, for example, the extinguishing water or the extinguishing foam are added.

EXAMPLES PREPARATION Preparation Example H1: Polymer condensate A

400 g of brewing yeast (30% strength by weight) were mixed with 150 g of 40% strength by weight aqueous sodium hydroxide solution and 40 g of PEG 300 and stirred for 30 minutes at a temperature of 80 ° C. Then, 50 g of coconut oil (iodine value <1) and 75 g of coconut oil (iodine number 10) were added and the mixture stirred for a further 3 hours at a temperature of 75 ° C. After cooling, the reaction products were obtained in the form of a brownish aqueous solution having a solids content of about 43% by weight and a pH of 10.5.

Preparation example H2: polymer condensate B

400 g of brewing yeast (30% strength by weight) were mixed with 150 g of 40% strength by weight aqueous sodium hydroxide solution and 30 g of PEG 400 and stirred for 30 minutes at a temperature of 80 ° C. Then, 70 g of hardened beef tallow (iodine value <1, acid number 4) and 80 g of palm oil (iodine value 50) were added and the batch was stirred for a further 4 hours at a temperature of 80 ° C. After cooling, the reaction products were obtained in the form of a brownish aqueous solution having a solids content of about 51% by weight and a pH of 10.0.

Preparation Example H3: Polymer condensate C

400 g of baker's yeast (25 wt .-% strength) were mixed with 120 g of 40 wt .-% aqueous sodium hydroxide solution and with 20 g of citric acid and 10 g of sorbitol and stirred for 30 minutes at a temperature of 80 ° C. Then a mixture of 100 g of milk fat and 20 g of hardened palm oil (iodine value <3) was added and the mixture was stirred for a further 3 hours at a temperature of 70 ° C. After cooling, the reaction products were obtained in the form of a brownish aqueous solution having a solids content of about 47% by weight and a pH of 9.5.

Preparation Example H4: Polymer condensate D

1000 g of activated sludge (25 wt .-%) were mixed with 300 g of 40 wt .-% aqueous sodium hydroxide solution and 15 g of citric acid, 15 g of maleic acid, 40 g of PEG 600 and 20 g of PEG 200 and for 1 hour at a temperature of 80 ° C stirred. Then a mixture of 150 g of sunflower oil (iodine value 130) and 100 g of erucareiches rapeseed oil (iodine number 100) is added and the mixture stirred for a further 3 hours at a temperature of 70 ° C. After cooling, the reaction products were obtained in the form of a brownish gray aqueous solution having a solids content of about 43% by weight and a pH of 9.5.

Preparation example H5: polymer condensate E

1000 g of activated sludge (35% strength by weight) are mixed with 500 g of 40% strength by weight aqueous sodium hydroxide solution and 10 g of butanol, 10 g of butanediol, 40 g of PEG 400, 10 g of PEG 1000 and 50 g of maleic acid and stirred for 1 hour at a temperature of 80 ° C. Then, 250 g of poultry waste fat was added and the batch was stirred for a further 3 hours at a temperature of 75 ° C. After cooling, the reaction products were obtained in the form of a brownish gray aqueous solution having a solids content of about 50% by weight and a pH of 10.5.

Production Example H6: Polymer Condensate F

400 g of digested sludge (90 wt .-% dry matter) were mixed with 600 g of water, 150 g of 40 wt .-% aqueous sodium hydroxide solution and 40 g of PEG 300 and stirred for 30 minutes at a temperature of 80 ° C. Then, 50 g of coconut oil (iodine value <1) and 75 g of coconut oil (iodine number 10) were added and the mixture stirred for a further 3 hours at a temperature of 75 ° C. After cooling, the reaction products were obtained in the form of a brownish gray aqueous solution having a solids content of about 55% by weight and a pH of 9.5.

Table 1 below shows various concentrates according to the invention for the production of wetting water or extinguishing foams. <b> Table </ b> 1 Composition of aqueous concentrates for water-extinguishing agents (amounts in% by weight) component 1 2 3 4 5 6 Polymer condensate A 30.0 - - - - - Polymer condensate B - - - - - - Polymer condensate C - - 50.0 - - - Polymer condensate D - - - 30.0 - - Polymer condensate E - - - - 35.0 - Polymer condensate F - - - - - 45.0 Texapon ^® N 15.0 - - 10.0 - - Glucopon ^® APG 100 - 20.0 - 5.0 - - Dehyton ^® K - - 5.0 - - - Novec 1230 ^® - - - - 15.0 - Dimethicone - - - - - 5.0 ethylene glycol 4.2 4.2 4.2 4.2 4.2 4.2 sodium alginate 0.2 0.2 0.2 0.2 0.2 0.2 water Ad 100

DETERMINATION OF DYNAMIC SURFACE VOLTAGE

To evaluate the performance of the preparations, the dynamic surface tension γ of a 0.1% strength by weight aqueous solution of concentrates 1 to 6 was determined. The assessment was carried out according to the bubble pressure method with a tensiometer from SITA (model t60). The measuring solutions were heated to 20 ° C and the air bubbles at different speeds through a capillary pressed. From the occurring pressure change, the surface tension can be determined as a function of the bubble life according to the following equation: $$\mathrm{\gamma }=\mathrm{r}\left({\mathrm{\rho }}_{\mathrm{Max}}-\mathrm{\rho }*\mathrm{G}*\mathrm{H}\right)/\mathrm{2}$$

Here, ρ _{max means} the maximum pressure, p the density of the liquid, h the immersion depth and r the radius of the capillary. The measured values are shown in Table 2. As a comparison (V1) was a solution containing only Texapon ^® N as a surfactant. <b> Table 2 </ b> Dynamic surface tension γ [mn / m] Bubble life [ms] V1 1 2 3 4 5 6 32 72.6 72.5 72.7 72.6 72.6 72.6 72.5 38 72.6 72.5 72.6 72.6 72.6 72.4 72.5 52 71.6 71.5 71.6 71.6 71.4 71.5 71.4 65 69.5 69.5 69.4 69.3 69.4 69.5 69.5 84 69.3 68.9 68.9 69.0 69.0 69.1 69.0 111 68.5 68.3 68.4 68.4 68.3 68.4 68.4 144 67.4 67.0 67.1 67.1 67.2 67.3 67.3 189 66.0 65.1 65.2 65.3 65.5 65.3 65.5 243 64.5 63.9 63.9 64.0 64.1 64.1 64.1 311 61.0 59.7 59.8 60.0 60.1 60.1 60.0 407 58.4 56.1 56.4 57.8 57.7 57.9 57.9 529 52.0 49.8 49.9 50.0 50.1 50.2 50.1 678 46.3 44.0 44.1 44.3 44.5 44.7 44.7 900 35.0 30.2 30.1 31.4 31.6 31.7 31.5 1033 30.7 26.5 26.5 26.8 26.9 26.4 26.9 1318 25.7 22.8 22.9 22.9 23.1 23.1 23.1 1798 21.1 17.4 17.7 17.9 18.0 18.0 18.1 2615 19.4 16.3 16.3 16.5 16.7 16.9 17.1 9738 17.1 15.1 15.3 15.5 15.6 15.7 15.6 12349 16.2 14.0 14.1 14.3 14.4 14.5 14.6 16176 15.9 13.2 13.3 13.5 13.6 13.7 13.6 19920 15.7 12.8 12.7 12.8 13.0 12.9 12.9 31841 15.3 12.6 12.8 13.0 13.1 12.9 12.9 33091 15.2 12.0 12.4 12.5 12.5 12.6 12.6 47713 15.0 11.4 11.8 11.6 11.5 11.7 11.9 60227 15.0 11.0 11.3 11.5 11.7 11.7 11.7

The examples show compared to the same, that the preparations according to the invention a much stronger reduction of the dynamic surface tension effect as the standard Texapon ^® N.

APPLICATIONS Example A1

On the basis of the foaming agents of composition 1 to 6, an extinguishing foam was produced with the aid of a foam generator, which had a non-aqueous content of 5% by weight and a foaming number of more than 3. Such a composition extinguished ethanol, butanol, kerosene and light fuel oil within 5 seconds of application.

Example A2

Concentrate 1 was added to the extinguishing water in the tank of the tanker in a concentration of 1% by weight. From the tank, the extinguishing water was passed at a pressure of 5 to 40 bar through a pressure hose to a suitable and a conventional fire protection spray pipe with the help of a pump. The spray tube gave the extinguishing water in the finest distribution in the direction of the fire. The use was made against class A, B, C and E fires.

Example A3

An extinguishing water stream, which was passed through pipes or hoses by means of suitable pumps at a pressure of 10 bar, the concentrate according to the invention 4 3 vol .-% ig was mixed with the aid of an injection mixer. The mixture was then fed to an air foam jet tube which delivered a jet of foam to a fire object. The foam in this case showed a foaming, which accounted for about 6 to 8 times the Löschwassenergemisches. Foam of this nature can be used against Class A, B and E fires. Expediently class E fires are only combatted by stationary foam pipes.

Example A3

A low-foam generator, which had a self-priming admixing device, was supplied with extinguishing water and the concentrate F according to the invention such that the concentrate constituted about 2% by weight of the extinguishing water. This mixture was sprayed as usual in a stream of air, whereupon a plasticizer formed before a finishing network, whose volume made up the 1000 times the original liquid. Light foam produced in this way is suitable for combating class A, B, C fires and with limitations D and E.

Claims (15)

Aqueous preparations containing (a) polymer condensates obtainable by treating microorganisms with aqueous alkali bases and subsequently reacting the intermediates thus obtained with triglycerides and optionally polybasic carboxylic acids and / or polyols having 2 to 12 carbon atoms and 2 to 6 hydroxyl groups, and (b) at least one additive selected from the group formed by (b1) surfactants based on renewable raw materials, (b2) fluorine compounds, and (b3) Silicone compounds. Composition according to Claim 1, characterized in that the polymer condensates which form component (a) have an average molecular weight in the range from 20,000 to 250,000 daltons. Composition according to Claims 1 and / or 2, characterized in that the polymer condensates which form component (a) are obtained on the basis of yeasts. Composition according to at least one of claims 1 to 3, characterized in that the polymer condensates which form the component (a) are obtained on the basis of microorganisms which are further reacted after alkaline digestion with triglycerides and citric acid. Composition according to at least one of claims 1 to 4, characterized in that the surfactants based on renewable raw materials are selected from the group formed by alkyl ether sulfates, alkyl polyglycosides and betaines. Composition according to at least one of claims 1 to 5, characterized in that the fluorine compounds are selected from the group formed by perfluorinated hydrocarbons having 6 to 18 carbon atoms and fluorinated protein derivatives. Composition according to at least one of claims 1 to 6, characterized in that the silicone compounds are selected from the group consisting of dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine , glycoside- and / or alkyl-modified silicones and simethicones. Preparations according to at least one of claims 1 to 7, characterized in that they (a) 10 to 40% by weight of polymer condensates, (b1) 0 to 30% by weight of surfactants based on renewable raw materials, (b2) 0 to 30% by weight of fluorine compounds, (b3) 0 to 30% by weight of silicone compounds, (c) 0 to 5 wt% antifreeze, and (d) 0 to 2% by weight of thickener containing the provisos that the components of group (b) are present in amounts of at least 1 wt .-% together and all quantities with water and optionally other customary additives to 100 wt .-% complement. Preparations according to at least one of claims 1 to 8, characterized in that they are concentrates with a non-aqueous content of 40 to 60 wt .-% is. A method of controlling fires, comprising diluting preparations of claim 1 with water and directing them in the form of a jet of water or as a water dust against the source of the fire. Method of combating fires, in which one foams preparations of claim 1 and covers the source of the fire with it. Process according to claims 10 and / or 11, characterized in that one uses concentrates which have a non-aqueous content of 40 to 60 wt .-%. Use of polymer condensates which are obtainable by treating microorganisms with aqueous alkali bases and then reacting the intermediates thus obtained with triglycerides and optionally polybasic carboxylic acids and / or polyols having 2 to 12 carbon atoms and 2 to 6 hydroxyl groups as fire-extinguishing agents. Use according to claim 14, characterized in that the polymer condensates are added to the extinguishing water. Use according to claim 15, characterized in that the polymer condensates are added to the extinguishing foam.