EP3956382A1

EP3956382A1 - Polymeric compound for stabilizing fluorine-free fire extinguishing foam and method of making same

Info

Publication number: EP3956382A1
Application number: EP20719195.8A
Authority: EP
Inventors: Stéphane SZONYI; Saïd RACHIDI
Original assignee: Incendin NV
Current assignee: Incendin NV
Priority date: 2019-04-18
Filing date: 2020-04-17
Publication date: 2022-02-23
Also published as: WO2020212591A1

Abstract

In a first aspect, the present invention discloses a polymeric compound, suitable for use in a fire extinguishing composition, comprising a polyethylene imine base with a first moiety selected from the group of linear or branched C2-C15-alkyl, CH3-O-(C2-alkyl-O)r-C2-alkyl, C2-C15-alkyl-O-CH2-CH(-OH)-CH2, C3-C15-cycloalkyl-O-CH2-CH(-OH)-CH2, C6-C15-aryl-O-CH2-CH(-OH)-CH2, linear or branched C2-C15-alkyl-C(=O), C4-C18-alkyl-NH-C(=O), trimethoxysilane-C3-alkyl-O-CH2-CH(-OH)-CH2, polydimethylsiloxane-C3-alkyl-O-CH2-CH(-OH)-CH2 and combinations thereof; a second moiety selected from the group of CH2-C(=O), linear or branched (C2-C3-alkyl-O)r, linear or branched CH2(-OH)-CH-CH2-O-C2-C15-alkyl-O-CH2-CH(-OH)-CH2, linear or branched CH2(-OH)-CH-CH2-O-(C2-C3-alkyl-O)r-CH2-CH(-OH)-CH2, (O=)C-C2-C8-alkyl-C(=O), (O=)C-NH-C4-C8-alkyl-NH-C(=O), CH2-CH(-OH)-CH2- O-bisphenolA-O-CH2-CH(-OH)-CH2, CH2-CH(-OH)-CH2-O-C3-alkyl-polydimethyl- siloxane-C3-alkyl-O-CH2-CH(-OH)-CH2, and combinations thereof; a third moiety selected from the group of C1-C5-alkyl-C(=O)-OH, C1-C5-alkyl-S(=O)2-OH, and combinations thereof. A second aspect relates to a use of said polymeric compound in the production of a fire extinguishing composition. A third and a fourth aspect respectively relate to a fire extinguishing composition and a method of making the polymeric compound comprised therein.

Description

POLYMERIC COMPOUND FOR STABILIZING FLUORINE-FREE FIRE

EXTINGUISHING FOAM AND METHOD OF MAKING SAME

FIELD OF THE INVENTION

The present invention relates to a polymeric compound, more in particular a compound for stabilizing fire extinguishing foams.

BACKGROUND

Fire extinguishing compositions generally contain mixtures of surfactants that act as foaming agents, together with solvents and other additives that provide the desired mechanical and chemical properties to the foam. In particular aqueous fire-fighting foams suitable for fighting fires of classes A and B comprise a plurality of fluorinated products such as fluorinated surfactants or fluoropolymers, in order to improve their physicochemical properties, e.g. enhanced foaming characteristics. These compounds are often referred to as foam stabilizers. The actual fluorine level in said fire-fighting foams is dependent on the required performance specifications, with higher fluorine content providing a faster extinguishing performance and a greater burn back resistance.

A foam stabilizer suited for this purpose comprising a poly-perfluoro-alkyl substituted polyethylene imine is described in WO 2014 153 122. However, fluorinated surfactants have recently come under scrutiny in the light of environmental safety. Perfluoro-octane sulphonates (PFOS) for example, are considered to be bio- accumulative and toxic by environmental authorities. Hence, the use of PFOS has been abandoned by the majority of fire extinguishing foam manufacturers. Accordingly, manufacturers of fire-fighting foams have decided to look for possible alternatives in order to lower or eliminate fluorinated surfactants and fluorinated polymers in fire extinguishing compositions.

US 9 669 246 discloses an aqueous film forming fire extinguishing composition, which comprises a C6 perfluoro-alkyl surfactant, at least one non-fluorinated surfactant and a foam stabilizing agent. The composition contains less than 0,8 % fluorine and therefore is considered to be an honorable step in the right direction. These fluorine-reduced or fluorine-free foams however have two main defects. First of all, the fire extinguishing properties are greatly reduced, and secondly aquatic toxicity is observed due to the use of a large amount of hydrocarbon surfactants to compensate for the removal of fluorinated products. Moreover, by eliminating fluorinated compounds, the efficacy of the fire-fighting foams is possibly lowered towards different types of fires, e.g. class A or class B fires. Accordingly, there is a need for a compound or additive which can replace fluorinated surfactants and fluorinated polymers in fire-fighting foams, without compromising said foam's fire extinguishing properties and foam stability. A high fire extinguishing capability towards different types of fires should be guaranteed, without said fire-fighting foams causing additional environmental risk.

The present invention aims to resolve at least some of the problems and disadvantages mentioned above.

SUMMARY OF THE INVENTION

The present invention and embodiments thereof serve to provide a solution to one or more of above-mentioned disadvantages. To this end, the present invention relates to a polymeric compound according to claim 1.

The polymeric compound is provided with an amphiphilic character. As a result, said polymeric compound shows excellent foaming properties in water-based compositions. The polymeric compound further provides in an enhanced water solubility. This aspect is highly important regarding its intended use in water-based fire extinguishing compositions. In particular the compound with general formula (II), where cross-linking is in order, has the advantage of providing a denser and more stable foam, especially on liquid surfaces.

Preferred embodiments of said polymeric compound are shown in any of the claims 2 to 7.

In a second aspect, the present invention relates to a use of said polymeric compound in, or in the production of, a fire extinguishing composition according to claim 8. More in particular, a preferred embodiment according to claim 9 relates to the use of said compound in a fluorine-free fire extinguishing composition for extinguishing fires of classes A and / or B.

A third aspect relates to a fire extinguishing composition according to claim 10. Preferred embodiments of said fire extinguishing composition are shown in any of the claims 11 to 16. In a specific preferred embodiment according to claim 13 the fire extinguishing composition comprises two polymeric compounds of the first aspect of the invention, said polymeric compounds both being present in a concentration of between 0,05 and 30,00 wt%. The combined use of two compounds provides a synergetic effect towards flowability and foam stability.

In a fourth aspect, the present invention relates to a method for the production of a polymeric compound according to claim 17. Preferred embodiments of said method are shown in any of the claims 18 to 25.

DETAILED DESCRIPTION OF THE INVENTION

In a first aspect, the present invention concerns a polymeric compound of general formula (I)

or of general formula (II)

wherein X is a moiety selected from the group of linear or branched C2-C15-alkyl, CH3-0-(C2-alkyl-0)r-C2-alkyl, C2-C15-alkyl-0-CH2-CH(-0H)-CH2, C3-C15- cycloalkyl-0-CH2-CH(-OH)-CH2, C6-C15-aryl-0-CH2-CH(-0H)-CH2, linear or branched C2-C15-alkyl-C(=0), C4-C18-alkyl-NH-C(=0), trimethoxysilane-C3-alkyl- 0-CH2-CH(-0H)-CH2, polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2, and combinations thereof; Y is a moiety selected from the group of CH2-C(=0), linear or branched (C2-C3-alkyl-0)r, linear or branched CH2(-0H)-CH-CH2-0-C2-C15-alkyl- 0-CH2-CH(-0H)-CH2, linear or branched CH2(-0H)-CH-CH2-0-(C2-C3-alkyl-0)r- CH2-CH(-OH)-CH2, (0=)C-C2-C8-alkyl-C(=0), (0=)C-NH-C4-C8-alkyl-NH-C(=0),

CH2-CH(-OH)-CH2-0-bisphenolA-0-CH2-CH(-OH)-CH2, CH2-CH(-0H)-CH2-0-C3- alkyl-polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2, and combinations thereof; Z is a moiety selected from the group of Cl-C5-alkyl-C(=0)-0H, C1-C5- alkyl-S(=0)2-0H, and combinations thereof; wherein r is an integer from 3 to 10, and wherein n-2, n'-2 are integers from 1 to 40.

Unless otherwise defined, all terms used in disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.

As used herein, the following terms have the following meanings:

"A", "an", and "the" as used herein refers to both singular and plural referents unless the context clearly dictates otherwise. By way of example, "a compartment" refers to one or more than one compartment. "About" as used herein referring to a measurable value such as a parameter, an amount, a temporal duration, and the like, is meant to encompass variations of +/- 20% or less, preferably +/-10% or less, more preferably +/-5% or less, even more preferably +/-1% or less, and still more preferably +/-0.1% or less of and from the specified value, in so far such variations are appropriate to perform in the disclosed invention. However, it is to be understood that the value to which the modifier "about" refers is itself also specifically disclosed.

The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range, as well as the recited endpoints.

The expression "% by weight", "weight percent", "%wt" or "wt%", here and throughout the description unless otherwise defined, refers to the relative weight of the respective component based on the overall weight of the formulation.

As can be seen from general formulas (I) and (II), said compounds are derivatives of polyethylene imine. Polymeric compounds according to the present invention are particularly useful as additives in fire extinguishing compositions, with the aim of lowering, more preferably excluding, the use of fluorinated compounds in said fire extinguishing compositions.

The expressions "fire extinguishing composition" and "fire extinguishing foam" in the context of the present invention need to be interpreted as any composition or foam suitable for fire suppression. Within fire extinguishing foams, a distinction between different foam types and / or fire classes is made. In the context of the present invention, class A fires and class B fires are stressed. Class A fires involve the combustion of solid materials, while class B fires involve fires in flammable liquids. The fire extinguishing foams accordingly need different properties in order to exhibit a high fire extinguishing capability.

The notation "n-2" or "n'-2" regarding the chemical formulae as disclosed herein, refers to the chain length of a polymeric compound, excluding the two terminal monomer units. For example, when for a polymeric compound n = 10, said polymeric compound has a chain length of 10 monomer units. Accordingly the notation n-2 equals 8, excluding the terminal monomer units. In this light, foams suited to fight class A fires intend to lower the surface tension of water, which assists in the wetting and saturation of solid materials. This aids the fire suppression in these materials and can also prevent reignition. Foams suited to fight class B fires on the other hand, are designed to contain explosive vapors produced by flammable liquid and accordingly intend to contain liquid fires within a small area. Properties like flow and spreading of liquid surfaces are desirable in this case, as well as formation of a protective film resistant to the action of e.g. alcohols in the flammable liquid.

Various beneficial effects are assigned to the presence of the substituents according to the current disclosure. Moiety X is found to provide an amphiphilic character to the polymeric compound. As a result, said polymeric compound shows excellent foaming properties in water-based compositions. In the context of the present invention, due to said amphiphilic nature of the polymeric compound, it is possible to reduce the overall amount of hydrocarbon surfactants in foam formulations, or more in particular, fire extinguishing foams. In addition, said polymeric compound shows an enhanced associative character. In particular, some parts of said polymeric compound are found to be especially water-soluble, while some parts are found to be especially hydrophobic. As a result, said polymeric compound tends to interact and assemble with both itself and / or other molecules, which molecules can be of both hydrophilic and hydrophobic nature.

The incorporation of moiety Z adds to this beneficial effect as said moiety Z is responsible for the enhancement of the water solubility of the polymeric compound. This aspect is highly important regarding its intended use in water-based fire extinguishing compositions. Furthermore, moiety Z has the effect of lowering the pH of said polymeric compound in water-based solutions, which possibly benefits the foam stability.

The incorporation of moiety Y furthermore provides a cross-linked structure to the polymeric compound, in particular the compound with general formula (II). Cross- linking has the advantage of providing a denser and more stable foam, especially on liquid surfaces.

A synergetic effect is further found to exist between the incorporation of moieties X, Y and Z, as the polymeric compound according to the present invention shows exceptionally good foaming properties in water-based fire-fighting compositions. By preference, X is a moiety selected from the group of 2-ethylhexyl-0-CH2-CH(- OH)-CH2, octyl-0-CH2-CH(-OH)-CH2, decyl-0-CH2-CH(-0H)-CH2, dodecyl-0-CH2- CH(-OH)-CH2, tetradecyl-0-CH2-CH(-0H)-CH2, neodecyl-0-CH2-CH(-OH)-CH2, trimethoxysilane-C3-alkyl-0-CH2-CH(-OH)-CH2, polydimethylsiloxane-C3-alkyl-0- CH2-CH(-OH)-CH2, and combinations thereof. The polymeric compound is with these incorporated moieties are found to possess a particularly pronounced amphiphilic character, being advantageous for flowing and wetting characteristics of the composition in which it is used.

In one preferred embodiment, X is a dodecyl-0-CH2-CH(-OH)-CH2 and / or tetradecyl-0-CH2-CH(-0H)-CH2 moiety. The polymeric compound shows exceptionally good flowability.

In another preferred embodiment, X is a trimethoxysilane-C3-alkyl-0-CH2-CH(-OH)- CH2 or polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2 moiety. The introduction of a siloxane or silane segment within the macromolecular structure of the polymeric compound of the invention gives a better fluidity and a better spreading of the foam, especially on the surface of non-polar liquids such as hydrocarbons. The presence of silane and / or siloxane yields exquisite alcohol resistant properties to the polymeric compound of the present invention. The compound produces a vapour-sealing film that spreads rapidly over hydrocarbon surfaces to provide rapid control and extinguishment. On polar solvents, especially in combination with a gum polymer such as xanthan gum, an insoluble polymer membrane is formed between the burning surface and the foam, which protects the foam and prevents its breakdown. As a result, the fire extinguishing composition and the polymeric compound as comprised therein are especially effective for extinguishing and securing flammable hydrocarbon and polar solvent fires.

According to an embodiment of the present invention, Y is a moiety selected from the group of CH2(-0H)-CH-CH2-0-CH2-CH(-CH3)2-CH2-0-CH2-CH(-0H)-CH2, CH2(-0H)-CH-CH2-0-C4-C6-alkyl-0-CH2-CH(-0H)-CH2, (0-CH2-CH(-CH3)-0)r, (O- CH2-CH2-0)r, wherein r is between 8 and 10, CH2-CH(-OH)-CH2-0-bisphenolA-0- CH2-CH(-OH)-CH2, CH2-CH(-OH)-CH2-0-C3-alkyl-polydimethylsiloxane-C3-alkyl- 0-CH2-CH(-0H)-CH2, and combinations thereof. The introduction of cross-linking within the macromolecular structure of the polymeric compound of the invention allows to form an oleophobic barrier within the foam, preventing its contamination by non-polar liquids such as hydrocarbons. This barrier also slows the decantation of the foam and thus improves its stability on the surface of non-polar liquids such as hydrocarbons. This property is exceptionally important in the light of fire class B.

In one preferred embodiment Y comprises a CH2(-0H)-CH-CH2-0-C4-C6-alkyl-0- CH2-CH(-OH)-CH2 and / or (0-CH2-CH(-CH3)-0)r moiety, wherein r is between 8 and 10. The polymeric compound shows a fast oleophobic barrier formation within the foam and further improves foam stability.

In another preferred embodiment, Y comprises a CH2-CH(-OH)-CH2-0-bisphenolA- 0-CH2-CH(-0H)-CH2 or CH2-CH(-OH)-CH2-0-C3-alkyl-polydimethylsiloxane-C3- alkyl-0-CH2-CH(-0H)-CH2. The introduction of a siloxane or silane segment via di epoxides of the glycidic type within the macromolecular structure of the polymeric compound of the invention gives a better fluidity and a better spreading of the foam, especially on the surface of non-polar liquids such as hydrocarbons. Meanwhile, the formation of an oleophobic barrier reduces the risk of fire spreading, thus attempting to contain the fire in a small area. In the context of the present invention, in order to optimize foam stabilization of fire extinguishing foams, according to some embodiments X is polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2.

Another especially advantageous embodiment for the stabilization of fire fighting foams concerns the polymeric compound, wherein moiety Y is CH2-CH(-0H)-CH2-0- C3-alkyl-polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2 and X is a moiety selected from the group of 2-ethylhexyl-0-CH2-CH(-0H)-CH2, octyl-0-CH2-CH(- OH)-CH2, decyl-0-CH2-CH(-0H)-CH2, dodecyl-0-CH2-CH(-OH)-CH2, tetradecyl-O- CH2-CH(-OH)-CH2, neodecyl-0-CH2-CH(-OH)-CH2, and combinations thereof. The specific combination of said moieties gives rise to a polymeric compound which combines all of the above beneficial effects. Moreover, these effects work together synergistically, thus providing an excellent foam stabilization and a remarkably low surface tension. According to an embodiment of the present invention, said polymeric compound is a foam stabilizer.

According to further or another embodiment of the present invention, at least said moiety X is trimethoxysilane-C3-alkyl-0-CH2-CH(-OH)-CH2 or polydimethylsiloxane- C3-alkyl-0-CH2-CH(-0H)-CH2 and / or said moiety Y is CH2-CH(-0H)-CH2-0-C3- alkyl-polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2. The presence of silane and / or siloxane yields exquisite alcohol resistant properties to the polymeric compound of the present invention. The compound produces a vapour-sealing film that spreads rapidly over hydrocarbon surfaces to provide rapid control and extinguishment. On polar solvents, especially in combination with a gum polymer such as xanthan gum, an insoluble polymer membrane is formed between the burning surface and the foam, which protects the foam and prevents its breakdown. As a result, the polymeric compound as comprised herein is especially effective for extinguishing and securing flammable hydrocarbon and polar solvent fires.

In a further or another embodiment, Z is selected from the group of Cl-C2-alkyl- C(=0)-OH, C3-alkyl-S(=0)2-0H, and combinations thereof. This allows lowering the surface tension of the water-based composition in which the polymeric compound is applied, thereby being perfectly suited for fighting fires of class A. By preference, Z is an acetyl moiety.

According to an embodiment of the present invention, the following moieties X and Z are combined in a polymeric compound of general formula (I) : dodecyl-0-CH2- CH(-OH)-CH2 and / or tetradecyl-0-CH2-CH(-0H)-CH2 with acetyl; octyl-0-CH2- CH(-OH)-CH2 and / or decyl-0-CH2-CH(-0H)-CH2 with acetyl; neodecyl-0-CH2- CH(-OH)-CH2 with acetyl; polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2 with acetyl; or trimethoxysilane-C3-alkyl-0-CH2-CH(-OH)-CH2 with acetyl. According to another embodiment of the present invention the following moieties X, Y and Z are combined in a polymeric compound of general formula (II) : dodecyl-0-CH2-CH(-OH)- CH2 and / or tetradecyl-0-CH2-CH(-0H)-CH2 with (0-CH2-CH(-CH3)-0)r and with acetyl, wherein r is an integer between 8 and 10; 2-ethylhexyl-0-CH2-CH(-0H)-CH2 with (0-CH2-CH(-CH3)-0)r and with acetyl, wherein r is an integer between 8 and 10; neodecyl-0-CH2-CH(-OH)-CH2 with (0-CH2-CH(-CH3)-0)r and with acetyl, wherein r is an integer between 8 and 10; octyl-0-CH2-CH(-OH)-CH2 and / or decyl- 0-CH2-CH(-0H)-CH2 with (0-CH2-CH(-CH3)-0)r and with acetyl, wherein r is an integer between 8 and 10; neodecyl-0-CH2-CH(-OH)-CH2 with CH2-CH(-OH)-CH2- 0-neopentyl-0-CH2-CH(-OH)-CH2 and with acetyl; or dodecyl-0-CH2-CH(-OH)-CH2 and / or tetradecyl-0-CH2-CH(-0H)-CH2 with CH2-CH(-OH)-CH2-C3-alkyl- polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2 and with acetyl.

A second aspect of the present invention is related to the use of at least one polymeric compound according to any of the embodiments above in a fire extinguishing composition, or in the production of a fire extinguishing composition, by preference in a fire extinguishing foam. More by preference, said polymeric compound is a foam stabilizer. An embodiment of the invention relates to a use of said polymeric compound directed to extinguishing fires of classes A and / or B with a fluorine-free fire extinguishing composition. Use of said polymeric compound in said composition allows the use of lower amounts of other surfactants than are commonly used in comparable compositions, thereby lowering the environmental hazardous nature of known compositions. In a preferred embodiment said fire extinguishing composition is a fire extinguishing foam.

According to a further or another embodiment said polymeric compound has a concentration of between 0,10 and 10,00 wt% of the total fire extinguishing foam. Within this range it was found that the polymeric compound provided said foam with excellent flow characteristics while obtaining a stable foam. This allows to lower commonly used hydrocarbon surfactants in the composition without affecting the fire extinguishing capacity nor stability of the foam.

By preference, two polymeric compounds are present in the fire extinguishing foam, said polymeric compounds respectively having a concentration of between 0,10 and 2,00 wt% and between 0,50 and 5,00 wt%. The combined use of two compounds provides a synergetic effect in favor of foam stability, flow characteristics and amphoteric character as a diverse group of X, Y and Z moieties is possibly applied in the composition.

In a third aspect the present invention discloses a fire extinguishing composition comprising at least one polymeric compound according to any of the previous embodiments. The fire extinguishing composition herein disclosed has enhanced properties over commonly known compositions in that it provides an enhanced capability for efficiently fighting fires of both classes A and B. This effect is due to, among others, enhanced flow characteristics and a better foam stability. Moreover, the fire extinguishing composition comprising said polymeric compound allows a lower concentration of surfactants in the composition without compromising the beneficial properties towards fire-fighting and fire control.

By preference, the fire extinguishing composition is fluorine-free. This property is considered to be of high importance in the light of presently known environmental and health issues. Fluorinated compounds are a group of chemicals which have been manufactured and used in a variety of industries around the globe, which are very persistent in the environment and in the human body. Moreover, there is evidence that exposure to fluorinated compounds can lead to adverse human health effects. Studies indicate that fluorinated compounds possibly cause reproductive and developmental, liver and kidney, and immunological problems. The most consistent findings are increased cholesterol levels among exposed populations, with more limited findings related to low infant birth weights, effects on the immune system, cancer, and thyroid hormone disruption. It is self-evident that the use of fire extinguishing compositions comprising fluorinated compounds is very undesirable in this context. The present invention therefore provides in fluorine-free formulations, which cause far less risk towards the environment and human health, without compromising the fire extinguishing capability of said compositions.

In an embodiment, said polymeric compound has a concentration of between 0,10 and 60,00 wt% of the total fire extinguishing composition. Within this range it was found that the polymeric compound provided said composition with excellent flow characteristics while obtaining a stable foam. This allows to lower commonly used hydrocarbon surfactants in the composition without affecting the fire extinguishing capacity of the foam.

According to a further or another embodiment, said polymeric compound has a concentration of between 0,10 and 20,00 wt%, providing a ready-to-use fire extinguishing composition. By preference, said polymeric compound has a concentration of between 0,50 and 15,00 wt%, more be preference between 5,00 and 10,00 wt%.

In a further or another embodiment, the fire extinguishing composition is a fire extinguishing concentrate or fire-fighting foam concentrate, and comprises 20,00 to 60,00 wt% of said polymeric compound. By preference, said concentrate comprises 25,00 to 50,00 wt% of said polymeric compound. Foam concentrates can achieve fire control faster and with lower product volumes than similar agents, which can substantially lessen property damage and environmental impact.

In some embodiments, said composition comprises at least two different polymeric compounds of the first aspect of the invention, said polymeric compounds both being present in a concentration of between 0,05 and 30,00 wt%. The combined use of two compounds provides a synergetic effect in favor of foam stability, flow characteristics and amphoteric character as a diverse group of X, Y and Z moieties is possibly applied in the composition. It is found that when a combination of at least two different polymeric compounds is used, one of said compounds can act as a surfactant, while another of said compounds can act as a foam stabilizer.

Further embodiments of the present invention comprise at least 3 different polymeric compounds, by preference at least different 4 polymeric compounds, more by preference at least 5 different polymeric compounds. By incorporating a multitude of different polymeric compounds, the fire-extinguishing composition according to the present invention can be fine-tuned to very specific conditions, allowing optimal control and efficacy in a very diverse variety of conditions.

The fire extinguishing composition according to an embodiment comprises at least one surfactant chosen from the group of non-ionic surfactants, anionic surfactants and amphoteric surfactants. Said surfactants, especially in combination, allow the fire extinguishing composition to form a homogeneous mixture, to produce a stable foam which interacts with a broad range of materials and to provide excellent fire fighting properties

Suitable non-ionic surfactants for the present disclosure include, but are not limited to, polyethylene derivatives of alkylphenols, linear or branched alcohols, fatty acids, alkylamines, alkylamides, and acetylenic glycols, alkyl glycosides and alkyl polyglycosides, block polymers of polyethylene and polypropylene units. Anionic surfactants may be selected from the exemplary group of alkyl surfactants, alkyl carboxylates, alkyl sulfates, sulfonates, and ethoxylated derivatives thereof. Amphoteric surfactants applicable in the present composition include, but are not limited to, surfactants which contain in the same molecule, amino and carboxy, sulfonic, and sulfuric ester moieties, such as amine oxides, aminopropionates, sultaines, sulfobetaines, alkyl sulfobetaines, alkyl betaines, alkylaminobetaines, dihydroxyethyl glycinates, imidazoline acetates, imidazoline propionates, and imidazoline sulfonates.

By preference, said composition comprises 0,50 to 10,00 wt% of a non-ionic surfactant, 0,50 to 10,00 wt% of an anionic surfactant and 0,25 to 10,0 %wt of an amphoteric surfactant. Said combination offers excellent fire-fighting properties, mobility, viscoelasticity and foam stability to the composition, while said composition forms a minimal hazard towards the environment and / or human health. By preference, said composition comprises 2,50 to 6,00 wt% of a non-ionic surfactant, 2,50 to 6,00 wt% of an anionic surfactant and 0,10 to 2,50 %wt of an amphoteric surfactant.

The present invention in a fourth aspect provides a method for the production of a polymeric compound of general formula (I) or of general formula (II). The method according to the present invention is based on the reactivity of the amine functions of polyethylenimines having different molecular weights.

According to an embodiment, said amine functions react with reactive compounds of the following classes:

- monofunctional compounds such as alkyl tosylates, polyethyleneglycol methylether tosylates, epoxydes, acyl chlorides and / or alkyl isocyanates;

- difunctional compounds such as ethyl monochloroacetate, di-tosylates, dicarboxylic acid chlorides, di-epoxides and / or di-isocyanates;

- sodium monochloroacetate, acrylic acid, beta-propiolactone, 1,3-propane sultone and / or 1,4-butane sultone.

According to an embodiment, the method comprises the steps of:

a. providing a polyethylene imine of formula (CH2-N(-CH2-CH2-NH2)-CH2- CH₂-NH-CH₂)n-2, comprising a plurality of reactive Nhh-groups, b. reacting said polyethylene imine with a glycidyl ether of general formula (III), a tosylate of general formula X-O-Ts, an acyl chloride of general formula CI-C(=0)-Cl-C12-alkyl, an isocyanate of general formula 0=C=N-Cl-C12-alkyl, or combinations thereof,

wherein X is a moiety selected from the group of linear or branched C2- C15-alkyl, CH3-0-(C2-alkyl-0)r-C2-alkyl, C3-C15-cycloalkyl, C6-C15- aryl, linear or branched C2-C15-alkyl-C(=0), C4-C18-alkyl-NH-C(=0), trimethoxysilane-C3-alkyl, polydimethyl-siloxane-C3-alkyl, and combinations thereof,

c. optionally, reacting the reaction product of step b with a diglycidyl ether of general formula (IV), a di-tosylate of general formula Ts-0-(CH2-CH2- 0)r-Ts, a dicarboxylic acid chloride of general formula CI-C(=0)-(CH2)r- C-(=0)-CI or CI-C(=0)-(0-CH2-CH2)r-C-(=0)-CI, a di-isocyanate of general formula 0=C=N-(CH2)r-N=C=0, or combinations thereof, wherein Y is a moiety selected from the group of CH2-C(=0), linear or branched (C2-C3-alkyl-0)r, linear or branched C2-C15-alkyl, linear or branched (C2-C3-alkyl-0)r, (0=)C-C2-C8-alkyl-C(=0), (0=)C-NH-C4-C8- aikyl-NH-C(=0), bisphenolA, C3-alkyl-polydimethylsiloxane-C3-alkyl, wherein r is an integer between 3 and 10, and combinations thereof, and d. reacting the reaction product of step b or c with a compound selected from the group of sodium chloroacetate, acrylic acid, beta-propiolacton, 1,3- propane sultone, and combinations thereof.

The mode of synthesis which has been chosen is very versatile, since the structure of the resulting polymeric compounds can be easily modulated according to the properties that one wishes to obtain with the fluorine-free extinguishing foams. According to an embodiment of the present method, said polyethylene imine has a molecular weight of between 800 and 25000 Da.

By preference, said glycidyl ether is selected from the group of 2-ethylhexyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, dodecyl glycedyl ether, tetradecyl glycidyl ether, glycidyl neodecanoate, and combinations thereof. Used in fluorine-free extinguishing compositions, the long hydrocarbon-based chains grafted onto the polyethylene imine precursor polymers via glycidic-type monoepoxide compounds make it possible to give the extinguishing composition better foamability, mobility and viscoelasticity. The aim is to provide the resulting polymeric compound with an amphiphilic character, thereby providing excellent foaming properties of the resulting polymeric compound in water-based compositions. Due to said amphiphilic nature of the polymeric compound, it is possible to reduce the overall amount of hydrocarbon surfactants in foam formulations, or more in particular, fire extinguishing foams, while still obtaining excellent flowing and wetting characteristics of the composition in which it is used.

In an embodiment of the method, said diglycidyl ether is selected from the group of neoptentyl glycol diglycidyl ether, 1-4-butanediol diglycidyl ether, 1,6-hexanodiol diglycidyl ether, polypropyleneglycol diglycidyl ether, and combinations thereof. The introduction of cross-linking agent via glycidic diepoxide compounds allows the polymers of the invention to form an oleophobic barrier within the foam, preventing contamination by non-polar liquids such as hydrocarbons. This barrier also slows the decantation of the foam and thus improves its stability on the surface of non-polar liquids such as hydrocarbons.

A further or another embodiment of the method encompasses the reaction product of step b being reacted with a glycidyl ether terminated propyl-polydimethylsiloxane or propyl-trimethoxysilane before proceeding to step c. The introduction of a siloxane or silane segment via mono-epoxides of the glycidic type within the macromolecular structure of the polymers of the invention gives a better fluidity and a better spreading of the foam on the surface of non-polar liquids such as hydrocarbons. The presence of silane and / or siloxane yields exquisite alcohol resistant properties to the resulting polymeric compound of the present invention. The compound produces a vapour-sealing film that spreads rapidly over hydrocarbon surfaces to provide rapid control and extinguishment. On polar solvents, especially in combination with a gum polymer such as xanthan gum, an insoluble polymer membrane is formed between the burning surface and the foam, which protects the foam and prevents its breakdown. As a result, the fire extinguishing composition and the polymeric compound as comprised therein are especially effective for extinguishing and securing flammable hydrocarbon and polar solvent fires.

The reaction product of step b or c is, according to a further or another embodiment, reacted with a diglycidyl ether terminated propyl-polydimethylsiloxane before proceeding to step d. Said reaction adds to the lowering of surface tension and improves foam stability, while obtaining a cross-linked polymeric compound with enhanced fire-fighting properties.

In step b, said polyethylene imine is reacted with the glycidyl ether of general formula (III) at a temperature of between 45,0 and 80,0 °C. According to an embodiment, the polyethylene imine is reacted with the glycidyl ether in the presence of butyldiglycol or propyleneglycol. Butyldiglycol or propyleneglycol are added to the polyethylene imine at a temperature of between 45,0 and 60,0 °C. By preference butyldiglycol or propyleneglycol are added at a temperature of between 45,0 and 55,0 °C, most preferably at 50,0°C. It is noted that the reaction is possibly slightly exothermic and that after adding the glycidyl ether, the reaction preferably takes place at a temperature of between 60,0 and 80,0 °C during 30 to 90 minutes. In a more preferred embodiment, after addition of the glycidyl ether, said reaction takes place at 70,0 °C during 60 minutes.

The reaction product of step c is reacted with the diglycidyl ether of general formula (IV) in step c at a temperature of between 60,0 and 80,0 °C during 30 to 90 minutes. According to a preferred embodiment, said reaction takes place at a temperature of 70,0 °C during 60 minutes.

In step d, the reaction product of step c is reacted with sodium chloroacetate, beta- propiolacton or 1,3-propiosultone at a temperature of between 75,0 and 85,0 °C during 30 to 90 minutes. Said sodium chloroacetate, beta-propiolacton or 1,3- propiosultone according to an embodiment is added as an aqueous solution to the reaction mixture. By preference, the reaction takes place at 75,0 to 80,0 °C during 60 minutes.

In a further or another embodiment, a polymeric compound according to the first aspect of the present invention is produced by the method as herein disclosed.

The invention is further described by the following non-limiting examples which further illustrate the invention, and are not intended to, nor should they be interpreted to, limit the scope of the invention.

EXAMPLES

The present invention will now be further exemplified with reference to the following examples.

Example 1

This example illustrates the production of a polymeric compound according to an embodiment of the present invention. Production of said compound comprises the following steps: a. 250 mmol of polyethylenimine with a molecular weight of around 800 Da is introduced into a reactor equipped with a reflux condenser and a stirrer, butyldiglycol is added and the reactor is heated to 50,0 °C,

b. 250 mmol of dodecyl and / or tetradecyl glycidyl ether is added to the reactor, said reactor being heated at 70,0 °C for 1 hour, c. 25 mmol of polypropylene glycol diglycidyl ether is added to the reactor, said reactor being heated at 70,0 °C for 1 hour,

d. an aqueous solution of 1,25 mol of sodium monochloroacetate is added slowly to the reactor (the reaction is exothermic), said reactor being heated at 75,0 to 80,0 °C for 1 hour.

A polymer is obtained in the form of a viscous liquid with a refractive index of about 1,35, a pH of about 10,2 and a surface tension of about 24,6 mN/m. The obtained polymeric compound is suitable for use in a fire extinguishing composition, providing said composition with excellent fire-fighting properties, a good mobility, viscoelasticity and foam stability.

Example 2 A polymeric compound suitable for use in a fire-fighting composition according to the present invention is obtained by following steps: a. 18,5 mmol of polyethylenimine with a molecular weight of around 1300 Da is introduced into a reactor equipped with a reflux condenser and a stirrer, propyleneglycol is added and the reactor is heated to 50,0 °C,

b. 9,2 mmol of octyl and / or decyl glycidyl ether is added to the reactor, said reactor being heated at 70,0 °C for 1 hour,

c. 18,5 mmol of polypropylene glycol diglycidyl ether is added to the reactor, said reactor being heated at 70,0 °C for 1 hour,

d. an aqueous solution of 1,85 mol of sodium monochloroacetate is added slowly to the reactor (the reaction is exothermic), said reactor being heated at 75,0 to 80,0 °C for 1 hour.

A polymer is obtained in the form of a viscous liquid with a refractive index of about 1,44, a pH of about 9,2 and a surface tension of about 29,4 mN/m. The obtained polymeric compound is suitable for use in a fire extinguishing composition, providing said composition with excellent fire-fighting properties, a good mobility, viscoelasticity and foam stability.

Example 3 This example illustrates the production of a polymeric compound according to an embodiment of the present invention. Production of said compound comprises the following steps: a. 125 mmol of polyethylenimine with a molecular weight of around 2000 Da is introduced into a reactor equipped with a reflux condenser and a stirrer, butyldiglycol is added and the reactor is heated to 50,0 °C,

b. 250 mmol of dodecyl and / or tetradecyl glycidyl ether is added to the reactor, said reactor being heated at 70,0 °C for 1 hour,

c. 12,7 mmol of polypropylene glycol diglycidyl ether is added slowly to the reactor (the reaction is exothermic), said reactor being heated at 70,0 °C for 1 hour,

d. an aqueous solution of 1,25 mol of sodium monochloroacetate is added to the reactor, said reactor being heated at 75,0 to 80,0 °C for 1 hour.

A polymer is obtained in the form of a viscous liquid with a refractive index of about 1,46, a pH of about 10,2 and a surface tension of about 25,6 mN/m. The obtained polymeric compound is suitable for use in a fire extinguishing composition, providing said composition with excellent fire-fighting properties, a good mobility, viscoelasticity and foam stability.

Example 4

A polymeric compound suitable for use in a fire-fighting composition according to the present invention is obtained by following steps: a. 12 mmol of polyethylenimine with a molecular weight of around 25000 Da is introduced into a reactor equipped with a reflux condenser and a stirrer, propyleneglycol is added and the reactor is heated to 50,0 °C,

b. 251 mmol of dodecyl and / or tetradecyl glycidyl ether is added to the reactor, said reactor being heated at 70,0 °C for 1 hour,

c. 36 mmol of polypropylene glycol diglycidyl ether is added slowly to the reactor (the reaction is exothermic), said reactor being heated at 70 °C for 1 hour, d. an aqueous solution of 2,73 mol of sodium monochloroacetate is added slowly to the reactor (the reaction is exothermic), said reactor being heated at 75,0 to 80,0 °C for 1 hour. A polymer is obtained in the form of a viscous liquid with a refractive index of about 1,44, a pH of about 9,4 and a surface tension of about 27,5 mN/m. The obtained polymeric compound is suitable for use in a fire extinguishing composition, providing said composition with excellent fire-fighting properties, a good mobility, viscoelasticity and foam stability. As the polymeric compound of Example 4 uses a polyethylene imine of a higher molecular weight as a starting material, the resulting polymeric compound has a considerably larger cross-linked structure than the compound described in Examples 1, 2 and 3. Using the compound of the present example in a fire extinguishing composition would therefore provide in a denser and slightly more stabilized foam.

Example 5

A polymeric compound suitable for use in a fire-fighting composition according to the present invention is obtained by following steps: a. 170 mmol of polyethylenimine with a molecular weight of around 2000 Da is introduced into a reactor equipped with a reflux condenser and a stirrer, propyleneglycol is added and the reactor is heated to 50,0 °C,

b. 172 mmol of dodecyl and / or tetradecyl glycidyl ether is added to the reactor, said reactor being heated at 70,0 °C for 1 hour,

c. 9,0 mmol of (3-glycidyloxypropyl)-trimethoxysilane is added to the reactor, said reactor being heated at 70,0 °C for 1 hour,

d. an aqueous solution of 1,7 mol of sodium monochloroacetate is added slowly to the reactor (the reaction is exothermic), said reactor being heated at 75,0 to 80,0 °C for 1 hour.

A polymer is obtained in the form of a viscous liquid with a refractive index of about 1,46, a pH of about 10,5 and a surface tension of about 30,5 mN/m. The obtained polymeric compound is suitable for use in a fire extinguishing composition, providing said composition with excellent fire-fighting properties, a good mobility, viscoelasticity and foam stability.

Example 6

A polymeric compound suitable for use in a fire-fighting composition according to the present invention is obtained by following steps: a. 63 mmol of polyethylenimine with a molecular weight of around 2000 Da is introduced into a reactor equipped with a reflux condenser and a stirrer, butyldiglycol is added and the reactor is heated to 50,0 °C,

b. 203 mmol of dodecyl and / or tetradecyl glycidyl ether is added to the reactor, said reactor being heated at 70,0 °C for 1 hour,

c. 45 mmol of polyethylene glycol diglycidyl ether 70 °C for 1 hour, 19,5 mmol of poly(dimethylsiloxane diglycidyl ether 70 °C for 1 hour,

d. an aqueous solution of 618 mmol of sodium monochloroacetate is added slowly to the reactor (the reaction is exothermic), said reactor being heated at 75,0 to 80,0 °C for 1 hour.

A polymer is obtained in the form of a viscous liquid with a refractive index of about 1,42, a pH of about 10,0 and a surface tension of about 33,4 mN/m. The obtained polymeric compound is suitable for use in a fire extinguishing composition, providing said composition with excellent fire-fighting properties, a good mobility, viscoelasticity and foam stability.

Example 7

A polymeric compound suitable for use in a fire-fighting composition according to the present invention is obtained by following steps: a. 0,36 mol of polyethylenimine with a molecular weight of around 1300 Da is introduced into a reactor equipped with a reflux condenser and a stirrer, the reactor is heated to 50,0 °C,

b. 0,36 mol of dodecyl and / or tetradecyl glycidyl ether is added slowly to the reactor (the reaction is exothermic), said reactor being heated at 70,0 °C for 2 hours,

c. 0,36 mol of ethyl monochloroacetate is added slowly at 70 °C (the reaction is exothermic), and heated at 80-90°C for 3 hours,

d. an aqueous solution of 1,08 mol of sodium monochloroacetate is added slowly to the reactor (the reaction is exothermic), said reactor being heated at 75,0 to 80,0 °C for 3 hours. A polymer is obtained in the form of a viscous liquid with a refractive index of about 1,41, a pH of about 10,5 and a surface tension of about 35,3 mN/m. The obtained polymeric compound is suitable for use in a fire extinguishing composition, providing said composition with excellent fire-fighting properties, a good mobility, viscoelasticity and foam stability.

Example 8

The table below shows a variety of combinations for moieties X, Y and Z which provide the polymeric compound according to the current invention of excellent fire-fighting properties. moiety X moiety Y moiety Z

1 octyl-0-CH2-CH(-OH)-CH2 acetyl

and/or decyl-0-CH2-CH(-0H)- CH2

2 dodecyl-0-CH2-CH(-OH)-CH2 acetyl

and/or tetradecyl-0-CH2-CH(- OH)-CH2

3 neodecyl-0-CH2-CH(-OH)-CH2 acetyl

4 2-ethylhexyl-0-CH2-CH(-0H)- (CH2)4 acetyl

CH2

5 dodecyl-0-CH2-CH(-OH)-CH2 CH2-CH(-0H)-CH2-0- acetyl

and/or tetradecyl-0-CH2-CH(- bisphenolA-0-CH2-CH(- OH)-CH2 OH)-CH2

6 neodecyl-0-CH2-CH(-OH)-CH2 CH2-CH(-0H)-CH2-(0- acetyl

CH2-CH(-CH3)-0)r-CH2- CH(-OH)-CH2 wherein r =

8-10

7 octyl-0-CH2-CH(-OH)-CH2 CH2-CH(-0H)-CH2-(0- acetyl

and/or decyl-0-CH2-CH(-0H)- CH2-CH(-CH3)-0]r-CH2- CH2 CH(-OH)-CH2 wherein r =

8-10

8 octyl-0-CH2-CH(-OH)-CH2 CH2-CH(-0H)-CH2-[0- acetyl

and/or decyl-0-CH2-CH(-0H)- CH2-CH(-CH3)-0]r-CH2- CH2, dodecyl-0-CH2-CH(-OH)- CH(-OH)-CH2 wherein r =

CH2 and/or tetradecyl-0-CH2- 8-10 CH(-OH)-CH2 dodecyl-0-CH2-CH(-OH)-CH2 acetyl and/or tetradecyl-0-CH2-CH(- OH)-CH2 and propyl- polydimethylsiloxane-0-CH2- CH(-OH)-CH2 dodecyl-0-CH2-CH(-OH)-CH2 CH2-CH(-0H)-CH2-0- acetyl and/or tetradecyl-0-CH2-CH(- propyl

OH)-CH2 polydimethylsiloxane- propyl-0-CH2-CH(-OH)-

CH2

C8-alkyl-C(=0) (0=)C-C4-aklyl-C(=0) propionyl C8H17-NH-C(=0)- CH2-CH(-0H)-CH2-(0- acetyl

CH2-CH(-CH3)-0)r-CH2- CH(-OH)-CH2 wherein r =

8-10

CH3-O-(C2-alkyl-O)10-C2-alkyl l-propyl-3- hydroxy- sulfonic acid dodecyl (0=)C-NH-C6-alkyl-NH- acetyl

C(=0)

octyl-0-CH2-CH(-OH)-CH2 C2-alkyl-(0-C2-alkyl) l-propyl-2- and/or decyl-0-CH2-CH(-0H)- hydroxy-3-

CH2 sulfonic acid propyl-polydimethylsiloxane-O- acetyl CH2-CH(-OH)-CH2

dodecyl-0-CH2-CH(-OH)-CH2 CH2-CH(-0H)-CH2-0- acetyl propyl

polydimethylsiloxane- propyl-0-CH2-CH(-OH)-

CH2

tetradecyl-0-CH2-CH(-0H)-CH2 CH2-CH(-0H)-CH2-0- acetyl propyl polydimethylsiloxane- propyl-0-CH2-CH(-OH)-

CH2

The polymeric compounds are suitable for use in a fire extinguishing composition, providing excellent fire-fighting properties, a good mobility, viscoelasticity and foam stability.

Example 9

The table below shows a typical fluorine-free formulation containing two polymers according to embodiments of the present invention, and usable as a water additive in extinguishers for fighting fires of classes A and B. component wt%

water 81,0 - 61,0

glycol ether 0,0 - 0,5

biopolymer 0,0 - 0,3

sugar compound 10,0 20,0

antigel agent 1,0 - 3,0

polymeric compound of the invention A 0,2 1,0

polymeric compound of the invention B 0,6 - 3,0

non-ionic surfactant 3,0 - 5,0

amphoteric surfactant 0,5 - 1,0

anionic surfactant 4,0 - 5,0

buffer solution 0,0 0,1

anticorrosion agent 0,0 0,2

foam stabilizer 0,0 0,2

The fire extinguishing composition yields a stable foam with excellent fire-fighting properties, without the need for fluorinated surfactants or fluorinated polymers. Said composition is considered to be more environmentally safe than other compositions known at present. The fire-fighting composition is in particular suited for fighting fires of classes A and B and has a particularly high foam stability.

Example 10 The table below shows typical fluorine-free foam concentrates containing polymers of the invention and usable at 1 % and 3 % in water for fighting hydrocarbon fires, providing an exceptionally high foam stability.

component 1% concentrate 3% concentrate

(wt %) (wt %)

water 3,7 70,9

sugar compound 8,5 2,3

glycerine 8,0 1,4

polyethyleneglycol 9,5 1,4

anionic surfactant 8,0 1,9 non-ionic surfactant 8,0 3,0

amphoteric surfactant 6,0 2,3

polymeric compound of the invention 48,0 16,6

buffer solution 0,1 0,1 anticorrosion agent 0,2 0,1

Claims

1. A polymeric compound of general formula (I)

wherein

- X is a moiety selected from the group of linear or branched C2-C15-alkyl, CH3-

0-(C2-alkyl-0)r-C2-alkyl, C2-C15-alkyl-0-CH2-CH(-0H)-CH2, C3-C15- cycloalkyl-0-CH2-CH(-OH)-CH2, C6-C15-aryl-0-CH2-CH(-0H)-CH2, linear or branched C2-C15-alkyl-C(=0), C4-C18-alkyl-NH-C(=0), trimethoxysilane-C3- alkyl-0-CH2-CH(-0H)-CH2, polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2, and combinations thereof,

- Y is a moiety selected from the group of CH2-C(=0), linear or branched (C2- C3-alkyl-0)r, linear or branched CH2(-0H)-CH-CH2-0-C2-C15-alkyl-0-CH2-CH(- OH)-CH2, linear or branched CH2(-0H)-CH-CH2-0-(C2-C3-alkyl-0)r-CH2-CH(-

OH)-CH2, (0=)C-C2-C8-alkyl-C(=0), (0=)C-NH-C4-C8-alkyl-NH-C(=0), CH2- CH(-OH)-CH2-0-bisphenolA-0-CH2-CH(-OH)-CH2, CH2-CH(-0H)-CH2-0-C3- alkyl-polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2, and combinations thereof,

- Z is a moiety selected from the group of Cl-C5-alkyl-C(=0)-OH, Cl-C5-alkyl- S(=0)₂-OH, and combinations thereof, and

- wherein r is an integer from 3 to 10,

- wherein n-2, n'-2 are integers from 1 to 40.

2. Polymeric compound according to claim 1, wherein X is a moiety selected from the group of 2-ethylhexyl-0-CH2-CH(-0H)-CH2, octyl-0-CH2-CH(-OH)-CH2, decyl-0-CH2-CH(-0H)-CH2, dodecyl-0-CH2-CH(-OH)-CH2, tetradecyl-0-CH2- CH(-OH)-CH2, neodecyl-0-CH2-CH(-OH)-CH2, trimethoxysilane-C3-alkyl-0- CH2-CH(-OH)-CH2, polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2, and combinations thereof.

3. Polymeric compound according to claim 1 or 2, wherein Y is a moiety selected from the group of CH2(-0H)-CH-CH2-0-CH2-CH(-CH3)2-CH2-0-CH2-CH(-0H)- CH2, CH2(-0H)-CH-CH2-0-C4-C6-alkyl-0-CH2-CH(-0H)-CH2, (0-CH2-CH(-

CH3)-0)r, (0-CH2-CH2-0)r, wherein r is between 8 and 10, CH2-CH(-OH)-CH2- 0-bisphenolA-0-CH2-CH(-OH)-CH2, CH2-CH(-OH)-CH2-0-C3-alkylpolydimethyl- siloxane-C3-alkyl-0-CH2-CH(-OH)-CH2, and combinations thereof.

4. Polymeric compound according to any of the previous claims 1-3, wherein at least said moiety X is trimethoxysilane-C3-alkyl-0-CH2-CH(-OH)-CH2 or polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2 and / or said moiety Y is CH2-CH(-OH)-CH2-0-C3-alkyl-polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)- CH2.

5. Polymeric compound according to claim 4, wherein X is polydimethylsiloxane-C3- alkyl-0-CH2-CH(-0H)-CH2.

6. Polymeric compound according to claim 4, wherein Y is CH2-CH(-0H)-CH2-0-C3- alkyl-polydimethylsiloxane-C3-alkyl-0-CH2-CH(-OH)-CH2 and X is a moiety selected from the group of 2-ethylhexyl-0-CH2-CH(-0H)-CH2, octyl-0-CH2-CH(- OH)-CH2, decyl-0-CH2-CH(-0H)-CH2, dodecyl-0-CH2-CH(-OH)-CH2, tetradecyl- 0-CH2-CH(-0H)-CH2, neodecyl-0-CH2-CH(-OH)-CH2, and combinations thereof.

7. Polymeric compound according to any of the previous claims 1-6, wherein Z is selected from the group of Cl-C2-alkyl-C(=0)-OH, C3-alkyl-S(=0)₂-0H, and combinations thereof.

8. Use of at least one polymeric compound according to any of the previous claims 1-7 in, or in the production of, a fire extinguishing composition.

9. Use according to claim 8, wherein said fire extinguishing composition is a fluorine- free composition for extinguishing fires of classes A and / or B.

10. Fire extinguishing composition comprising one or more polymeric compounds according to any of the claims 1-7.

11. Fire extinguishing composition according to claim 10, wherein said composition is fluorine-free.

12. Fire extinguishing composition according to claim 10 or 11, wherein said polymeric compounds have a concentration of between 0,10 and 60,00 wt% of the total composition.

13. Fire extinguishing composition according to any of the previous claims 10-12, wherein said composition comprises at least two different polymeric compounds according to any of the claims 1-7, said polymeric compounds both being present in a concentration of between 0,05 and 30,00 wt%.

14. Fire extinguishing composition according to any of the previous claimslO-13, wherein said composition comprises at least three different polymeric compounds according to any of the claims 1-7.

15. Fire extinguishing composition according to any of the previous claimslO-14, wherein said composition comprises at least one surfactant chosen from the group of non-ionic surfactants, anionic surfactants and amphoteric surfactants.

16. Fire extinguishing composition according to claim 15, wherein said composition comprises 0,50 to 10,0 wt% of a non-ionic surfactant, 0,50 to 10,0 wt% of an anionic surfactant and 0,50 to 10,50 wt% of an amphoteric surfactant.

17. A method for the production of a polymeric compound of general formula (I)

or of general formula (P) comprising the steps of:

a. providing a polyethylene imine of formula (CH₂-N(-CH2-CH2-NH₂)-CH2- CH₂-NH-CH₂)n-2, comprising a plurality of reactive NH₂-groups,

b. reacting said polyethylene imine with a glycidyl ether of general formula (III), a tosylate of general formula X-O-Ts, an acyl chloride of general formula CI-C(=0)-Cl-C12-alkyl, an isocyanate of general formula 0=C=N-Cl-C12-alkyl, or combinations thereof,

c. optionally, reacting the reaction product of step b with a diglycidyl ether of general formula (IV), a di-tosylate of general formula Ts-0-(CH2-CH2- 0)r-Ts, a dicarboxylic acid chloride of general formula CI-C(=0)-(CH2)r- C-(=0)-CI or CI-C(=0)-(0-CH2-CH2)r-C-(=0)-CI, a di-isocyanate of general formula 0=C=N-(CH2)r-N=C=0, or combinations thereof, wherein Y is a moiety selected from the group of CH2-C(=0), linear or branched (C2-C3-alkyl-0)r, linear or branched C2-C15-alkyl, linear or branched (C2-C3-alkyl-0)r, (0=)C-C2-C8-alkyl-C(=0), (0=)C-NH-C4-C8- alkyi-NH-C(=0), bisphenolA, C3-alkyl-polydimethylsiloxane-C3-alkyl, wherein r is an integer between 3 and 10, and combinations thereof, and d. reacting the reaction product of step b or c with a compound selected from the group of sodium chloroacetate, beta-propiolacton, acrylic acid, 1,3- propiosultone, and combinations thereof.

18. Method according to claim 17, wherein said glycidyl ether is selected from the group of 2-ethylhexyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, dodecyl glycedyl ether, tetradecyl glycidyl ether, glycidyl neodecanoate, and combinations thereof.

19. Method according to claim 17 or 18, wherein said diglycidyl ether is selected from the group of neoptentyl glycol diglycidyl ether, 1-4-butanediol diglycidyl ether, 1,6-hexanodiol diglycidyl ether, polypropyleneeglycol diglycidyl ether, and combinations thereof.

20. Method according to any of the previous claimsl7-19, wherein the reaction product of step b is reacted with glycidyl ether terminated propyl- polydimethylsiloxane or propyl-trimethoxysilane before proceeding to step c.

21. Method according to any of the previous claimsl7-20, wherein the reaction product of step b or c is reacted with a diglycidyl ether terminated propyl- polydimethylsiloxane before proceeding to step d.

22. Method according to any of the previous claimsl7-21, wherein said polyethylene imine is reacted with the glycidyl ether of general formula (III) in step b at a temperature of between 60,0 and 80,0 °C during 30 to 90 minutes.

23. Method according to any of the previous claimsl7-22, wherein the reaction product of step b is reacted with the diglycidyl ether of general formula (IV) in step c at a temperature of between 60,0 and 80,0 °C during 30 to 90 minutes.

24. Method according to any of the previous claimsl7-23, wherein the reaction product of step c is reacted with sodium chloroacetate, beta-propiolacton or 1,3- propiosultone in step d at a temperature of between 75,0 and 85,0 °C during 30 to 90 minutes.

25. Method according to any of the previous claimsl7-24 for the production of a polymeric compound according to any of the claimsl-7.