DE102007050839A1 - Carbohydrate-based additives with adhesive effect for aqueous fire and fire protection agents, their preparation and use - Google Patents

Abstract

The present invention describes the preparation and use of crosslinked gel materials based on cationically modified polysaccharides which can be used on both porous surfaces, e.g. B. of wood or paper, as well as adhere to smooth surfaces and thereby have a much longer effectiveness as a fire-resistant additive. Also, the use of crosslinked cationized polysaccharide derivatives as an additive in aqueous formulations that make both preventive fire protection and extinguishing fires more efficient is the subject of the present invention.

Description

The The present invention describes the preparation and use of crosslinked gel materials based on cationically modified Polysaccharides, which can be used on both porous surfaces, z. As wood or paper, as well as on smooth surfaces adhere and thereby a much longer effectiveness than Fire protection additive have. Likewise, the use of networked cationized polysaccharide derivatives as an additive in aqueous Formulations that include both preventive fire safety as well make the extinguishing of fires more efficient, Subject of the present invention.

Out In practice, a variety of water additives for active and known preventive firefighting. In the active Firefighting serve these u. a. to, the rheological Properties of the extinguishing agent (surface tension), Delayed water release more extinguishing agent to transport into the fire zone and thus a more efficient fire fighting to allow, as well as by suitable flame retardant additives significantly enhance the effect of the extinguishing agent. Preventive fire fighting means u. a. the Applying temporary protective coatings on nearby the surface of the fire to spread delay the fire as effectively as possible. Important additional properties for such Water additives are therefore u. a. environmental, good adhesion to all types of surfaces and excellent swelling capacity.

In The patent literature is a large number of such Water additives based on both synthetic as well as from renewable raw materials obtained polymers were. They are based on different synthesis and formulation principles almost exclusively unmodified or anionically modified Polymers used.

That's how it describes DE 43 36 319 the use of a crosslinked polycarboxylate, which is granulated with the addition of silicates, polyethylene glycol and ammonium polyphosphate and added to the extinguishing water as needed. Comparable systems, which additionally contain a dye to mark already sprayed areas, are available in WO 2005/014115 described.

Water-in-water polymer dispersions using crosslinked acrylate and acrylamide polymers are disclosed in U.S. Pat DE 100 41 394 called. These systems can also be polymerized with the addition of certain emulsifiers in inverse emulsion, wherein ligroin or white oil acts as a continuous phase, described in DE 100 41 395 . US 6,245,252 and AU 2002 257 580 , These patents are mentioned for a variety of other patents describing variations in the polymer composition and in the use of other additives or manufacturing technologies. However, the essential polymer component here are always polycarboxylates or polysulfonates.

The use of fire protection additives from renewable raw materials is already carried out in some writings. This is how In DE 198 59 123 starch phosphate prepared by using urea as extinguishing water additive without further details. Gels made from carbohydrates with metal-containing crosslinkers, such as. B. guar gum, be in WO 2006/032130 described as efficient, salt-stable extinguishing water additives.

Also monomeric carbohydrates (sodium heptagluconate) can act as a fire retardant in combination with certain amino phosphonates by the formation of a dense fullerene layer upon exposure to heat ( DE 10 2005 003 167 ). All these patents have in common that the adhesion of the fire protection additive to different surfaces (horizontal, vertical, on the ceiling) is insufficient.

essential Deficiency of many aqueous fire protection formulations is their insufficient adhesion especially on non-horizontal Surfaces. It is well known that these are generally are negatively charged. Technically, so far the liability of the extinguishing agent through the use of surfactant-containing extinguishing foams realized. The disadvantage here, however, the temporary Durability of the foam and the surfactant load of the environment.

outgoing It was thus the task of these disadvantages of the prior art the present invention to provide crosslinked gel materials, which has excellent liability or adhesion, in particular on non-horizontal surfaces. These gel materials should also be characterized by an excellent fire retardant Property, both fire extinguishing and fire prevention of wetted objects.

These Task is with the method for the production of crosslinked gel materials according to claim 1 and the crosslinked gel materials solved according to claim 22. Likewise present invention, an adhesion promoting fire and fire retardant according to claim 24, wherein the aforementioned Gel materials are included. Uses of the fire and Fire retardants are mentioned in claim 27. The respectively Dependent dependent claims make it advantageous Further developments.

• a) mindestens ein aus einem entsprechenden Polysaccharid hergestelltes, mit einer kationischen Funktionalität versehenes, kationisch geladenes Poly saccharidderivat in mindestens einem Lösungsmittel suspendiert und
• b) mit mindestens einem Vernetzungsmittel homogenisiert und zur Reaktion gebracht wird.

Thus, according to the invention, there is provided a process for producing crosslinked gel materials, wherein

• a) at least one prepared from a corresponding polysaccharide, provided with a cationic functionality, cationically charged poly saccharidderivat in at least one solvent and suspended
• b) is homogenized with at least one crosslinking agent and reacted.

there It was surprisingly found that the crosslinking of commercial cationic polysaccharides with various fire retardant crosslinkers too cold swelling gel materials with very good effectiveness as Fire protection or fire extinguishing additive leads. When Basic materials are in principle all carbohydrates, the bear quaternary nitrogen atoms, in particular cationized Guar gum and cationic starches. Will these with Crosslinking substances which themselves have flame retardant properties, brought to reaction, formed in water cold swelling gel materials, which have a clear flame-retardant effect.

The Implementation with the carbohydrates is technologically advantageous in the dry process, for example in the kneader with subsequent Contact drying (eg waffle iron, plate, roller,) or in a twin-screw extruder. For better processability, plasticizers, preferably should also have flame retardant properties (eg dimethylurea) be used. The resulting dry product is subsequently ground, sifted and then dissolved in water / swollen become.

mindestens eines Ammoniumalkyl(meth)acrylat-Derivats der allgemeinen Formel II

und/oder mindestens eines Ammoniumalkylderivats der allgemeinen Formel III

herstellen, wobei in den Formeln I, II und/oder III unabhängig voneinander
R lineares oder verzweigtes C₁-C₈ Alkyl, C₆-C₁₂ Aryl oder lineares oder verzweigtes C₆-C₁₈ Aralykly,
R¹ Wasserstoff, lineares oder verzweigtes C₁-C₈ Alkyl, C₆-C₁₂ Aryl oder lineares oder verzweigtes C₆-C₁₈ Aralkly,
X Fluorid, Chlorid, Bromid, Iodid, Triflat, Tosylat,
n 1 bis 12 und
Y Chlor, Brom, Iod, Triflat oder Tosylat
bedeuten.In an advantageous embodiment, the cationically charged polysaccharide derivative can be prepared by reaction with at least one or grafting of at least one (2,3-epoxyalkyl) ammonium derivative of the general formula I

at least one ammonium alkyl (meth) acrylate derivative of the general formula II

and / or at least one Ammoniumalkylderivats of the general formula III

in which, in the formulas I, II and / or III independently of one another
R is linear or branched C ₁ -C ₈ alkyl, C ₆ -C ₁₂ aryl or linear or branched C ₆ -C ₁₈ aralyclyl,
R ^{1 is} hydrogen, linear or branched C ₁ -C ₈ alkyl, C ₆ -C ₁₂ aryl or linear or branched C ₆ -C ₁₈ aralkly,
X fluoride, chloride, bromide, iodide, triflate, tosylate,
n 1 to 12 and
Y is chlorine, bromine, iodine, triflate or tosylate
mean.

such Reaction products are already in large numbers from the State of the art and are preferred as starting materials in the present used according to the invention crosslinking reaction.

• a) das (2,3-Epoxyalkyl)ammonium-Derivat der allgemeinenen Formel I 2,3-Epoxypropyl-N,N,N,-trimethylammoniumchlorid ist,
• b) das Ammoniumalkyl(meth)acrylat-Derivat der allgemeinen Formel II ausgewählt ist aus der Gruppe bestehend aus (N,N,N-Trimethylammoniumethyl)acrylat, (N,N,N-Trimethylammoniumethyl)methacrylat,
• c) das Ammoniumalkylderivat der allgemeinen Formel III ausgewählt ist aus der Gruppe bestehend aus N,N,N-Trimethylammoniumehtylchlorid.

A special, advantageous selection of the aforementioned reagents provides that

• a) the (2,3-epoxyalkyl) ammonium derivative of the general formula I is 2,3-epoxypropyl-N, N, N, -trimethylammonium chloride,
• b) the ammonium alkyl (meth) acrylate derivative of the general formula II is selected from the group consisting of (N, N, N-trimethylammoniumethyl) acrylate, (N, N, N-trimethylammoniumethyl) methacrylate,
• c) the ammonium alkyl derivative of the general formula III is selected from the group consisting of N, N, N-trimethylammonium ethyl chloride.

The underlying polysaccharide by reaction with the previously mentioned reagents, for example, the reagents of the formulas I, II and / or III to the cationically charged polysaccharide derivative is implemented and thereby with a cationic functionality is preferably selected from the group consisting of carbohydrates, guar gum, chitosan, starches, Amyloses, amylopectin and / or mixtures thereof. The underlying lying polysaccharide scaffold is thereby by the reaction not with the reagents of the general formulas I, II and / or III touched, there is only a partial cationization or grafting the corresponding reagents to an OH functionality the underlying monosaccharide units.

Preferably The implementation is not complete, but only partial, resulting in polysaccharide derivatives whose Degree of substitution (DS) with respect to cationic functionalities 0.005 ≤ DS ≤ 0.5, preferably 0.02 ≦ DS ≦ 0.2, more preferably 0.05 ≤ DS ≤ 0.15.

The polysaccharide derivatives used according to the invention preferably have a weight-average molecular weight of 5 × 10 ⁴ to 5 × 10 ⁷ g / mol, preferably 1 × 10 ⁵ to 2 × 10 ⁷ g / mol.

In a further advantageous embodiment, the aforementioned molecular weight while a broad distribution.

Farther it is also advantageous if the crosslinking agent is at least two, the free OH functionalities of the cationic polysaccharide derivative having crosslinking, functional groups.

A special selection of the crosslinking agent provides that that at least a crosslinking agent is selected from the group consisting from melamine-formaldehyde precondensates, methylolmelamines, urea derivatives, especially reactive urea derivatives, methylol ureas, Orthosilicates, sodium trimetaphosphate, borates, polyborates, dimethyloldihydroxyethyleneurea and / or mixtures thereof.

Especially There are advantages when the at least one crosslinking agent with respect to the polysaccharide derivative in a weight ratio from 0.1% by weight to 50% by weight, preferably from 1% by weight to 20% by weight, particularly preferably from 1 wt .-% to 10 wt .-% is used.

Prefers is the reaction for the preparation of the inventive crosslinked gel materials in water. The weight ratio of the solvent based on the cationic polysaccharide derivative is from 50 to 300 wt .-%, preferably 75 to 250 wt .-%, particularly preferably 80 to 120% by weight.

at The reaction may also contain other additives in the reaction mixture be incorporated. Advantageously, additives are used, which have self-fire retardant properties. Especially the additives are selected from the group from plasticizers, such. As alkyl ureas, antioxidants, surfactants, Salts and / or mixtures thereof. The weight ratio the other additives with respect to the polysaccharide derivative is 1 wt .-% to 50 wt .-%, preferably 5 wt .-% to 25% by weight.

The Reaction mixture is in a further advantageous embodiment at temperatures between 5 and 95 ° C, preferably between 10 and 50 ° C, more preferably between 15 and 35 ° C homogenized.

To Completion of the homogenization or the implementation is advantageously carried out a drying, in particular a reactive drying of the product. It is preferred if the reactive drying at a temperature above 40 ° C, preferably between 90 and 200 ° C, more preferably carried out between 110 and 170 ° C. becomes.

The Reactive drying takes place in particular with simultaneous mechanical Mixing the product, for example in a contact dryer, by roller drying and / or by extrusion.

Further it is beneficial if, after the reactive drying, the product to a mean particle size of 0.02 and 2 mm, preferably from 0.05 and 1.5 mm, particularly preferably from 0.05 ground to 1 mm and more preferably from 0.1 to 0.5 mm and screened becomes.

The can be defined above reaction steps a) and b) be carried out sequentially or simultaneously. This also applies to the addition of additives, which accordingly both in step a) and in step b) can be added.

According to the invention also provided a crosslinked gel material that after a can be prepared in the above-described method.

The crosslinked gel material is characterized in particular by the advantageous property of having one per gram of gel material Water absorbency of 50 to 1000 g of water, preferred from 75 to 750 g of water, more preferably from 150 to 450 g of water having.

Farther According to the invention, an adhesion-promoting fire and fire retardant provided by the one in the foregoing contains described crosslinked gel material. advantageously, the gel material is included as an aqueous dispersion. In particular, in this case, the concentration of the gel material in the dispersion 0.1 to 50 wt .-%, preferably 0.5 to 5 wt .-%

According to the invention the fire and fire retardant fire extinguishing and / or for flame retardation of articles. there is provided that the objects with the fire and fire retardant impregnated, sprayed, soaked and / or be painted.

This Invention will be based on the following examples and investigations are explained in more detail without the embodiments mentioned therein, the invention in any Way to restrict.

embodiments

Synthesis of the invention Adhesive fire and fire retardants

example 1

Uncrosslinked cationic potato starches as reference substances (sample A)

50 g of cationic potato starch (2-hydroxypropyl-1-trimethylammonium chloride ether of starch, corresponding to the cationized starch derivative from a reaction of starch with the reagent of general formula 1, wherein R = Me, R ¹ = H, n = 1, X = Cl) with a DS of 0.07 (Empresol NE 60, Emsland-Stärke GmbH, Emlichheim, Germany) are slurried at room temperature in 45 g of demineralized water and homogenized for 60 minutes in a 250 ml laboratory kneader. After ßend another 5 g of demineralized water are added and kneaded at RT for a further 30 minutes. The batch is transferred to a 150 ml contact dryer with an internal thermometer (waffle iron TCM 1000 W) and the water contained in the batch is evaporated at 120 ° C. within 20 minutes. The product obtained from the drying is ground to powder by means of a universal mill (at 20,000 rpm, 1 minute). Subsequently, the coarse particulate fraction in the product by sieving with a sieve bottom ( DIN 4188 ) of mesh size 0.500 mm, the fines of the remaining sieve passage are separated by re-classifying through a test sieve of mesh size 0.125 mm.

(Sample D)

The product remaining in the sieve (sieve overflow) accordingly contains particles of size 0.125 to 0,500 mm. There were obtained 42 g of fractionated product.

Analogous to the procedure of Sample A, sample D was a cationic potato starch (2-hydroxypropyl-1-trimethylammonium chloride ether of starch corresponding to the cationized starch derivative from a reaction of starch with the reagent of general formula 1 wherein R = Me, R ¹ = H, n = 1, X = Cl) with a DS of 0.12 (ZFT 1092, Zuckerforschung Tulln GmbH, Tulln, Austria).

Example 2

Crosslinking of cationic potato starch using melamine-formaldehyde condensates (sample B)

50 g of cationic potato starch (2-hydroxypropyl-1-trimethylammonium chloride ether of starch, corresponding to the cationized starch derivative from a reaction of starch with the reagent of general formula 1, wherein R = Me, R ¹ = H, n = 1, X = Cl) with a DS of 0.07 (Empresol NE 60, Emsland-Stärke GmbH, Emlichheim, Germany) are slurried at room temperature in 45 g of demineralized water and homogenized for 60 minutes in a 250 ml laboratory kneader. Subsequently, a mixture of 5 g of deionized water and 3 g of a melamine-formaldehyde precondensate (Helizarin Fixator LF, BASF) is added and kneaded at RT for a further 30 minutes. The batch is transferred to a 150 ml contact dryer with internal thermometer (waffle iron TCM 1000 W) and the water contained in the batch is evaporated at 150 ° C. within 20 minutes. The product obtained from the drying is ground to powder by means of a universal mill (at 20,000 rpm, 1 minute). Subsequently, the coarse-particulate fraction in the product by sieving with a sieve plate ( DIN 4188 ) of mesh size 0.500 mm, the fines of the remaining sieve passage are separated by re-classifying through a test sieve of mesh size 0.125 mm. The product remaining in the sieve (screen overflow) accordingly contains particles of the size 0.125 to 0.500 mm. There were obtained 38 g of fractionated product.

(Sample E)

Analogously to the procedure of Sample B, Sample E was prepared by crosslinking a cationic potato starch (2-hydroxypropyl-1-trimethylammonium chloride ether of starch corresponding to the cationized starch derivative from a reaction of starch with the reagent of general formula 1 wherein R = Me, R ¹ = H, n = 1, X = Cl) with a DS of 0.12 (ZFT 1092, Zuckerforschung Tulln GmbH, Tulln, Austria).

Example 3

Crosslinking of cationic potato starches by melamine-formaldehyde condensates with the addition of dimethylurea (Sample C)

a) Discontinuous procedure

50 g of cationic potato starch (2-hydroxypropyl-1-trimethylammonium chloride ether of starch, corresponding to the cationized starch derivative from a reaction of starch with the reagent of general formula 1, wherein R = Me, R ¹ = H, n = 1, X = Cl) with a DS of 0.07 (Empresol NE 60, Emsland-Stärke GmbH, Emlichheim, Germany) are slurried at room temperature in 40 g of deionised water in which 8 g of dimethylurea have been dissolved and suspended for 60 minutes in a 250 ml Laboratory kneader homogenized. Subsequently, a mixture of 5 g of deionized water and 3 g of a melamine-formaldehyde precondensate (Helizarin Fixer LF, BASE) is added and kneaded at RT for a further 30 minutes. The batch is transferred to a 150 ml contact dryer with internal thermometer (waffle iron TCM 1000 W) and the water contained in the batch is evaporated at 150 ° C. within 20 minutes. The product obtained from the drying is ground to powder by means of a universal mill (at 20,000 rpm, 1 minute). Subsequently, the coarse-particulate fraction in the product by sieving with a sieve plate ( DIN 4188 ) of mesh size 0.500 mm, the fines of the remaining sieve passage are separated by re-classifying through a test sieve of mesh size 0.125 mm. The product remaining in the sieve (screen overflow) accordingly contains particles of the size 0.125 to 0.500 mm. There were obtained 43 g of fractionated product.

(Sample F)

Sample F is prepared analogously to the procedure of Sample C, there is a cationic potato starch (2-hydroxypropyl-1-trimethylammonium chloride ether of starch, corresponding to the cationized starch derivative from a reaction of starch with the reagent of general formula 1, wherein R = Me , R ¹ = H, n = 1, X = Cl) with a DS of 0.12 (ZFT 1092, Zuckerforschung Tulln GmbH, Tulln, Austria) as a starch component used.

b) Semicontinuous procedure (Extrusion sample G)

For extrusion is the use of a plasticizer, e.g. Dimethylurea, essential.

In a 250 ml laboratory kneader 60 g of cationic potato starch (2-hydroxypropyl-1-trimethyl ammonium chloride ether of starch, corresponding to the cationized starch derivative from a reaction of starch with the reagent of general formula 1, wherein R = Me, R ¹ = H, n = 1, X = Cl) with a DS of 0.12 (ZFT 1092, Zuckerforschung Tulln GmbH, Tulln, Austria), 10 g of dimethylurea and 3.6 g of a melamine-formaldehyde precondensate (Helizarin Fixer LF, BASF ) mixed with 26 g of water at RT and homogenized for 60 minutes. 10 g of the obtained rubbery material are extruded in a counterrotating twin-screw extruder (MiniLab HAAKE Rheomex CTW5, Thermo Electron Corporation, 90 min ^-1 ) at 120 ° C. The residence time of the material is 15 minutes. The procedure is analogous to Example 3a). There are obtained 4 g of powdery product.

Application example 1

Fire engineering investigation as an adhesion-promoting flame retardant

To quantify the effectiveness of the substances B, C, E, F and G as adhesion promoting fire retardants are based on DIN-EN 532 (Combustion chamber test with sample holder, 1995) and DIN 54336 (Determination of the burning behavior of textiles, perpendicular method, ignition by edge ignition, 1986) carried out the following experiments:
From a filter sheet (500 mm x 500 mm, 80 g / m ² ) of soft filter paper, a specimen of edge length of 200 mm and width of 80 mm is taken so that the specimen has a mass of 1.28 ± 0.01 g ,

The specimen is then immersed in a 1% aqueous solution of the sample to be examined (A-G) and moistened. After soaking, the test specimen is removed from the solution, suspended on a sample holder, dried for 15 or 20 minutes and the mass increase of the specimen determined by differential weighing. Then the specimen is clamped vertically in a ventilated combustion chamber and at the bottom with a propane gas burner defined flame length permanent (different from DIN 54336 ) flames. The time of ignition and the spread of fire within the specimen are measured. For each sample solution (A-G), four test specimens are prepared, of which two test pieces are dried at RT for 15 and 20 minutes, respectively. The values given in Table 1 are thus mean values from 4 measurements each. Table 1 - Results of Specimens A to G sample Mass increase after immersion in [g] Ignition time [s] Fire spread in [cm] water 3.37 ± 0.24 2.5 ± 0.6 Burning after 51 ± 9 s Sample A reference 3.76 ± 0.01 5.0 ± 1.6 7.3 ± 8.5 cm Sample B 4.04 ± 0.02 4.3 ± 1.0 2.9 ± 0.5 cm Sample C 4.23 ± 0.10 4.8 ± 1.3 3.4 ± 0.5 cm Sample D reference 4.13 ± 0.30 8.0 ± 1.4 2,0 ± 0,4 cm Sample E 5.97 ± 0.10 8.0 ± 1.4 2.9 ± 1.0 cm Sample F 6.02 ± 0.20 18.8 ± 7.5 2.9 ± 0.6 cm Sample G 5.83 ± 0.20 16.0 ± 5.5 3,0 ± 0,4 cm

Application Example 2

Fire technical application investigation as adhesion-promoting extinguishing water additive

A stack of wood (wooden crib 8A after DIN EN 3 , Length 800 cm) is ignited with 0.5 l of gasoline, which is mounted in a fire tank of 0.4 m × 0.8 m on a water cushion of 5 cm height. After a burning time of approx. 1 minute the ignition flame goes out. The woodpile is left to free burn for another 5 minutes. After a total firing time of 6 minutes, the extinguishing test begins with a manual fire extinguisher (Lechler axial full cone nozzle type 460.404, pressure in the fire extinguisher 6 bar continuous pressure, throughput of the nozzle 1.54 l / mm) containing 10 l of corresponding extinguishing agent. A successful deletion attempt must lead to extinguishing success within the next 6 minutes, since otherwise too much of the fire object is already burned.

First pure tap water is used as extinguishing agent in the second fire test the tap water is a mass percent Sample F added. The deletion test with pure tap water shows that the fire object with the applied application rate on extinguishing agent can not be deleted. At all burning wood surfaces will be after a short time again flammable gases and vapors for the flames delivered.

at Use of the extinguishing agent, which is an admixture of sample F, the fire object will be safe within 5 minutes deleted, it remains 1.5 1 solution in the hand fire extinguisher.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 4336319 [0004]
• WO 2005/014115 [0004]
• - DE 10041394 [0005]
• - DE 10041395 [0005]
• US 6245252 [0005]
• - AU 2002257580 [0005]
• - DE 19859123 [0006]
• - WO 2006/032130 [0006]
• - DE 102005003167 [0007]

Cited non-patent literature

• - DIN 4188 [0036]
• - DIN 4188 [0039]
• - DIN 4188 [0041]
• - DIN EN 532 [0045]
• - DIN 54336 [0045]
• - DIN 54336 [0046]
• - DIN EN 3 [0047]

Claims (27)

Process for the preparation of crosslinked gel materials, in which a) at least one of a corresponding polysaccharide manufactured, provided with a cationic functionality, cationically charged polysaccharide derivative in at least one solvent suspended and b) homogenized with at least one crosslinking agent and reacted. A method according to claim 1, characterized in that the cationically charged polysaccharide derivative is selected from the group consisting of reaction products of the corresponding polysaccharide with a) at least one (2,3-Epokyalkyl) ammonium derivative of the general formula I.

b) at least one ammonium alkyl (meth) acrylate derivative of the general formula II

and / or c) at least one ammonium alkyl derivative of the general formula III

where in the formulas I, II and / or III independently of one another R is linear or branched C ₁ -C ₈ -alkyl, C ₆ -C ₁₂ -aryl or linear or branched C ₆ -C ₁₈ -aryl, R ^{1 is} hydrogen, linear or branched C ₁ -C ₈ alkyl, C ₆ -C ₁₂ aryl or linear or branched C ₆ -C ₁₈ aralklyl, X ^- fluoride, chloride, bromide, iodide, triflate, tosylate, n 1 to 12 and Y is chlorine, bromine, iodine, triflate or Signify tosylate. Method according to the preceding claim, characterized that  a) the (2,3-epoxyalkyl) ammonium derivative of the general Formula I is 2,3-epoxypropyl-N, N, N, -trimethylammonium chloride,  b) the ammonium alkyl (meth) acrylate derivative of general formula II is selected from the group consisting of (N, N, N-trimethylammoniumethyl) acrylate, (N, N, N-trimethylammonium ethyl) methacrylate, c) the ammonium alkyl derivative the general formula III is selected from the group consisting of N, N, N-trimethylammonium ethylchloride. Method according to one of the preceding claims, characterized in that the polysaccharide is selected is from the group consisting of carbohydrates, guar gum, chitosan, Starches, amyloses, amylopectin and / or mixtures thereof. Process according to the preceding claim, characterized in that the polysaccharide derivatives have a degree of substitution (DS) with respect to the cationic functionalities of 0.005 ≤ DS ≤ 0.5, preferably 0.02 ≤ DS ≤ 0.2, more preferably of 0.05 ≤ DS ≤ 0.15. Method according to one of the preceding claims, characterized in that the polysaccharide derivatives have a weight average molecular weight of 5 x 10 ⁴ to 5 x 10 ⁷ g / mol, preferably 1 x 10 ⁵ to 2 x 10 ⁷ g / mol. Method according to one of the preceding claims, characterized in that the crosslinking agent comprises at least two, the free OH functionalities of the cationic polysaccharide derivative having crosslinking, functional groups. Method according to one of the preceding claims, characterized in that the at least one crosslinking agent is selected from the group consisting of melamine-formaldehyde precondensates, Methylol melamines, urea derivatives, in particular reactive urea derivatives, Methylolureas, orthosilicates, sodium trimetaphosphate, borates, Polyboraten, Dimethyloldihydroxyethylenharnstoff and / or mixtures thereof. Method according to one of the preceding claims, characterized in that the at least one crosslinking agent with respect to the polysaccharide derivative in a weight ratio from 0.1% by weight to 50% by weight, preferably from 1% by weight to 20% by weight, particularly preferably from 1 wt .-% to 10 wt .-% is used. Method according to one of the preceding claims, characterized in that the solvent is water. Method according to one of the preceding claims, characterized in that the weight ratio of Solvent based on the cationic polysaccharide derivative from 50 to 300% by weight, preferably from 75 to 250% by weight, especially preferably from 80 to 120 wt .-% is. Method according to one of the preceding claims, characterized in that in the implementation of further additives, selected from the group consisting of additives with fire retardant Properties, plasticizers, such. As alkyl ureas, antioxidants, Surfactants, salts and / or mixtures thereof are added. Method according to the preceding claim, characterized characterized in that the further additives with respect Polysaccharide derivatives in a weight ratio of 1 Wt .-% to 50 wt .-%, preferably from 5 wt .-% to 25 wt .-% used become. Method according to one of the preceding claims, characterized in that the homogenization at temperatures between 5 and 95 ° C, preferably between 10 and 50 ° C, more preferably carried out between 15 and 35 ° C. becomes. Method according to one of the preceding claims, characterized in that after completion of the homogenization a reactive drying of the product takes place. Method according to the preceding claim, characterized characterized in that the reactive drying at a temperature above 40 ° C, preferably between 90 and 200 ° C, especially preferably carried out between 110 and 170 ° C. becomes. Method according to one of the two preceding claims, characterized in that the drying in a contact dryer, by roller drying and / or by extrusion. Method according to one of the preceding claims, characterized in that after the reactive drying, the product to a mean particle size of 0.02 and 2 mm, preferably from 0.05 and 1.5 mm, particularly preferably from 0.05 to 1 mm and more preferably from 0.1 to 0.5 mm is ground and screened. Method according to one of the preceding claims, characterized in that steps a) and b) successively or simultaneously. Method according to one of the preceding claims, characterized in that during step a) the further Additives are added. Crosslinked gel material, producible according to one of the previous claims. Crosslinked gel material according to the preceding claim, characterized in that the gel material per gram of gel material a water absorption capacity of 50 to 1000 g of water, preferably from 75 to 750 g of water, more preferably from 150 to 450 g of water. Adhesive fire and fire retardant, containing a cross-linked gel material according to one of the two preceding Claims. Fire and fire retardant after previous Claim, characterized in that the crosslinked gel material is present as an aqueous dispersion. Fire and fire retardant after previous Claim, characterized in that the concentration of the gel material in the dispersion of 0.1 to 50% by weight, preferably 0.5 to 5% by weight is. Use of a fire and fire retardant after one of claims 23 to 25 for fire extinction and / or for flame retardation of articles. Use according to the preceding claim, characterized characterized in that the objects with the fire and Fire retardant impregnated, sprayed, soaked and / or painted.