DE3024738A1 - Fire and heat protection material - comprising (in)organic binder and hydrated aluminium sulphate - Google Patents

Abstract

Fire- and heat protection material comprises binder and filler consisting of hydrated aluminium sulphate Al2(SO4)3.nH2O in which n=14-18, in an amt. of more than 30 wt.% w.r.t. the mixt. Typical binders are natural and synthetic polymers, asphalts, bitumens, latexes and solns. of the above, and inorganic materials such as cement, concrete, gypsum and silicates. The hydrated aluminium sulphate may be produced in situ by adding the aluminium sulphate as an aq. soln. and forming the hydrated salt in the mixt. by heating when used as the protection material. The prods. may be made e.g. in the form of hard sheets, tapes, films, putties or paints and may be reinforced with materials such as glass cloths, asbestos cloth, textile fabric or metal wires. The prods. are esp. useful as fire protection in building applications and for proteeting explosive and inflammable materials such as ammunition, fuel, explosives, etc., against heat. The materials are used for the construction of or the lining or coating of receptacles, cases, boxes, doors, rooms, bulkheads in aircraft and ships, etc..

Description

HEAT AND FIRE PROTECTION MATERIAL AND PROCEDURE FOR

ITS PRODUCTION HEAT AND FIRE PROTECTION MATERIAL AS WELL AS A METHOD FOR THE PRODUCTION THEREOF, heat and fire protection materials are used in addition, flammable and explosive materials as well as buildings and other units from exposure to high temperatures and open flames (e.g. in the event of a fire) to protect. The basic task of such materials is that Prevent or prevent the penetration of intense heat for a maximum period of time to block.

Flammable, explosive and other materials, buildings and structures, which require protection from the effects of high temperatures and naked flames, can either be covered with a layer of a heat and fire protection material be or it can be the flammable, explosive and other materials in rooms, Containers, boxes and packaging made of or with the protective material are coated with it, are stored. This protects the materials in question from catching fire or exploding in the event of a fire breakout.

The above heat and fire protection material can be used around stationary containers that contain fuels and combustible substances (e.g. crude oil, Petrol, paraffin, gas oil, etc.).

However, it can also be used to coat fuel containers use of means of transport such as airplanes, helicopters, automobiles, Tanks, launches and ships and the like .. It can also be used to protect stationary storage are used by explosives and ammunition as well as for the protection of ammunition, transported by airplanes, helicopters, ships, launches, tanks, etc. will. It is also used to manufacture safes, lockers, warehouses, Magazines, for museum exhibitions, collections, etc.

It can also be used for fire-resistant partitions, partitions, walls, Doors etc. used in various buildings as well as ships and airplanes will.

In addition, the heat and fire protection material can also be used to protect load-bearing Components of various buildings are used where it is likely is that in case of fire they are destroyed due to the loss of strength, what e.g.

for steel components of high-rise buildings, aluminum components etc. applies.

The examples given above are of course by no means exhaustive the conceivable areas of application of a heat and fire protection material.

The basic shortcomings of known heat protection materials are given below: a) The protection time is short. The Heat protection time is measured as follows: one side of a sample is set to 7000C to 8000C heated. The time it takes to get the other side to 1500C to 2000C to heat is measured.

This results in the heat insulation on this side. The currently known best materials have a protection time of no more than 30 to 45 minutes for a layer with a thickness of 10 mm. The protection time is a fundamental one Property of such a material.

b) Each material has a limited number of uses. It can either be used as a covering or merely as a paint layer or only 'used as a sealant. A very limited number of materials is only suitable for several of the purposes mentioned above. ° c) Very few Materials can be used for structural purposes as they are not sufficient Have strength, e.g. to produce components or parts intended for this purpose. Few of them are easily machinable.

d) The majority of known heat protection materials give when burning releases toxic substances, smoke, gases and vapors.

The invention is based on the prior art described above the underlying task is to remedy the disadvantages indicated, in particular a heat and To propose fire retardant material that ensures longer heat protection. Further the invention is intended to provide a particularly suitable method of production one Propose such heat and fire protection material.

The invention is a material for protection against fire and Heat, which is characterized by being a binder and a filler from a hydrated aluminum sulfate of the general formula Al2 (SO4) 3 n H2O, wherein n = 14 to 18, in an amount of more than 30 wt .-%, based on the Mixture, contains.

The heat and fire protection material according to the invention has an exceptional one long heat protection time that is more than twice as long as the best currently available available materials. This heat protection time is 90 to 100 minutes instead from 30 to 45 minutes with the best current materials, the material can be manufactured as a type of plastic suitable for construction purposes. Different Objects, structural units, partitions, containers, boxes and the like. Can without further can be made from it.

The heat and fire protection material according to the invention can therefore a wide range of application areas. It can be tough or a soft cover or pad, insulation, paint, sealant or processed into a high-strength building material. You can easily do this any materials can be used for reinforcement.

The distinguishing feature of the heat and fire protection material according to the invention exists in comparison to other materials intended for the same purpose are, in that there is some type of polymeric binders along with hydrated Contains aluminum sulphate, which is incorporated as a filler.

This salt absorbs a large amount of heat as it decomposes forms a hard, light residue in the form of a foam. This residue leads to a protection of the decomposition zone against the penetration of heat into the Interior of the zone. This salt combines practically all types of plastics and Rubbers or

Rubber materials. Therefore, depending on the plastic and its treatment or manufacture various products, such as hard tablets, Tapes, films, sealants, paints or paints in general, etc. are manufactured will. In all of the specified cases, the heat protection salt acts as a filler of the polymeric binder and is mixed with it before curing.

Basically the use of aluminum sulfate for the production of fire protection materials together with strongly basic compounds, e.g. NaHCO3 and salts of strong acids are known. It must be pointed out, however, that that Al2 (S04) 3, i.e. common aluminum sulphate, was proposed, while the invention uses a special hydrated aluminum sulfate the formula Al2 (SO4) 3 (14-18) H2O is required. Mixtures of Al2 (SO4) and NaHCO3 tried. It was found that the heat protection time is only 17 minutes. Hydrated aluminum sulfate and aluminum sulfate are what the table below 1 shows to be rated absolutely differently. Thus, the use of conventional Al2 (SO4) 3 does not give the same results as llydated Aluminum sulfate. The exact mechanism that could account for this difference is still there not been resolved.

Table 1 Aluminum sulfate and hydrated aluminum sulfate (for Comparison of opposing properties) Properties of aluminum sulfate hydrated aluminum sulfate chemical formula A12 (SO4) 3 A12 (SO4) 3-18H2O M 342.15 666.42 color white colorless crystal form non-transparent monocrystalline refractive index Powder 1.48 Density (g / cm3) 2.71 1.69 Decomposition temperature in CC 770 86.5 Solubility in hot water (g per 100 g of water) 89 unlimited The in the invention Heat and fire protection material preferably contained amount of hydrated aluminum sulphate, that provides the heat and fire protection effect is between 50 and 75% or even more.

It was found that no heat and fire protection is achieved, when the amount of hydrated aluminum sulfate introduced into the material is below 30%. This can be clearly seen from Example 9. It has been so far No theoretical explanation has yet been found for why the Salary of hydrated aluminum sulfate over 30% and preferably over 50% in principle Changes in the characteristics of the material, especially the new property an exceptionally effective heat and fire protection.

The essence of the invention can be described as follows: 1) A heat and fire protection material based on organic natural and synthetic Compounds (polymers, rubber and rubber materials, oligomers and resins) and inorganic compounds (cement, gypsum, sodium and potassium silicates) as binders as well as containing hydrated aluminum sulfate has the distinguishing feature Marks that to create the heat and fire protection properties a hydrated Aluminum sulfate in an amount greater than 30% by weight of the mixture and preferably greater than 50% by weight of the mixture is incorporated.

2) The hydrated aluminum sulfate has the general formula Al2 (SO4) 3-n H2O (cf. any publication dealing with this material), in which n = 14-18.

This formula applies to the chemically pure form of the hydrated Aluminum sulphate (cf. e.g.

the Merck Index, 1976 edition), whereas the technical product an n-value of 14 to 16, (i.e. 17 to 18% Al 2 O 3, see e.g. the publication by Rhone Progil Co.) has. The use of chemically pure products is obvious in the invention from an economic point of view not justified what is due to the high price of such products. This is especially true because of this, because the heat protection time in the case of chemically pure and technically pure or industrial Products is the same. For this reason, the hydrated aluminum sulfate becomes the Formula Al2 (SO4) 3- 16H2O preferred according to the invention.

The present invention is thus concerned with heat and fire protection materials based on organic and inorganic binders that have a hydrated Contain aluminum sulfate, the fact that to greatly reduce the Materials are used that contain technical aluminum sulphate, is a distinguishing feature.

Another distinguishing feature of the invention is that that a wide number of materials, unsaturated polyesters, epoxy resins, natural and synthetic rubbers and gutta-percha, etc., can be used as binders.

US Pat. No. 2,132,969 discloses a method for the preparation of a surface with a heat-impermeable, insulating layer made of a cell-like substance based on asphalt materials, bitumen materials, phenol / formaldehyde resins (Bakelite) and natural resins (rosin) as binders in a vaporizable Solvent described.

There are various hydrated materials, urea and ammonium carbonate proposed as reactants that have the property of propelling or gas to release. Hydrated aluminum sulfate is also listed in Table II of this Patent specified as a foaming agent in amounts of 5 to 20%.

As shown in Example 9 below, the known method can be used to achieve a heat and fire protection effect as aimed at according to the invention will not pull successfully.

The invention also relates to the heat and heat described Fire protection material a process for the production of such a material. Corresponding In one embodiment of the method according to the invention, all components are including the polymer, resin or any other binder, the hardener and the hydrated aluminum sulfate, mixed together, until a homogeneous mass has been obtained.

In the mass produced, the aluminum sulphate is in the matrix embedded in the binder.

According to a further embodiment of the invention, it is possible initially to form the resin in its polymerized form and then the hydrated aluminum sulfate to be added in the required proportions.

The heat and fire protection material according to the invention can also are thereby consolidated by glass fibers, asbestos fibers or any textile Fabric or even metal wires can be incorporated.

Of course, composite materials can also be envisaged made of two or more layers in the form of a sandwich structure.

According to a further embodiment of the invention, it is possible to have a Use solution of aluminum sulfate so that the hydrated salt is in the required Form formed by a regulated heating step and in the matrix of the binder is embedded. In another proposal, aluminum sulfate is done in-situ the reaction of two or more reactants produced the required Let form of hydrate arise. It is readily apparent that those skilled in the art subject the above measures or features to various modifications can without detracting from the essence of the invention to solve.

The following examples are intended to explain the invention in more detail. The quantities given therein relate to weight, unless otherwise it is said. Examples 2 (description of a double salt), 3 (different Cation), 4 (different anion) and 9 (amount of aluminum sulfate lower than proposed according to the invention) - are not to be assigned to the invention and are only used Comparison purposes.

Example 1 100 parts of Al2 (SO4) 3-16H2O are used as a salt, 30 parts unsaturated polyester resin, 1 part hardener for the polyester resin in the form of methyl ethyl ketone peroxide and 0.1 part of cobalt naphthenate was used as a curing accelerator. The salt will crushed to a fine powder and mixed carefully with the polyester resin.

The curing agent and the accelerator are added to the mixture below Stir given. The mixture is poured into the form of a 10 mm thick plaque and tested for heat protection properties after curing (30 minutes). For the purpose of the test, the board is installed as a roof on a muffle furnace and on Heated to 7500C. A thermocouple and an asbestos sheet are on the opposite side Arranged side of the chalkboard.

The time it takes for the temperature to rise from room temperature to 1700C is required and which is indicated by the thermocouple is determined. This is the heat protection time. The time it takes to heat the opposite Side of the material while this attempt is required is 97 minutes.

Example 2 AlNH4 (SO4) 2.24H2O is used as the salt. All other Components (polyester resin, hardener, accelerator) and test conditions (starch the board -10 mm, oven temperature - 7500C) are as in example 1.

The heat protection time is 30 minutes.

Example 3 Under otherwise the same conditions as in Example 1 only used as salt (NH4) 2SO4 12H2O.

The heat protection time is 20 minutes.

Example 4 Under otherwise the same conditions as in Example 1 used as salt Al Cl3-6H2O. The heat protection time is 16 minutes.

Thus, combining an aluminum cation will give the best results achieved with an anion SO4 (example. 1) with a heat protection time of 97 minutes.

When the chlorine anion is replaced by the sulfate anion, the heat protection time becomes reduced from 97 minutes to 16 minutes (Example 4). When an ammonium cation for which aluminum cation is set, the heat protection time is reduced from 97 Minutes to 20 minutes (example 3). Even if a partial substitution of the Aluminum cation is made by the ammonium cation, the lower the Heat- protection time from 97 minutes to 30 minutes (example 2).

Example 5 100 parts of Al2 (SO4) 3 16H2O as salt, 30 parts unsaturated polyester resin, 10 parts of acetone, 0.2 part of methyl ethyl ketone peroxide (Hardener) and 0.03 parts hardening accelerator in the form of cobalt naphthenate. The semi-liquid mixture given above can be used as a heat protection dye or coating be used. It hardens after application. A 10 mm thick layer of one such a coating shows a heat protection time of 90 minutes.

Example 6 The same composition as in Example 1 is used. Before molding, apply the mixture on both sides with a glass cloth of a starch reinforced by 0.25 mm. A solid building material is obtained, the heat protection time a 10 mm thick layer is 92 minutes.

Example 7 There are 100 parts of powdered Al2 (SO4) 316H2O salt and 25 parts of rubber used. The mixture is on a fine roll mill (sheet mill) molded and in the form of flexible panels, tapes, thick films, etc.

convicted. The heat protection time of a 10 mm thick layer is 105 minutes.

Example 8 100 parts of powdered salt in the form of Al2 (SO4) 3-16H2O, 28 parts of furfural / acetone resin, 0.05 part of benzoyl peroxide (hardener) and 5 parts of acetone are used. The mixture forms a sealant that becomes a strong against Acid and alkali-resistant plastic with high mechanical strength hardens. The heat protection time of a 10 mm thick layer is 95 minutes. Appropriate Results are also obtained when aqueous solutions of sodium silicate, Urea and phenol / formaldehyde resins and other polymeric and oligomeric compounds be used.

Example 9 The experiment described in Example 1 was carried out under the same conditions using the same unsaturated polyester resin repeated, but the amount of Al2 (SO4) 3 16H2O in this case is only 12 Parts fraud. The resulting mixture was made into a 10 mm thick board, as in Example 1, cast. The heat protection time is only 20 minutes.

Claims (12)

Claims T heat and fire protection material, thereby g e k e It should be noted that there is a binder and a filler made from a hydrated Aluminum sulfate of the general formula Al2 (SO4) 3 n H2O, where n = 14 to 18, in an amount of more than 30% by weight, based on the mixture. 2. Heat and fire protection material according to claim 1, characterized in that that it contains one or more of the following materials as a binder: natural and synthetic polymers, rubber, gum and gutta-percha, natural and synthetic resins, natural and synthetic asphalt and bitumen materials, including latex solutions of the above substances and inorganic compounds, such as cement, concrete, plaster of paris and silicates. 3. Heat and fire protection material according to claim 1 or 2, characterized characterized in that the mixture contains more than 50% by weight of A12 (SO4) 3 n H20 are. 4. Heat and fire protection material according to one of claims 1 to 3, characterized in that it is in the form of hard sheets, tapes, films, sealants or paints or paints have been produced. 5. Heat and fire protection material according to at least one of the claims 1 to 4, characterized in that there is Al2 (SO4) 3. 16H2O in technical quality contains as a filler. 6. Heat and fire protection material according to one of claims 1 to 5, characterized in that it is made with glass fabric, asbestos fabric, textile fabric or metal wire is reinforced. 7. Heat and fire protection material according to one of claims 1 to 6, characterized in that it is in the form of a composite material of two or more Layers. 8. Procedure for the production of heat and fire protection material, characterized in that a binder and a filler of a hydrated Aluminum sulfate of the general formula Al2 (SO4) 3 n H2 in which n = 14 to 18, homogeneous are mixed with one another in such proportions that more than 30 wt .-% Aluminum sulfate are included in the mixture. 9. The method according to claim 8, characterized in that the binder organic polymers, natural and synthetic, rubbers, gum and gutta-percha, natural and synthetic resins, natural and synthetic asphalt and bitumen materials including latex solutions of the above substances, inorganic Materials in the form of cement, concrete, plaster and / or silicates can be used. 10. The method according to claim 8 or 9, characterized in that the binder is first processed to its final shape and subsequently Al2 (S04) 3 'n. is incorporated. 11. The method according to any one of claims 8 to 10, characterized in that that the aluminum sulfate is added in the form of an aqueous solution, wherein the hydrated salt in the mixture when used as a protective material, is formed by heating. 12. The method according to any one of claims 8 to 11, characterized in that that the hydrated aluminum sulfate is in-situ in the mixture of two or more Reactants, if it is used as a protective material, is produced.