DE3344156T1 - Fireproof material - Google Patents

Description

P 18 455

Fireproof material

¹ ^ The invention relates to a fire or flame resistant material. In particular, the invention relates to a high-temperature thermal insulation material with selective thermal protection properties at higher temperatures.

Background of the invention

Various materials have heretofore been proposed as flame or fire retardants. For example, were in the field of fire-resistant cable bushings materials based on neoprene, silicone foam, inorganic molding compounds and mineral wool mats. It is true that these known materials result in different ones Usable insulation and fire resistance properties, but none of them at the same time (1) good thermal conductivity under normal conditions of use, (2) expansion and plugging properties at elevated levels Temperatures and (3) heat insulating and mechanically protective properties at very high temperatures, as they occur during a fire.

The invention is to a fire or flame resistant Directed material showing the characteristics mentioned above and, in addition, simultaneously Has processing and flame or fire resistance properties, and when used relatively more cost-effective process and components produced

can be.

General description of the invention

When the material of the invention is on fire or elevated When exposed to temperatures, it shows two basic properties that together make active thermal insulation result, whereby objects to be protected are protected:

(1) when heated to certain elevated temperatures, an endothermic reaction occurs. One of the by-products this reaction is water that in the course of the

. p. Evaporation, which cools the surface exposed to heat;

(2) When the material according to the invention is directly exposed to elevated temperatures, it forms a foaming layer which has a solid, ceramic-like foam structure. This foaming layer shields the remaining non-exposed portion of the thermal protection material from, and has good heat insulating properties at temperatures up to 2300 ⁰ F and

__ higher up.

The thermal insulating properties of the fire or flame resistant material according to the invention, are present only at temperatures above 480 ⁰ F (25O ⁰ C). Under this

Temperature, the material according to the invention is a re-30

relatively good conductor of heat, eliminating excess heat is distributed.

When heating the material according to the invention, when suitable elevated temperature, the foaming layer is formed in the material near the heat source, while the portion of the material that is further away from the heat source is only the

standing endothermic reaction and does not progress to the foamed state.

c The fire or flame resistant material of the present invention, which is halogen free, gives off a small amount of light gray smoke during a fire. In an investigation of its heat protection properties, when a 5 "χ 5" χ 3/8 "-thick specimen was .Q heating on one side to '2200 ⁰ Ff, the temperature on the non-heated side exceeded the temperature on the non-heated side after 30 minutes of treatment, 45O ⁰ F not.

The flame or fire resistant material of the invention can according to one embodiment a thermoplastic Be material that can be extruded, molded, and machine processed. The inventive Material can be stiff or flexible to a certain extent (20% elongation at break). It can also _ be laminated or reinforced with common materials.

The flame or fire resistant material of the invention can be usefully used, for example in the manufacture of walls, floors, ceilings, rooms __ and cabins in which fire protection is required or is desired. It can also be used as a protective cover or be used as a cover for mechanical and electrical equipment, such as electrical cabins or enclosures, Fitting devices, pipes, hoses, cables, plates, cable ducts, doors and hatches. Furthermore

it can be usefully used in the manufacture of covers for containers and pipes that are explosive Ingest or convey content and located in chemical plants, refineries, vehicles, ships and aircraft.

The flame or fire resistant material of the invention can also take the form of granules, where-

where the granules are produced as such or be provided as segmented extrudates. These granules, which are either spherical or any c suitable shape and dimensions can be useful as an insulating material between an inner and an outer surface of a storage unit, such as a storage tank or vessel, in particular with larger dimensions can be used. Because of the

, Q granular form of flame or fire retardant material, it can easily be filled in any space between these surfaces, and the The shape and dimensions of the granules, as well as their properties as bulk material, result in the most suitable Density of the insulation materials.

In its granular form, this forms flame or fire resistant Material, under normal conditions, a "resilient" insulation, which has certain differences between

_o _ the inner and outer surfaces, in the event of a change in structural tolerances and in the event of thermal expansion. Should a fire occur, the granulate becomes an active thermal insulation due to the increased temperature, as mentioned above. Because of the loose

__ Storage of the granules, the granules can become expand during a fire and fuse together, eventually forming a solid, foamed Form an intermediate layer without exerting unfavorable pressure on these surfaces.

Detailed description of the invention

The fire or flame resistant material according to the invention comprises an organic or inorganic matrix ~ _ or a mixture thereof; 50-450 parts by weight of a filler material, the aluminum hydroxide contains, per 100 parts of the matrix, - and 100-600 parts by weight of calcium carbonate or calcium magnesium carbonate per 100 parts of the

trix

The fire or flame resistant material according to the invention

r. material can also be 30-40 parts by weight of one or ο

several of a lubricant, an elasticizing agent, a drying agent, a coloring agent means or an antioxidant, per 100 parts the matrix.

According to one embodiment of the invention, the fire-resistant or flame-resistant material can be purely inorganic Components mixed with water contain.

According to a further embodiment, the matrix

Contain up to 90% by weight of inorganic components, with the remainder being organic building materials, loosening agents, thermoplastic materials, tempered plastic materials, Elastomers, rubbers and the like. Choosing a special composition can depend on how the finished material is to be processed, for example molded, injected, extruded or manufactured as a coating material that is applied to the object to be protected against fire or heat should be applied.

According to a preferred embodiment of the invention, the matrix is the fire or flame resistant material an organic polymer, preferably an ethylene-ethyl acrylate copolymer. At this pre-

The preferred embodiment comprises the filler material Aluminum hydroxide, up to 200 parts by weight thereof may be replaced by mica, per 100 parts of the organic polymer matrix. Also in this embodiment 0-100 parts by weight of the calcium carbonate 35

replaced by sodium silicate, the lubricant being Is paraffin wax, which is present in an amount of about 10 parts by weight per 100 parts of the copolymer matrix

_ ^ _ 33AA Ί

located.

In addition, in this preferred embodiment c form, the elasticizing agent ethylene propene

Rubber, present in an amount of about 11 parts by weight per 100 parts of the copolymer matrix, and the drying agent is a mixture of calcium oxide and wax present in an amount of about 11 parts by weight per 100 parts _in the copolymer matrix.

In addition, in this preferred embodiment, the colorant carbon black is present in one Amount of about 1 part by weight and the antioxidant is poly-trimethyl-dihydroquinoline present in one Amount of about 1.5 parts by weight, each based on 100 parts of the copolymer matrix.

According to a further embodiment of the invention, the fire or flame resistant material can be rigid being. In this embodiment the material contains per 100 parts of organic matrix, preferably ethylene-ethyl acrylate, 50 to 450 parts by weight of a tulle material comprising aluminum hydroxide, 100 to 600 parts "P. Parts by weight of a material selected from the group of calcium carbonate and calcium magnesium carbonate, 8 to 15 parts by weight of a lubricant, 8 to 15 parts by weight of an elasticizing agent, 10 to 15 parts by weight of a drying agent, 1 to 2 parts by weight

of a colorant and 0 to 1.5 parts by weight of an anti-30

oxidans.

A representative fire or flame retardant material according to the invention is one that is used per 100

Parts of ethylene-ethyl acrylate as a matrix, 220 35

Parts by weight of aluminum hydroxide, 2 20 parts by weight of calcium carbonate, 10 parts by weight of a lubricant, 11 parts by weight of an elasticizing agent, 11 parts by weight

a drying agent, 1 part by weight of a colorant and 1.5 parts by weight of an antioxidant.

According to a further embodiment of the invention, the fire-resistant or flame-resistant material can be flexible being. In this embodiment, the material comprises, per 100 parts of organic matrix, again preferably ethylene-ethyl acrylate, 130 to 170 parts by weight

, Q of a filler material comprising aluminum hydroxide, 130 to 170 parts by weight of a material selected from the group of calcium carbonate and calcium magnesium carbonate, 8 to 15 parts by weight of a lubricant, 25 i to 40 parts by weight of an elasticizing agent,

_lt - 10 to 15 parts by weight of a drying agent, 1 to 2 parts by weight of a colorant and 0 to 1.5 parts by weight of an antioxidant.

A representative, flexible fire or flame - "_ permanent material, according to the invention, is one that contains 30 parts by weight of ethylene-ethyl acrylate as a matrix, 150 parts by weight of aluminum hydroxide, 150 parts by weight of calcium carbonate, 10 parts by weight of a lubricant, 30 Parts by weight of an elasticizing agent, 11 parts by weight of a drying agent and 1 part by weight of a Colorant.

If the material according to the invention is used to produce a fire-resistant cable bushing, it expands due to the aluminum hydroxide contained therein, under the influence of strong heat, for example fire or radiant heat, so that the material prevents any passage of smoke, warm gases and flames along the Passages blocked. If _oc a part of the aluminum hydroxide is replaced by mica, either natural or hydrate, so the degree of expansion can be varied within rather wide limits, since the addition of mica material

gives a dough-like consistency and a greater expansion of the material at higher temperatures leads.

In addition, the function of the aluminum hydroxide as an expansion agent can partly, through an organic Expansion agents, such as azodicarbonamide, can be replaced and controlled.

At temperatures above the combustion temperature of the organic components, for example in the case of a fire, the fire-resistant material according to the invention forms a strong foamed layer, with good thermal insulation properties and great thermal stability, ie it withstands heat up to temperatures of 1100 ^° C. The foamed Layer contributes to an effective thermal and mechanical insulation of the coated or with the invention

__ include material covered articles or objects.

Before firing, the material according to the invention is elastic and it resists vibrations and mechanical Load.

According to a further embodiment of the invention, the matrix can be a cement mortar.

Another alternative is to use a __ component as a matrix, so that the finished Product that can be used to coat or paint the object to be protected from fire. Such a component is, for example, a solution or suspension of an alkyd, a polyurethane, a vinyl acetate, an acrylate, or the like.

The invention also relates to a method for producing the above-defined fire or flame

• Ρ-

stable material, which method consists in mixing the components thereof dry, at ambient temperature, ^{extruding the resulting mixture, at a melting temperature of about 150-200 0} C, to form extrudates, in continuous form and dividing these extrudates.

The extrudates in continuous form, for example in strand-like form, can be cut into shorter lengths or into cubes for temporary storage. These divided extrudates are then extruded at a temperature of about 150-200 ⁰ C, so that the covers for protecting against fire products

._ or objects are created.
Ib

Hi

In addition, the inventive flame or fire-resistant material easily extruded to form coatings for cables that are exposed or, more importantly, for cables hidden in walls.

Tests carried out with the flame or fire-resistant material according to the invention show that in the class A fire test, the material is fire

__ resisted for 180 minutes, at which time -2b

point the test was canceled. For comparison purposes, known PVC materials resisted, including im essentially the same conditions for the fire test of class A, the fire only for about 60 minutes, wp-

at this point in time the PVC material is chemically 30th

produced decomposed and hazardous chlorine gas.

According to a further embodiment of the invention, includes the flame or fire retardant material 90-

140 parts by weight of a polymeric matrix material, 14-24 35

Parts by weight of a production lubricant, 8-13 parts by weight Calcium oxide, 140-160 parts by weight calcium carbonate and 140-160 parts by weight aluminum hydroxide. In addition

of this material may also contain an effective amount of a colorant such as carbon black contained.

c. The polymeric material preferably contains 70-100 parts by weight Ethylene-ethyl acrylate copolymer and 20-40 parts by weight synthetic rubber, e.g. EPDM. The manufacturing lubricant preferably comprises 8-12 parts by weight of polyisobutylene and 6-12 parts by weight of paraffin wax.

The flame or fire retardant material of those according to the invention Embodiment described immediately above can be made by mixing its components, essentially in powder form, at a temperature of about

3O ⁰ C, forming a loose mixture. The resulting dry mixture is extruded through a twin-screw extruder, at a temperature of about 130 ⁰ C. The resulting extrudate is partially cooled and passed through a perforated plate where it is cut into granular shape at the exit of the plate. The granules can be stored temporarily at room temperature. The granules can then be processed into tubes or in the form of pipes, using an extrusion press, by gradually heating them up to 125 ° C.

The extruded conduit can be provided with a reinforcement coating and optionally with one

outer protective cover, for example from a 30th

Plastic material is made.

A pipe made of the flame or fire retardant material reinforced in this way is

particularly suitable as a flame-resistant cover for 35

electrical cables.

The reinforced line described above forms, ^

You: exposed to fire conditions, a strong, ; foaming layer with good thermal insulation properties and great thermal stability, the foamed, foamed Layer contributes to an effective thermal and mechanical insulation of the contained therein ■ Cable up. The foamed layer is reinforced by the reinforcement coating supported.

As an example of a flame-resistant or fire-resistant material according to the invention, which is produced in particular in the form of a line for protecting electrical cables, the following components ^{were mixed with one another at a temperature of about 30 °} C., the components being essentially in powder form templates: BOi parts by weight. Ethylene-ethyl acrylate copolymer, 30 parts by weight of a synthetic rubber such as EPDM-rubber, 10 parts by weight of polyisobutylene, 10 parts by weight of hPäraffdnwax, 11 parts by weight of calcium oxide, 1 part by weight of vRttßi,; l, 50 parts by weight of aluminum hydroxide and 150 parts by weight of calcium carbonate. The resulting dry mixture is then passed through a twin screw extruder, at a temperature of 130 ^° C., and the extrudate is then passed, in a partially cooled state, through a perforated plate, and out at the outlet

· ■ ■ ■ ·

the plate cut into granulate form.

The resulting granules can, if necessary be stored dung at normal room temperature for the subsequent Verwen- _ΟΛ or they may directly to a

Extruder, with gradual heating to 125 ⁰ C for extrusion to pipe or pipe shape.

, - _κ The extruded pipe is provided with an external reinforcement, whereupon the reinforced pipe is covered with an external protective coating made of, for example, polyvinyl chloride, if desired.

'j-

The polymeric matrix material, i.e., ethylene-ethyl acrylate copolymer and the synthetic rubber constitute the elasticizing ingredients of the resulting c line, and the respective amounts of these two ingredients can be balanced as desired Degree of elasticity, based on the amount of filler material absorbed in the polymer mixture shall be. Polyisobutylene is used as an adjuvant. «Q in the process of mixing the filler material is added to the polymer mixture and paraffin wax is added as a lubricant to give the mixture a to impart sufficient pliability during the manufacturing process.

Calcium oxide, which absorbs moisture in the mixture,

is added in sufficient quantities as a drying agent, to reduce the risk of pore effects when the polymeric materials and the different __ additives are mixed. The calcium oxide also contributes

to a more homogeneous mass.

Carbon black is used as a colorant. He gives the mixture a certain extent protection against the oxy _ _c dation.

The filler components, aluminum hydroxide and calcium carbonate, when the material of the invention is exposed to combustion conditions

_Λ porous material that does not breant and that can be changed-30

side relationship between the additives gives the foam a correct consistency when burned occurs. This foam later stiffens to form a firm, foamed layer with good thermal properties Insulation properties and high thermal 35

Stability.

The tubular or wire-shaped protective objects of the

Invention provide good mechanical protection under normal conditions of use and do not lead to Formation of halogen gases or a noteworthy smoke c when burning. Apart from the organic materials, the protective line according to the invention burns not easy and at high temperatures it forms a thermally stable, ceramic-like foam-foaming layer, good thermal insulation -, Q has shafts, and with the help of the reinforcement devices, such as a braid made of metal or other common material, is held in the desired location.

._ Under combustion conditions, the chemical reaction results Water which, as stated above, has a cooling effect. The material according to the invention also has a low heat of combustion. The protective line according to the invention can be manufactured

__ using a standard device and

is relatively inexpensive due to the readily available raw materials.

Claims (34)

PATENT CLAIMS 1. Fire or flame resistant material containing an organic or inorganic matrix or a mixture thereof, 50 - 450 parts by weight of a filler material, the aluminum hydroxide contains, per 100 parts of the matrix; and 100-600 parts by weight of a material from the group of calcium carbonate and calcium magnesium carbonate per 100 parts of the matrix. 2. Fire or flame resistant material according to claim 1 in which the matrix is an organic matrix containing an ethylene-ethyl acrylate copolymer. 3. Fire or flame resistant material according to claim 1, which also contains 30-40 parts by weight of one or more of a lubricant, an elasticizing agent Agent, drying agent, coloring agent or antioxidant per 100 parts - Contains the copolymer. 4. Fire or flame resistant material according to claim 1, in which the filler material is 50-450 wt. Contains parts of aluminum hydroxide, with 0-200 parts by weight of which can be replaced by mica. 5. Fire- or flame-resistant material according to ·. ,, ■ '■.' Claim 1, wherein 0-100 parts by weight of the calcium carbonate are replaced by sodium silicate. 6. Fire or flame resistant material according to claim 3, wherein the lubricant comprises paraffin wax, which in an amount of about 10 parts by weight per 1Ö0 Parts of the copolymer is present. 7. Fire or flame resistant material according to claim 3, in which the desiccant is a mixture of Includes calcium oxide and wax present in an amount from about 11 parts by weight per 100 parts of the copolymer. 8. Fire or flame resistant material according to claim 3, in which the elasticizing agent is ethylene Propene rubber present in an amount of about 11 parts by weight per 100 parts of the copolymer. 9. A fire or flame retardant material according to claim 3, in which the colorant comprises carbon black, . present in an amount of about 1 part by weight per part of the copolymer. 10. Fire or flame resistant material according to claim 3, in which the antioxidant poly-tri- methyl dihydroquinoline present in an amount from about 1.5 parts by weight per 100 parts of the copolymer. 11. Fire or flame resistant material according to claim 3, in which the filler material also has an effective the same amount of azodicarbonamide as an organic expanding agent. 12. Fire or flame resistant material according to claim 1 in which the matrix is an inorganic matrix comprising cement mortar. 13. Fire or flame resistant material according to claim 1, in the form of a coating or paint composition, wherein the matrix is an organic matrix which is a solution or suspension of a , Q alkyds, a polyurethane, a vinyl acetate or an acrylate. 14. Rigid fire or flame retardant material, containing per 100 parts of an organic matrix, . _c 50-450 parts by weight of a filler material which Ib Aluminum hydroxide comprises 100-600 parts by weight of a material selected from the group of calcium carbonate and calcium magnesium carbonate, 8-15 parts by weight of a lubricant, 8-15 parts by weight of an elasticizing agent _ Means, 10-15 parts by weight of a drying agent, 1-2 parts by weight of a colorant and 0 to 1.5 Parts by weight of an antioxidant. 15. Rigid fire or flame retardant material "- according to claim 14, containing 100 parts of ethylene-ethyl acrylate as a matrix, 220 parts by weight of aluminum hydroxide as filler, 220 parts by weight of calcium carbonate, 10 parts by weight of a lubricant, 11 parts by weight of an elasticizing agent, 11 parts by weight of a drying agent, _on 1% by weight Part of a colorant and 1.5 parts by weight of an antioxidant. 16. Flexible fire or flame retardant material, containing per 100 parts of an organic matrix, 130 - __ 170 parts by weight of a filler material, the Aluininium- hydroxide contains 130-170 parts by weight of a material selected from the group of calcium carbonate and Calcium magnesium carbonate, 8-15 parts by weight of a _Λ "* 33441o6 Lubricant, 25-40 parts by weight of an elasticizing agent, 10-15 parts by weight of a drying agent, 1-2 parts by weight of a colorant and 0-1.5 Parts by weight of an antioxidant. 17 .. flexible fire or flame retardant material, containing 30 parts by weight of ethylene-ethyl acrylate as Matrix, 150 parts by weight of aluminum hydroxide as a filler, Q fabric, 150 parts by weight calcium carbonate, 10 parts by weight a lubricant, 30 parts by weight of an elasticizing agent, 11 parts by weight of a drying agent and 1 part by weight of a colorant. _lt - 18. A process for producing a fire or flamraenbeständigen material according to claim 1, by dry blending the ingredients at ambient temperature, extruding the resulting mixture at a melt temperature of about 150-200 ⁰ C, _ with the formation of extrudates, in continuous form, and subdividing these continuous extrudates. "" 19. Subdivided extrudates made by the process of claim 18. 20. Method of making a fire or flame resistant coating for against fire objects to be protected, by extruding the subdivided extrudate according to claim 19, wherein a temperature _ door of about 150-200 ⁰ C to a desired shape. 21. Fire or flame resistant material containing 90-140 parts by weight of a polymeric material, 14-24 Parts by weight of a lubricant, 8-13 parts by weight of calcium ^ ₁₁ . oxide, 140-160 parts by weight calcium carbonate and 140 ob ' 160 parts by weight of aluminum hydroxide. 22. Fire or flame resistant material after arrival ir * * 3344158 Claim 21, which also contains an effective amount of a colorant. . 23. Fire or flame resistant material according to claim 21, wherein the polymeric material consists of 70-100 parts by weight of ethylene-ethyl acrylate copolymer and 20 40 Parts by weight of synthetic rubber and wherein the lubricant consists of 8-12 parts by weight of polyisobutylene and 6-12 parts by weight of paraffin wax. 24. Process for making the fire or flame resistant Material according to claim 21, by mixing its components, essentially in powder form, .. _R with the formation of a loose mixture, at a temperature of about 30 ⁰ C door, extruding the resulting mixture at a temperature of about 13O ⁰ C, cooling the extrudate and subdividing the extrudate into granules for storage at ambient temperature. 25. Granules, produced according to the procedure of Claim 24. 26. A method for producing a fire or _{flame-O (_} resistant material in tubular form by extrusion of the granules of Claim 25 at a temperature up to 125 ° C. 27. Extruded fire or flame retardant Material in tube form, made by the process oU of claim 26. 28. Extruded fire or flame resistant material in tubular form according to claim 27, provided with _oc _ an outer steel braid and an outer protective ob coating. 29. Extruded fire or flame retardant .. ... ./ ... - <* = ■ ' 3344155 _χ ■■■■ "■"'·■■■.'. -α) -. ■ '', The material of claim 28, wherein the protective outer coating is a plastic material. j- 30. Using the fire or flame resistant Materials of claims 1 to 17 or 21 to 23 the production of covers for mechanical and / or electrical or any energy conversion devices, such as cabins or housings, adapters, pipes , Q houses, cables, panels, cable ducts, doors, Hatches and building structures. 31. Use of the fire-resistant or flame-resistant material according to claim 1 to 17 or 21 to 23, in the manufacture of covers for vessels, containers and pipes that hold or carry explosive contents and located in chemical plants, refineries, vehicles, ships and airplanes. 32. Using the fire or flame resistant Materials of claims 1 to 17 or 21 to 23 the production of granules or bulk materials, the granules having shapes and dimensions, which are adapted to remove any gaps or _ot . Can fill gaps made for fire insulation. 33. Use of granules or bulk material according to claim 32, wherein the granules have a shape and size _eri and have a bulk density at normal temperature, which allow their thermal expansion in the gaps or spaces in the event of fire. 34. Using the fire or flame resistant Materials of claims 1 to 17 or 21 to 23, in which Manufacture of fire-insulating covers that use conventional material are laminated or reinforced.