DE3625080C2 - Thermally expandable mass, process for its production and use - Google Patents

Description

The invention relates to a thermally expandable mass based on Expandable graphite, polyurethane resins and substances that are paracrystal in the event of fire lines form carbon skeleton, a process for the production of such masses, and the use of such compositions for effective sealing in the event of fire of openings in components, such as. B. joints, voids or gaps or the like.

AT-PS 360.130, for example, contains a thermally expandable seal material described, which is made of expanded graphite, phenol-formaldehyde resin, a Chloroprene rubber, such as B. polychlorobutadiene, an organic solution medium, and optionally also from aluminum hydroxide and organic Fa there is. It expands when exposed to heat and fire protective opening with relatively low flowability and developed a bloat even in a not completely closed opening in the event of a fire print. The expanding mass does not avoid obstacles and forms a tightly sealing barrier layer. This sealing material has a high Mechanic solidity. Disadvantageous in the manufacture and use of such materials However, large masses are their brittleness and low flexibility, as well as the Use of a solvent in the manufacture.

EP-A-51106 contains thermally expandable compositions based on polyurethane NEN described by the reaction of polyisocyanates with polyester polyo len, phosphorus-containing polyhydroxyl compounds and cyanuric acid derivatives as expandable component are obtained and plastic-elastic character to have. The good flowability of these fire protection materials brings the Disadvantage that due to the relatively small or practically missing Bloating pressure the formation of a tightly sealing barrier layer is very difficult and  is possible with large material consumption.

The invention has for its object this in the known fire to eliminate the disadvantages that occur with protective materials. The task failed be solved in that the rubber-elastic chloroprene component, the for the flexibility of the well-known fire protection materials on expandable graphite sis has been replaced with a polyurethane resin.

The present invention accordingly relates to a thermally expandable material containing

• 20 to 60% by weight expanded graphite,
• - 20 to 60 wt .-% polyurethane resin and
• - 5 to 20 wt .-% substances in the event of fire form paracrystalline carbon framework, as well
• - If necessary, other substances that modify fire behavior.

The fire protection compositions according to the invention are particularly characterized by that on the one hand they form an effective fire protection barrier layer have sufficiently high inflation pressure. On the other hand, the Va range of polyurethanes, according to the desired application, To produce fire protection compounds with different hardness and flexibility, the polyurethane may optionally also be foamed. It can Rigid plates as well as flexible tapes are used in fire protection the. Panels are used, for example, to seal ventilation ducts, Moldings on fire door edges, flexible tapes for sealing cables or pipes used for wall breakthroughs.

Another advantage of the invention is that in the manufacture of the Fire protection material no solvents are used, so none Dry lines are necessary, such as in systems that use solutions or Suspensions work. This results in the simpler way of working low energy and investment costs, as well as a solution solution reduced environmental impact and health risks at the Manufacturing and application.

The curing of the polyurethane resins can optionally by adding in  the usual catalysts in polyurethane chemistry are accelerated. Appropriate net are primarily organometallic compounds that make up the polyurethane reaction accelerate such. B. dibutyltin dilaurate, diphenyl mercury acetate, lead octoate, tin octoate, zinc octoate, tertiary amines such as diazabicyclooctane or Bis (dimethylaminoethyl) ether. There is also a delay in curing to a certain extent possible by adding inhibitors, such as. B. Acid chlorides or acids, for example benzoyl chloride, p-toluenesulfonic acid and Hydrochloric acid.

Suitable substances that have a paracrystalline carbon structure in the event of fire form, for example, polyvinylidene chloride, PVC, polyacrylonitrile, cellulose or their derivatives, phenol-formaldehyde resins, polyfurfuryl alcohol or Polyimides. When heated in the event of a fire, these substances cross-link next, the strong intermolecular bonds also in the further thermal stress, which leads to pyrolytic decomposition and finally to Formation of the paracrystalline carbon structure leads to being preserved.

Other additives that modify fire behavior are, for example Melamine and its derivatives, various graphite salts, cyanuric acid derivatives, Halogenated hydrocarbons, polyammonium phosphates and guanidine salts. This Substances also swell when decomposed when exposed to heat. Since she have a decomposition temperature different from expandable graphite increases in the event of a fire, the inflation pressure also increases, causing a firmer partitioning of the opening takes place.

It can also contain other additives, most importantly the firmness of you Improve compound in the expanded state, solidify the crust and the Increase cohesion, such as B. inorganic fibers, for example mineral or glass fibers, glass powder, vermiculite, silicates, starch, sugar, chlorinated paraf fine, aluminum hydroxide or magnesium hydroxide can also be used. It other flame retardants can be added, for example halo emitted or phosphorus-containing hydrocarbons, such as. B. Tris-chloropropyl phosphate or dibromo neopentyl glycol, flame retardant polyols and antimony trioxide. Furthermore, such additives come into consideration that foam formation in the  Help increase flaming. Examples include salicylic acid, p- Hydroxybenzoic acid, PVC, and nitrogen or sulfohydrazides, triazoles, Urea dicarboxylic anhydride and ammonium carbonate.

The compositions of the fire protection composition according to the invention ent hold 20-60% by weight expanded graphite, 20-60% by weight polyurethane resins and 5-20% by weight Substances that form a paracrystalline carbon structure in the event of a fire. Particularly suitable as substances that have a paracrystalline carbon structure form, prove three-dimensionally cross-linked thermosets, such as. B. phenol Formaldehyde resins. If desired, the polyurethane resins can be foamed be, whereby a regulation of the density of the fire protection compound is possible. The conversion into the foamed state is, for example, by water easily possible in the formulation.

The fire protection composition according to the invention is suitable not only for the production of Sheets, strips or strips also differed for the production of moldings shape. Bricks from this mass have proven themselves, for example, used to limit breakthroughs. In the event of fire, they bloat open and close the opening.

The application of the fire protection compound is particularly easy if it is laminated on a carrier web. As carrier materials come for example wise nonwoven webs, e.g. B. glass fiber fleece, plastic films, for. B. PVC films, Paper, aluminum sheet in question.

The fire protection compositions according to the invention are produced by Mi. and homogenizing the individual components, such as expanded graphite, polyol and isocyanate component, one in the event of fire, a paracrystalline carbon armor-forming substance, e.g. B. a phenol-formaldehyde resin or polyimide zes, as well as any other additive that modifies the fire behavior substances, possibly with the addition of water to produce foamed masses, for example in a kneader, dissolver or mixer. The one received Mass can either be used as such or it can be applied to a Carrier web, for example laminated onto a film or a fleece and be rolled out.  

Another advantageous way of producing the fire protection compound is that the individual recipe components or premixes first brought together and mixed immediately before use. The mixture is then introduced into the opening to be protected, in which they then fully reacted.

The fire protection compositions according to the invention are used to protect against fire Sealing openings in components forming a fire compartment, such as. B. Joints between walls, cavities or spaces, wall openings or the like used. Door seals or other seals, which foam up in the event of a fire and seal the upstream slot, here be put. It is also possible to manufacture entire bricks with which through breaks for cables or pipes are lined, and that when exposed to fire to form a lock. In the event of a fire, these masses foam through the action of heat and seal the opening so that the further passage of fire and Smoke and thus the further spread of the fire is prevented.

In the following examples, the inflation pressure was measured on samples with a diam water of 113 mm, which were inserted between two heatable metal plates, measured at 250 ° C. The pressure created during the inflation was from the transfer the lower plate to a force transducer with pressure display. The Inflating material was not delimited on the side and could be in the Spread out the level unhindered.

The expansion coefficient was determined on samples with a diameter of 50 mm, which were in a metal cylinder with a height of 100 mm and an inner diameter of 50 mm were inserted, measured. The cylinder with the sample over a stamp was preloaded with 100 g, heated in an oven at 300 ° C for 10 minutes. The expansion coefficient is calculated from the ratio of the heights of the expanded to the unexpanded sample.

The Shore A hardness was determined in accordance with ISO 868. In the examples The percentages and parts given mean parts by weight and parts by weight.  

example 1

A polyol component consisting of 32 parts of a polyether polyol with functionality 3 and a hydroxyl number of 36, 20 parts of tris-chloropropyl phosphate, 5 parts of antimony trioxide and 43 parts of a flame retardant polyether polyol which contained 6.5% Cl, 32% Br and 1% P, and had a functionality of 2 and a hydroxyl number of 345, was mixed with 100 parts of expanded graphite and 57 parts of phenol-formaldehyde resin, which was composed of t-butylphenol and formaldehyde. This mixture was then stirred with 40 parts of isocyanate component, consisting of 55% 4,4'-diphenylmethane diisocyanate and 45% multicore, with good homogenization for 5 minutes at room temperature. The homogeneous paste was applied to a polyethylene backing sheet, cold rolled into a sheet and stored for 5 minutes at room temperature for curing. The plate produced in this way was 3 mm thick and had a density of 1.4 g / cm ³ , an inflation pressure at 250 ° C. of 4.5 bar, an expansion coefficient at 300 ° C. of 14: 1 and a Shore A hardness of 81 The basis weight of the web was 4.2 kg / m ² .

Example 2

100 parts of the polyol component analogous to Example 1 were mixed with 100 parts of expandable graphite, 48 parts of phenol formaldehyde resin, 15 parts of aluminum hydroxide and 2.5 parts of mineral wool short fiber. Then, analogously to Example 1, it was mixed with 40 parts of isocyanate component and a 3.3 mm thick plate with a density of 1.29 g / cm ^{3 was} produced. An expansion pressure of 7 bar, an expansion coefficient of 7: 1 and a Shore A hardness of 93 were observed.

Example 3

A plate was produced analogously to Example 2, but with the difference that 1 part of water was added to the mixture before mixing with the isocyanate component. The sheet, which was about 2 mm thick after being rolled out, foamed to a thickness of 4.2 mm and a density of 0.77 g / cm ³ during curing. The inflation pressure was 5.8 bar, the expansion coefficient was 5: 1, the Shore A hardness was 80.

Example 4

A polyol component consisting of 35 parts of a polyol having the functionality 3 and a hydroxyl number of 36, 40 parts of dibromo neopentyl glycol (hydroxyl number 428), 5 parts of antimony trioxide and 20 parts of tris-chloropropylphosphate was mixed with 145 parts of expanded graphite and 50 parts of phenol formaldehyde resin. The mixture was then mixed analogously to Example 1, but with 45 parts of the isocyanate component and processed into a 2.5 mm thick plate with a density of 1.0 g / cm ³ and a Shore A hardness of 72. The inflation pressure was 6 bar, the expansion coefficient 6: 1.

Example 5

100 parts of the polyol component analogous to Example 1, but with the difference that 20 parts of guanidine phosphate were used instead of the tris-chloropropyl phosphate, were mixed with 70 parts of expanded graphite and 42.5 parts of phenol formaldehyde resin. Then, analogously to Example 1, it was mixed with 40 parts of the isocyanate component and processed into a 3 mm thick plate with a density of 0.97 g / cm ³ and a Shore A hardness of 90. The inflation pressure was 6.5 bar, the expansion coefficient 7: 1.

Example 6

100 parts of a polyol component analogous to Example 1 were mixed with 107.5 parts of expandable graphite and 42.5 parts of a polyimide powder which was prepared by reacting methylene dianiline bismaleimide with methylene dianiline. Then, analogously to Example 1, it was mixed with 40 parts of the isocyanate component and processed into a 1.9 mm thick plate with a basis weight of 1.9 kg / m ² and a density of 1.0 g / cm ³ . The Shore hardness was 95, the inflation pressure was 11.2 bar and the expansion coefficient was 10: 1.

Example 7

A polyol component consisting of 50 parts of a flame retardant polyester polyols with 27% Cl, functionality 2 and a hydroxyl number of 56, 25  Parts of dibromo neopentyl glycol (hydroxyl number 428), 5 parts of antimony trioxide and 35 parts of tris-chloropropyl phosphate, was with 140 parts of expanded graphite and 84 Parts of phenol formaldehyde resin mixed analogously to Example 1. Subsequently this mixture was mixed with 40 parts of isocyanate component analogously to Example 1 stirred and processed into a plate.

The plate produced in this way was 2.5 mm thick and had a density of 1.35 g / cm ³ , an inflation pressure of 6 bar, an expansion coefficient of 7: 1 and a Shore A hardness of 50.

Example 8

A polyol component consisting of 47 parts of a polyether polyol with the Functionality 3 and the hydroxyl number 36, 1.5 parts glycerol, 23.5 parts Melamine and 28 parts of one by reacting diethylphosphoric acid with Diethanolamine product obtained with the hydroxyl number 440, was with 214 Parts of expandable graphite and 64 parts of phenol formaldehyde resin analogous to Example 1 mixed. Then this mixture with 50 parts Isocyanate component stirred analogously to Example 1 and to a plate processed.

The plate produced in this way was 3.0 mm thick and had a density of 0.85 g / cm ³ , an inflation pressure of 7 bar, an expansion coefficient of 6: 1 and a Shore A hardness of 90.

Example 9

A polyol component consisting of 50 parts of a polyether polyol with the Functionality 3 and the hydroxyl number 36, 25 parts of dibromo neopentyl glycol, 5 Parts of antimony trioxide and 20 parts of tris-chloropropyl phosphate, was with 132 Parts of expandable graphite and 66 parts of phenol formaldehyde resin analogous to Example 1 mixed. Then this mixture with 32 parts of isocyanate compo nente stirred analogously to Example 1 and processed into a plate.

The plate produced in this way was 2.5 mm thick and had a density of 0.685 g / cm ³ , an inflation pressure of 7 bar, an expansion coefficient of 10: 1 and a Shore A hardness of 70.

Example 10

A polyol component consisting of 25 parts of a polyether polyol with the Functionality 3 and the hydroxyl number 36, 10 parts of a polyether polyol functionality 2, a hydroxyl number of 42 and an ethylene oxide content of over 70%, 40 parts dibromo neopentyl glycol, 5 parts antimony trioxide and 20 Parts of tris-chloropropyl phosphate, with 150 parts of expanded graphite and 50 parts Phenol formaldehyde resin mixed analogously to Example 1. Then this was Mixture with 45 parts of isocyanate component stirred analogously to Example 1 and processed into a plate.

The plate produced in this way was 4.5 mm thick and had a density of 1.25 g / cm ³ , an inflation pressure of 5 bar, an expansion coefficient of 12: 1 and a Shore A hardness of 83.

Example 11

A polyol component consisting of 39 parts of a polyether polyol with the Functionality 3 and the hydroxyl number 36, 39 parts of melamine and 22 parts of one Pro obtained by reacting diethylphosphoric acid with diethanolamine product with the hydroxyl number 440, was with 202 parts of expandable graphite and 61 parts Phenol formaldehyde resin mixed analogously to Example 1. Then this was Mixture with 42 parts of isocyanate component stirred analogously to Example 1 and processed into a plate.

The plate produced in this way was 4.0 mm thick and had a density of 1.15 g / cm ³ , an inflation pressure of 7 bar, an expansion coefficient of 6: 1 and a Shore A hardness of 55.

Example 12

A polyol component consisting of 58 parts of a polyether polyol with the Functionality 2, the hydroxyl number 42 and an ethylene oxide content of over 70%, 26 parts of melamine and 16 parts of one by reacting diethylphos phosphoric acid with diethanolamine product with the hydroxyl number 440, was analogous to 144 parts of expandable graphite and 54 parts of phenol formaldehyde resin mixed to Example 1. This mixture was then mixed with 62 parts The isocyanate component is stirred analogously to Example 1 and processed into a plate tet.  

The plate produced in this way was 3.5 mm thick and had a density of 0.755 g / cm ³ , an inflation pressure of 6 bar, an expansion coefficient of 8: 1 and a Shore A hardness of 84.

Example 13

In order to seal an opening effectively in the event of fire through the fiction To demonstrate moderate mass, was in a 200 mm thick plate made of foam concrete a pipe bulkhead installed. With a recess of 200 × 360 mm the concrete slab was a PVC pipe with a diameter of 160 mm and a wall thickness of 3.5 mm. Above and below the pipe in the opening each a 200 × 200 × 100 mm brick, which from the example 1 described paste according to the invention was prepared, so that the Pipe came to rest in the opening between the two bricks. Subsequently the concrete slab was converted into a small fire chamber based on DIN 4102 installed and flamed according to the standard temperature curve. The heat softened the PVC pipe and inflate the intumescent bricks, the pipe after 7 Minutes and the entire opening in the plate is sealed was locked. On the outside, there were neither flames nor Smoke or gas breakthroughs.

Claims (8)

1. Thermally expandable composition containing

• 20 to 60% by weight expanded graphite,
• - 20 to 60 wt .-% polyurethane resin and
• - 5 to 20 wt .-% substances that form a paracrystalline carbon structure in the event of fire, and
• - If necessary, other substances that modify the fire behavior.

2. Thermally expandable mass according to claim 1, characterized characterized in that in the event of fire a paracrystalline Carbon-forming substance is a phenolic resin. 3. Thermally expandable mass according to claim 1, characterized characterized in that in the event of fire a paracrystalline Carbon-forming substance is a polyimide resin. 4. Thermally expandable mass according to one of claims 1 to 3, characterized in that the polyurethane resin is foamed. 5. Thermally expandable mass according to one of claims 1 to 4, characterized in that they are on a carrier web is laminated. 6. Process for the production of thermally expandable Compositions according to one of claims 1 to 5, characterized characterized in that expandable graphite, a Polyol component, an isocyanate component, an im Fire creates a paracrystalline carbon structure Substance, and possibly other, the fire behavior modifying additives with a good mixture.   7. Process for the production of thermally expandable Masses according to claim 6, characterized in that the Components immediately after the completion of the Mixture is introduced into the component to be sealed, where the complete implementation may not be until the component. 8. Use of a thermally expandable mass according to one of claims 1 to 5 effective in the event of fire Sealing openings in components, such as. B. joints, Voids or gaps or the like.