CH619256A5 - Process for the preparation of porous compositions having improved fire behaviour, and the use thereof for the preparation of porous compositions in the form of coatings - Google Patents

Description

The invention relates to a process for the production of porous compositions with improved fire behavior and its use for the production of porous compositions in the form of coatings.

The weak point of all plastics is above all the fire and heat behavior. Furan resin mixed condensates influence the fire behavior, the heat and flame resistance as well as the smoke development of organic and / or inorganic substances, especially synthetic resins, such as. As polyester, polyurethane, epoxy, alkyd, latex and even bitumen, extremely cheap.

The inventive method for the production of porous compositions with improved fire behavior is defined in claim 1 and the application of the method for the production of porous compositions in the form of coatings in claim 20.

In the process, the high exothermic temperatures which arise when furan resin and acid are mixed and which can be controlled, completely or partially cure other admixed synthetic resins, possibly without further reaction systems.

In addition, the oxidizing and reducing agents known per se for blowing foams can be used. Phosphoric acid and oxalic acid have proven to be particularly advantageous as the acid. However, other organic acids, such as. B. formic acid and maleic acid, suitable. Other organic acids, apart from H3PO4, are also suitable per se, but are less advantageous for reasons of corrosion.

The advantage of using synthetic resins on an aqueous basis is that the mixing of a wide variety of aqueous or water-compatible organic or inorganic substances such as B. synthetic resins, alcohols, esters, acids, hydraulic binders and the like as powders, solutions, suspensions, emulsions by mixing, stirring, pouring or spraying is significantly easier, and that the water simultaneously with organic materials such. B. 60 cement and / or gypsum reacts to achieve additional structural strength, the exothermic heat and the resulting vapor pressure causing rapid hardening.

Since the exothermic temperatures can be set from 20 ° C to over 200 ° C 65, there is also a wide range of variations for the process. At higher temperatures, the chemical as well as the hydraulic reactions and / or organometallic crosslinking run smoothly.

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ter, faster and cheaper. A connection is created between hydraulic binders and synthetic resins, whereby one can also use adhesion promoters. For screed coatings and pressure compensation plates, the sand can also be used as a filler and / or bitumen polyester, see p

The substances made from synthetic resin condensates can be improved even more by adding other substances such as B. clay or kaolin and / or chinaclay and / or diatophate and / or aluminum chromium phosphate and / or aluminum alfthalate. In conjunction with the phosphoric acid io phate and / or aluminum chromium phosphate and / or aluminum alfthalate feeds. In connection with phosphoric acid, further chemical and organometallic cross-links take place.

When exposed to flame, the end product can adopt a glass-like, ceramic or metallic structure. This variant also uses substances such as bauxite, diaspore, metal oxides, sodium compounds, boron, sodium borate, aluminum silicate, aluminum hydroxide, feldspar, slate flour, calcium oxide, dolomite. 20th

The smoke development and the flame height of the materials, as well as the generation of flammable gases, is low. Another advantage of the method according to the invention is that not only the temperature but also the reaction times can be controlled, and that phosphoric acid is preferably used as the acid. Phosphoric acid forms phosphates with metals that are not corrosive. There are also no corrosion problems. At the same time, phosphoric acid increases the flame resistance of the fabrics.

The use of the versatile organic and inorganic or metallic, chemical, mineral products in the process according to the invention results in new, surprising technical and chemical processes in the resulting exothermic heat and the corresponding hot vapor pressure. 35

The process according to the invention creates completely new synthetic resin products which have the character of the respective additives. Such additives are e.g. B.

Cement, cement asbestos, gypsum, wood flour, bitumen, bitumen polyester, metal oxides, alumina, diatomaceous earth, porcelain earth, mica, asbestos, vermiculite, silicates, carbonates, glass beads, expanding materials (e.g. Siliperl).

The multitude of possible combinations creates a whole range of new products, which in turn can be used for a wide range of applications, since they combine a multitude of desired and required options and properties in a single product.

High insulation against cold, heat, noise, good fire behavior, in particular high flame resistance, no development of flammable gases, no after-flame, no after-glow, low smoke development, low flame height, significant increase in ignition temperature, strong reduction in heat radiation and transmission are the excellent properties that are obtained with the products produced by the process according to the invention. 55

Furthermore, the fabrics can be heat-insulating, heat-conducting, electrically insulating or electrically conductive and / or radiation-absorbing.

A porous material is more resistant to fire than a solid material because the porous material conducts heat significantly poorly. A material that turns into a porous carbon foam when exposed to heat is also better than a non-driving material, since the carbon foam also provides good thermal insulation. However, the end products can also be adjusted in such a way that they result in a non-floating, solid carbon layer. As additives for obtaining carbon foam from the coating compositions when exposed to heat or flame, sugar, dextrose,

Urea, mono- or polyhydric alcohols, e.g. As glycerin, manganese ammonium phosphates, magnesium ammonium phosphates can be called.

Many fire problems can be solved or improved with the aforementioned method. Almost all synthetic resins show significantly better fire behavior in connection with furan resin mixed condensates, so that in most cases halogenated conventional flame retardant chemicals can be dispensed with. Depending on the intended use of the end products, however, known flame solids can be used as additives. As such, e.g. B. be listed: flame retardant materials based on boron, phosphorus, bromine, chlorine, and / or their modifications, derivatives and derivatives. Furthermore, particularly suitable substances for this purpose are: antimony trioxide, sodium silicates, aluminum compounds, such as aluminum phosphate, aluminum chromium phosphate, kaolin, quinaclay, highly disperse silicic acid, silicones, chlorinated paraffins, optionally chlorinated rubber, salts of alginic acid, zirconium compounds, cerite earth, thorium, tridibromopropyl phosphate phosphate, phosphate Potassium tripolyphosphate, dicyandiamide, aniline, calcium carbonate, metal oxides.

The materials obtained can e.g. B. in gasoline, especially aircraft gasoline tanks, fire walls in mining, for fire bulkheads in factories or in steel buildings, in shipbuilding or as a preventive fire protection for cable and cable breakthroughs and the like.

According to the process, there is also the possibility of mixing in metallic, mineral, thermoplastic materials which melt or sinter under the influence of flame and heat and which form a solid cover layer when cooled.

Have been advantageous for. B. zirconium compounds, which radiate heat at 600 ° C as light, highly disperse silica, tridibromopropyl phosphate, chinaclay, dolomite and / or additives pretreated with silicates, such as wood flour, plastic products and / or plastic foam and / or plastic foam waste.

The use of porous organic and / or inorganic additives significantly reduces the heat transfer. The chemical products can be used as fire-resistant insulating materials. As porous inorganic additives such. As perlite, vermiculite, Siliperl, foamed clay and / or as organic additives, styrofoam, hard and / or soft polyurethane foam, polyester foam, aminoplast foam, crushed waste from all known synthetic resin foams, which may be pretreated with other substances.

Styrene derivatives or styrofoam and PU soft foam, which otherwise show a high level of flammability, no longer burn.

The coating composition can be set here

that they get a firm, slightly porous carbon layer of 2-3 mm or a strong driving carbon foam of 10-15 cm.

Since the carbon layer has a heat-insulating effect, the styrofoam balls are still present for approx. 20-30 minutes after flame treatment. The coating composition then adopts the porous structure of the porous additives, so that it has a heat-insulating effect even without a foaming carbon foam.

According to a preferred embodiment of the invention, the additives used are primarily waste materials based on plastic and / or cellulose, in particular foam plastic waste, which, in conjunction with the binders, give new insulating plates which show better thermal flame behavior than the known plastic foams

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do it alone, e.g. B. based on styrofoam, hard and soft polyurethane, aminoplast, polyethylene foam.

The reuse of plastic waste and / or paper and / or textiles represents a significant environmental problem, which can be alleviated by the invention.

They are characterized by low smoke development, low flammability and chemical resistance.

The coal scaffold can be floated or set as a fixed layer of coal. Even compared to the phenolic resin, the binders are characterized by less smoke and a firmer carbon structure.

If bitumen is also used, it can be seen that the material created no longer liquefies when it is flamed.

Other additives perform different tasks. For example, cresol, resorcinol, copper sulfate and paraformaldehyde help prevent rotting and mold; Bitumen and / or tar achieving a higher vapor tightness.

The masses produced according to the concept of the invention can be powdered and the powder can be mixed into organic and / or inorganic binders as a fire-improving additive.

With the large number of products that can be produced, it is understandable that the previous information is by no means to be regarded as an absolute upper limit for the possibilities offered by the method according to the invention. The possibilities of application are by no means exhausted.

It is of course also possible to use all of the known measures used to date in the case of polyurethane, acrylic, alkyd resin, latex or epoxy resin in the abovementioned process and / or to have plates, pipes, molded parts manufactured by the known production processes.

The plates, shaped pieces can be produced using the stirring, spraying or casting process or with belt systems. The known devices for the production of synthetic resin products can be used for this purpose. The previous fields of application and applications of synthetic resin foams and coating compositions are also possible for the compositions produced by the process according to the invention.

The invention is not limited to the exemplary embodiments described, but can be modified in various ways within the scope of the inventive concept.

When merging the components used, such as. B. by mixing, spraying, stirring, the furan resin condensate is usually submitted. If this is used, the foreign resin is added. Then the selected additives, individually or in a mixture, are added. It is advantageous here to choose the order in which the additives are added such that the liquid or low-viscosity substances are added before the solid or strongly thickening substances. The acid is advantageously added after all substances have been combined.

When polyester is added, unsaturated, highly polymerizable polyesters, which may contain little monostyrene, are particularly favorable.

Some materials are listed below, the use of which is particularly preferred in the process according to the invention. In general, it should be pointed out that water-compatible resins are particularly suitable as an additive to furan resin mixed condensate.

Commercially available products which have a solids content of 25-70% can be used particularly advantageously as furan resin mixed condensates based on urea, melamine or phenol.

have a furfuryl content of 10-80% and a pH of 6.5-7.5.

In a particularly preferred embodiment of the invention, furan resin mixed condensates which contain 25-30% furfuryl alcohol, 20-25% H2O, and

They had 12-14% N2 content and a viscosity of 180-220 cps (eg FH 75, from Klüser, Wuppertal, Germany).

Another preferred furan resin mixed condensate had a proportion of

48-50% furfuryl alcohol

9-9.3% N2 content 14-16% H2O and a viscosity of 180-220 cps

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(e.g. FH 200, Fa. Klüser, Wuppertal, Germany).

A product with 60% furan resin content and 40% phenol resin content was found as a particularly preferred phenol-furan resin.

25 However, other commercially available products can also be used.

As a polyester can advantageously z. B. can be used: Polygal casting emulsion E 81 (Bayer AG, Leverkusen, Germany) or Palatal 6 (BASF AG, Ludwigshafen, 30 Germany).

As advantageous water-compatible epoxy resins can be mentioned, for. B. Commercial products such as: Versadukt 429 and Europox 716 BN (Schering AG, Bergkamen, Germany).

35 A preferred urea-formaldehyde resin that gives particularly favorable results is, for. B. Foam resin 293 (BASF AG, Ludwigshafen, Germany).

Commercial products from Roehm & Haas, Darmstadt, can be used as acrylic or methacrylic resin, e.g. B. Monomer 40 sample 1.

Finally, Resydral VWA 3811 (Chemische Werke Albert, Wiesbaden, Germany) can be mentioned as an advantageous alkyd resin.

The following 45, each based on 100 parts by weight of furan resin mixed condensate (all parts in weights), are advantageously used as proportions of the respective components:

I Furan resin mixed condensate: 100 parts by weight

50 II foreign resin, if used:

Polyester resin: 1-75, particularly preferably 5-50 parts by weight epoxy resin: 1-65, particularly preferably 3-45 parts by weight polyurethane resin: 1-55, particularly preferably 3-40 parts by weight 55 acrylic resin: 1- 75, particularly preferably 5-55 parts by weight of alkyd resin: 1-70, particularly preferably 3-45 parts by weight latex: 1-70, particularly preferably 3-45 parts by weight

III aggregates:

60 inorganic additives: 1–250, particularly preferred (eg cement, quinaclay, etc.) 5–150 parts by weight organic additives: 1–200, particularly preferably 3–130 parts by weight

(Synthetic foams, such as PU foam, phenolic resin foam, etc.) 65 When using porous materials, such as. B. vermiculite, perlite, siliperl, amounts up to 90 parts are preferred.

a viscosity of 160-300 cps

IV acid: 2 to 40 parts by weight

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The process according to the invention for the production of porous compositions in the form of coatings is carried out in such a way that the reinforcement materials mentioned, such as glass wool, glass fleece, glass silk, rayon wool, carbon fibers, metal threads, are processed in a mixing, stirring or spraying process together with synthetic resins .

To form a stable carbon foam or a carbon layer when exposed to fire, polyacrylonitrile, polyvinyl chloride, novolak resin, coal tar pitch and / or indene resin can be added to the synthetic resins.

A special embodiment of the new method is to use synthetic resins in the form of aqueous dispersions and to incorporate or disperse powdered polyacrylonitrile, powdered polyvinyl chloride, powdered novolak resins, indene resins and / or coal tar pitch in these synthetic resin dispersions. The dispersion of the materials mentioned, which result in a stable carbon foam or a stable carbon layer when exposed to fire, is carried out, for example, using nonionic, cationic or anionic emulsifiers, with nonionic emulsifiers such as alkylphenol / ethylene oxide adducts being particularly preferably used.

A particularly stable carbon foam or a stable carbon layer is obtained when the mixture contains reinforcing materials, such as rock and glass wool, glass fleece, glass silk, rayon wool, carbon fibers, boron and boron carbide threads, metal threads and / or wiskers, the use of which of rock and glass wool is particularly preferred. Although carbon fibers, boron and boron carbide threads, metal threads and / or wiskers are very expensive materials per se, the production of these reinforcing materials, which are extremely tensile and compressive, and which are stable even at extremely high temperatures, are and are which are also resistant to larger fires, missing parts which cannot be used in the aerospace industry and which, like for example carbon fibers, are then used for seals and for areas of application in which only inexpensive reinforcement materials are used can. Such carbon fibers, boron and boron carbide threads and metal threads are very well suited for the process according to the invention for the production of coating compositions and porous materials with improved fire behavior, since they are heat-resistant even at temperatures up to 600 ° C. when exposed to fire Hold fire-forming carbon foam or the carbon layer together.

Partially carbonized or pre-pyrolyzed tars and pitches such as are described in DT-OS 2 341 702 are also suitable as additives to the furan resins. The preferred furan resins which can be used to produce the coating compositions and porous substances according to the invention are described in DT-AS 1 154 639 and DT-AS 1096 522, as well as in Ullmann's Encyclopedia of Technical Chemistry, 13th vol. (1962), Verlag Urban and Schwarzenberg, pp. 453 to 478.

Other polymers can also be used in the production of the coating compositions and porous substances which are favorable when exposed to fire, such as, for example, polyurethane, acrylic, epoxy and / or alkyd resins.

The new coating materials and porous materials can be applied to these materials in the form of plates, shaped pieces, pipes, in the form of layers or paints to protect wood, ceramic, plastic or metal.

The proportion of the reinforcing materials mentioned is in the range from 1 to 50%, based on the proportion of plastic in the mixture which is used as the starting material for the production of the coating compositions and porous substances according to the invention. The proportion of reinforcing materials, based on the proportion of plastic, is preferably between 5 and 35% by weight.

The proportion of the constituents which cause a carbon-rich layer or a carbon foam when exposed to fire, such as, for example, polyacrylonitrile, polyvinyl chloride, coal tar pitch, etc., is preferably 5 to 50% by weight, based on the proportion of plastic in the starting material.

For example, a water-soluble or water-soluble or water-emulsifiable phenolic or furan resin, which contains 50% by weight of resin, with 5% by weight of polyacrylonitrile powder and 16% by weight of polyvinyl chloride powder and 10% by weight. Glass fibers with a length of 4 cm are homogenized and optionally processed with the addition of inorganic fillers for the production of the coating compositions according to the invention. The above-mentioned phenolic resin, which was used for the production of the coating compositions according to the invention, is water-soluble and its production is described in Ullmann's Enzyklopadie der Technischen Chemie, 13th vol. Op. Cit., P. 465.

The inventive production of the coating compositions and porous materials with improved fire behavior in various forms, such as plates, molded pieces, layers etc., can be carried out in a stirring, spraying or pouring process and the curing of the resins using catalysts, in particular Acids take place. The individual catalysts and the curing conditions are mentioned, for example, in the specified reference, in “Ullmann's Encyclopedia of Industrial Chemistry”.

The reaction conditions under which a fiber-reinforced coating material or a fiber-reinforced porous material with improved fire behavior are obtained and under which a carbon foam or a carbon layer forms when exposed to fire are generally given under the effects of temperature from 50 to 1000.degree. The formation of carbon foam or carbon layers depends in each case on the duration of the temperature effect and the level of the respective temperature, for example also forms a charred porous or at relatively low temperatures, around 70 ° C, when these temperatures act on the coating composition for several hours or several days smooth carbon layer as well as at a temperature of 200 to 700 ° C for 1 min to 1h.

The addition of flame retardants, such as antimony trioxide, antimony pentoxide, red phosphorus, melamine, etc., is beneficial to the flame behavior during a fire of the coating compositions and porous substances produced according to the invention.

A phenol furan resin which contains the reinforcing materials mentioned and, if appropriate, resins which, upon exposure to fire, form a dense carbon foam or a carbon layer, such as, for example, polyvinyl chloride, polyacrylonitrile, coal tar pitch, preferably contain 60% furan resin components and 40% phenol resin components.

The advantage of the coating compositions and porous materials produced according to the invention is that the fire and heat behavior of furan resin mixed condensates is significantly improved, this fire behavior being characterized by a low smoke development. The method according to the invention makes it possible to obtain coating compositions and porous substances which, when exposed to fire, form a carbon foam or a carbon layer which is fire-retardant and by which the fire is contained. The formation of a carbon layer, for example, also insulates steel girders in high-rise buildings in the event of intense fire.

When using foamed styrofoam and polyurethane

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thanweich-foams or rigid foams in the production of the coating compositions and porous substances while simultaneously using the reinforcing materials mentioned and the additives promoting carbon formation, such as polyacrylonitrile, it is possible to reduce the usual high flammability of these organic foams, in particular polystyrene, that they don't burn anymore

The coating composition is constructed, for example, in such a way that, when exposed to fire, a solid, slightly porous carbon layer of 0.2 to 3 mm or a carbon foam up to 15 cm thick containing reinforcing materials is produced.

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Claims (20)

6X9256 1. Process for the production of porous compositions with improved fire behavior, characterized in that aqueous or aqueous-alcoholic furan resin mixed condensates in combination with cresol and / or melamine and / or phenol and / or urea, alone or in a mixture with other synthetic resins and / or mixes and hardens with organic and / or inorganic additives. 2. The method according to claim 1, characterized in that epoxy, polyester, acrylic, alkyd, polyurethane resins, styrenized resins or mixtures thereof are used as further synthetic resins. 2nd PATENT CLAIMS 3. The method according to claim 1, characterized in that one uses latex instead of or together with synthetic resin. 4. The method according to claim 1, characterized in that the curing is carried out with the addition of catalysts, for example acids. 5. The method according to claim 4, characterized in that phosphoric acid is used as a catalyst. 6. The method according to claim 4, characterized in that oxidizing and reducing agents are used as catalysts. 7. The method according to claim 1, characterized in that the individual solutions organic and / or inorganic additives as powder and / or solution and / or dispersions and / or suspensions of polymers and / or monomers and / or plasticizers, plasticizers, thickeners , stabilizing liquids in the stirring and / or pouring and / or spraying process, either alone or in a mixture, supplied, injected and / or mixed. 8. The method according to claim 1, characterized in that as additives mineral and / or hydraulic setting substances, such as. B. cement, gypsum, clays, diatomaceous earths, porcelain clays, mica, asbestos, vermiculite, silicates, oxides, carbonates. 9. The method according to claim 1, characterized in that as additives, porous organic and / or inorganic additives, such as perlite, expanded clay, vermiculite, styrene polymers, crushed rigid and flexible polyurethane foam, aminoplast foam, polyester foam, crushed waste of other synthetic foams, textile waste , Rubber waste can be used alone or in a mixture. 10. The method according to claim 1, characterized in that flame-retardant substances are used as additives. 11. The method according to claim 1, characterized in that additives are added, which result in a blowing carbon foam when exposed to flame and heat. 12. The method according to claim 10, characterized in that one draws sugar, dextrose, urea, mono- or polyhydric alcohols, boron, manganese ammonium phosphate and magnesium ammonium phosphate individually or in combination. 13. The method according to claim 1, characterized gekennzeich- net that wood flour, flax, starch, penthaerytrite, polyacrylonitrile, polyvinyl chloride, novolak resins, coal tar pitch, indene resins, resorcinol, polyvinyl acetate and / or cellulose are used as additives, the one good coal scaffolding. > 14. The method according to claim 1, characterized in that copper sulfate, hydrazine, aluminum phthalate, methacrylic ester tar, bitumen, silicone compounds, sulfite waste liquor are used alone or in a mixture as further additives. < 15. The method according to claim 1, characterized in that the additives are pretreated mechanically, chemically or minerally. 16. The method according to claim 1, characterized in that additives are used which transform into a glass-like and / or ceramic material when exposed to flame or heat. s 17. The method according to claim 1, characterized in that metal powder is used as additives. 18. Porous compositions with improved fire behavior, produced by the method according to claim 1. 19. Porous compositions according to claim 18, in powder form together with organic and / or inorganic additives and / or organic and inorganic binders. 20. Application of the method according to claim 1, for the production of porous compositions in the form of coatings, characterized in that fabrics made of wire, non-woven fabrics, synthetic fibers and asbestos, rock and glass wool, glass fleece, glass silk, cellulose, carbon fibers, boron and boron carbide threads, metal threads and / or wiskers, individually or in combination during mixing for reinforcement.