FI66017C - ANALYZING AV FURANHARTSERS BLAND CONDENSATION FOR FRAMSTAELLNING AV ELDFASTA ISOLATIONSMATERIAL - Google Patents

Description

R5FH w (ii) * uu.lutusjulkaisu /.nn ffiA lJ 'utlAcgni NGSSKRIFT 6 6U1 / C Patent nyonnotty 10 08 1984, (¾¾ Patent seddelat (51) K ».Wu / tatCI.3 C 09 K 3/28, C 08 L 71/06 FINLAND — FINLAND <»> Patent application - PatenamBknlng 753 138 (22) Hakemhpiivt - Anshknlngadag 07-11.75 * '(23) AlkupUvl — Glttlghcudag 07.11.75 (41) Translators (external - Bllvlt offMtKg 13-05-76

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Patent and registration authorities of the United Kingdom of Great Britain and Northern Ireland 30.04.84 (32) (33) (31) Requested atuolkeu »—Begird prlorltat 12.11.7¾ 26.O9.75 Federal Republic of Germany Förbunds-republiken Tyskland (DE) P 2 ^ 53658.1, p 2543035.7 (71) (72) Hans Wilmsen, AIfredstrasse 2 ^ 3, ^ 3 Essen, Federal Republic of Germany-Forbundsrepubliken Germany (DE) (7¾) Oy Heinänen Ab (5¾) Use of mixed condensates of furan resins for the production of refractory insulation materials - Anv The present invention relates to the preparation of refractory insulating materials. The object of the invention is thus to provide new insulating materials, such as insulating sheets, which are more fire-retardant and which have been improved in terms of chemicals, heat and fire resistance compared to known materials.

It is a further object of the invention to provide insulating materials which do not decompose and stick together even after exposure to fire, but form a stable carbon foam or carbon layer under the influence of high temperatures, whereby the carbon foam is also stable and does not decompose at high temperatures. for a long time.

The weak point of all active ingredients is, above all, that they retain fire and heat poorly. However, it has now been found that furan resin mixed condensate has a very advantageous effect on the fire, heat and flame resistance as well as smoke resistance of organic and / or inorganic substances, especially artificial resins such as polyester, polyurethane, epoxy, alkyl, latex and even bitumen. development.

6601 7 2 The present invention therefore relates to the use of aqueous, not yet cured furan resins and mixed condensates of cresol and / or melamine and / or phenol and / or urea mixed with porous organic or inorganic materials for the production of refractory insulating materials.

The combination of a phenolic aldehyde resin, a furan derivative and an organic or inorganic filler is known per se from DE-A-1,144,474. In addition, DE-A-1,014,319 discloses However, these known materials are not intended to be components of refractory insulation materials.

In the production of the insulating materials according to the invention, oxidation and reduction means which are already known from the connection of foams can be used in addition. Phosphoric acid and oxalic acid have proven to be particularly advantageous among the acids. However, other organic acids, such as formic acid and maleic acid, are also suitable. Other inorganic acids, with the exception of HgPO 4, are also suitable per se, but are still less preferred due to corrosion.

The advantage of using aqueous resins is based on the agitation of a wide variety of aqueous or water-tolerant organic or inorganic substances, such as resins, alcohols, esters, acids, hydraulic binders and the like, in the form of powders, solutions, suspensions or emulsions. pouring, spraying or mixing is considerably simpler, and that the water reacts simultaneously with organic materials such as cement and / or gypsum, etc., thus achieving additional structural strength, whereby exothermic heat and the resulting vapor pressure cause rapid curing,

According to the invention, it is thus possible to use synthetic resins which are water-tolerant and / or contain water.

Because exothermic temperatures from 20 ° C to above 200 ° C are possible, embodiments of the invention will also vary widely. Chemical reactions and / or organic cross-linking of metals at higher temperatures are easier, faster and more favorable. A bond is formed between the hydraulic binders and the synthetic resins, allowing an additional adhesion promoter to be used. Bitumen polyester and / or sand can be used as a filler in cementitious layers as well as in pressure equalization boards.

Materials made from synthetic resin mixed condensate can be further improved by adding other materials, such as e.g. clay or kaolin and / or Chinese clay and / or diatomaceous earth and / or asbestos and / or mica and / or aluminum and / or sodium silicate and / or aluminum phosphate and / or aluminum chromium phosphate and / or aluminum phthalate. Chemical and organometallic crosslinks still occur upon incorporation into phosphoric acid.

The final product can be fired, giving it a glassy, ceramic or metallic structure. These modifications additionally use other substances such as bauxite, diaspora, metal oxides, sodium compounds, boron, sodium borate, aluminate, aluminum hydroxide, feldspar, shale flour, calcium oxide, dolomite, etc.

The formation of smoke and the height of the flame as well as the formation of flammable gases from these materials is negligible. A further advantage of the invention is that not only the temperature but also the reaction times are adjustable, and that phosphoric acid is primarily used as the acid. Phosphonic acid forms phosphates with metals that do not have a corrosive effect. There are also no corrosion problems. At the same time, phosphoric acid increases the resistance of the substance to flames.

The use of versatile organic and inorganic or metallic, chemical and mineral products in connection with the invention results in new surprising technical and chemical methods due to the exothermic heat generated and the correspondingly high vapor pressure.

According to the invention, completely new synthetic resin products are provided which have the characteristic of the additive in each case. Such additives are, for example, cement, cement asbestos, gypsum, sand powder. bitumen, bitumen polyester, metal oxides.it, clay soil, diatomaceous earth, kaolin, mica, asbestos, vermiculite, silicates, carbonates, glass beads, swelling agents (e.g. silicon).

Numerous combination possibilities result in a whole range of new products, which in turn are useful in a wide range of applications, as they combine a wide range of desired and required capabilities and features in a single product.

The special properties obtained with the products according to the invention are good cold, heat and sound insulation and the fact that the product retains fire well and withstands the effects of flames particularly well, no flammable gases are evolved, no flames and glow afterwards, low smoke formation, low flame height , The ignition temperature rises considerably and thermal radiation and heat transfer continue to be greatly reduced.

Furthermore, the substances can be formed as thermally conductive or non-conductive tower, electrically insulating or electrically conductive and / or radiation-absorbing.

The porous material is more resistant to fire than the dense material because the porous material conducts heat much worse. A material that changes to carbon foam under the influence of heat is also better than an unchanged material because the thermal insulation capacity of carbon foam is also good. However, the final products can also be formed to form a constant solid carbon layer. Carbon foam is formed from the layering masses by heating or flames, and the necessary additives include sugar, dextrose, urea, monohydric or polyhydric alcohols, e.g., glycerin, manganese ammonium phosphates, magnesium ammonium phosphates, and the like.

Many combustion problems can be solved or alleviated by the above method. The ability of almost all synthetic resins to retain fire proves to be considerably better in the case of furan resin mixed condensates, so in most cases the mixing of conventional halogenated flame-controlling chemicals can be dispensed with. However, depending on the intended use of the final products, known flame retardants can be used as additives. As such, e.g. the following: boron-based flame retardants, phosphorus, bromine, chlorine, and / or their modifications and derivatives. Further particularly suitable substances for this purpose are: antimony trioxide, sodium silicates, aluminum compounds such as aluminum phosphate, aluminum chromium phosphate, kaolin, Chinese clay, finely divided silicic acid, silicone, chloroparaffin trioxide, optionally chlorinated rubber, copper phthalocyanine, potassium tripolyphosphate, dicyandiamide, aniline, calcium carbonate and metal oxide.

The obtained materials can be placed, for example, in petrol tanks, especially in fire engines, in fireproof walls in mining, in fire walls in factories and in steel coal buildings and in shipbuilding, or also as preventive fire protection at cable breaks, bushings and the like.

Furthermore, there is a process-related possibility of mixing metallic, mineral and thermoplastic materials which melt or sinter without the action of flames or heat and form a strong cover layer on cooling.

Preferred are, for example, zirconium compounds which, at 600 ° C, reflect heat as light, finely divided silicic acid, tridibromopropyl phosphate, Chinese clay, dolomite and / or silicate-pretreated additives, such as sawdust, plastic products and / or foam.

The use of porous organic and / or inorganic additives significantly reduces heat transfer. Chemical products can be used as refractory insulation materials. Examples of porous inorganic additives are, for example, perlite, vermiculite, siliperli, foamed clay and / or, as organic additives, polystyrene, hard and / or soft polyurethane foam, polyester foam, aminoplastic foam and, if appropriate,

6601 7 6

Styrene derivatives used as additives, such as foamed polystyrene and soft polyurethane foam, which are otherwise easily combustible, no longer burn.

The layering mass can then be formed so as to obtain a strong, slightly porous carbon layer with a thickness of 2-3 mm, or also a strongly bulging layer of carbon foam with a thickness of 10-15 cm.

Because the carbon layer acts as a thermal insulator, the polystyrene balls still exist for about 20-30 minutes after the onset of flame action. The deposition mass then adopts the porous structure of the porous additives so that they have a heat-insulating effect even without a bulging carbon foam.

In a preferred embodiment of the invention, plastics and / or cellulose-based wastes can be used as additives, in particular foam wastes which, in connection with binders, form new insulating sheets which retain heat and flames better than the known plastics alone and which are based, for example, on polystyrene. polyurethane, aminoplastic foam or polyethylene foam.

The reuse of plastic waste and / or paper and / or textiles poses a significant environmental problem which can be alleviated by the invention. Particularly advantageous in the invention are the low development of smoke, the low flammability and the resistance to the action of chemicals.

Carbon tissue can swell or form a strong carbon layer due to flames. Even compared to phenolic resin, the smoke evolution of the binders turns out to be lower and the carbon tissue stronger.

When bitumen is used, it turns out that the resulting material no longer turns into a liquid due to the flames.

Other additives such as cresol, resorcinol, copper sulphate and paraformaldehyde fulfill various functions, prevent rot and mold formation, bitumen and / or tar act to achieve higher vapor density, etc.

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The products prepared according to the inventive idea can be ground and the powder can be mixed with organic and / or inorganic ingredients as a refractory additive.

Given the large number of products that can be manufactured, it is clear that what has been presented so far can in no way be considered as an absolute limit to the possibilities offered by the invention. Thus, the possibilities of use have not been presented in any way exhaustively.

Of course, all hitherto known measures used in connection with polyurethane, acrylic and alkyd resin, latex or epoxy resin can also be used in connection with the invention and / or allow the production of sheets, pipes and pipe joints according to known production methods.

Sheets and pipe joints can be made by mixing, spraying or using transport equipment. In addition, known devices can be used in the production of synthetic resin products. The previous applications and uses of synthetic resin foams and deposition compounds are also possible for the compositions prepared according to the invention.

When combining the components used, e.g. by mixing, spraying or stirring, the furan resin internal condensate is usually started. To this is added other resin, if used. The selected additives are then added, individually or as a mixture. In this case, it is advantageous to select the order of addition of the additives so that liquid or low-viscosity substances are added before solid or highly thickened substances. It is preferred that the acid addition takes place after all the substances have been combined.

When blending the polyester, unsaturated, high molecular weight polymerizable polyesters, which may contain little monostyrene, are particularly preferred.

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The following are some materials which are particularly advantageous for use in connection with the invention. It should be emphasized quite generally that water-tolerant resins are particularly suitable for addition to a furan resin mixed condensate.

As furan resin mixed compounds based on urea, melamine or phenol, it is particularly advantageous to use conventional commercial products with a viscosity of about 160-300 cps, a solids content of about 25-70%, a furfuryl content of about 10-80% and a pH of 6.5-7 , 5

In a particularly preferred embodiment of the invention, furan resin mixed condensates are used with 25-30% furfuryl alcohol 20-25% H =, and 12-14% N 2 content and a viscosity of 180-220 cps (e.g. FH 75, Kluser, Wuppertal, West Germany )

Another preferred furan resin mixed condensate has the following composition: 48-50% furfuryl alcohol 9-9.3% nitrogen 14-16% H 2 O and viscosity 180-220 cps (e.g., F H 200, Kliiser, Wuppertal, West Germany)

A particularly preferred phenol-furan resin has been found to be a product having a 60% furan resin content and a 40% phenolic resin content.

However, other conventional commercial products can also be used.

As the polyester, the following can be used, for example: Polygal casting emulsion E 81 (Bayer AG, Leverkusen, West Germany) or Palatal 6 (BASF AG, Ludwigshafen, West Germany).

Preferred water-tolerant epoxy resins are, for example, commercial products such as Versadukt 429 and Europox 716 BN (Schring AG, Bergkamen, West Germany).

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A preferred urea-formaldehyde resin which gives particularly favorable results is, for example, Foam Resin 293 (BASF AG, Ludwigshafen, West Germany).

Commercial products from Roehm & Haas, Darmstadt, e.g. monomer Muster 1, are useful as acrylic or methacrylic resin.

Finally, a preferred alkyd resin is Resydval VWA 3811 (Chemische Werke Albert, Wiesbaden, West Germany).

As a proportion of the amount of each component, the following are preferably used, expressed in each case per 100 parts by weight of furan-nhar ts i mixed condensates (all parts are by weight): I Furan resin mixed condensate 100 parts by weight 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 4-30 parts by weight. Acrylic resin: 1-75, particularly preferably 5-55 parts by weight.

Alkyd resin: 1-70, particularly preferably 3-45 parts by weight.

Latex: 1-70, particularly preferably 3-45 parts by weight.

III. Additives:

Inorganic additives: 1-250, particularly preferably 5-150 parts by weight (e.g. cement, Chinese clay, etc.).

Organic additives: 1-200, particularly preferably 3-130 parts by weight (artificial foams such as polyurethane foam; phenolic resin foam, etc.).

When porous substances such as vermiculite, perlite or siliperli are used, amounts of less than 90 parts by weight are preferred.

IV Acids: 2-40 parts by weight

The production of layering masses and porous materials with improved fire retention according to the invention can also be carried out by bringing said production materials, such as glass wool, glass silk, cellulose wool, carbon fibers, metal wires, etc., together with synthetic resins, by stirring or spraying.

Furthermore, polyacrylonitrile, polyvinyl chloride, novolak resin, coal tar and / or indene resin can be mixed with the synthetic resins to form a stable carbon foam or carbon layer by the action of fire.

A particular embodiment of the invention is that a synthetic resin is used in the form of an aqueous dispersion and powdered polyacrylonitrile, powdered polyvinyl chloride, powdered Novo lacquer resin, indene resin and / or rock resin are introduced or dispersed in these synthetic resin dispersions. The grinding of said materials, which under the action of fire form a stable carbon foam or a stable carbon layer, is carried out, for example, using non-ionic, cationic or anionic emulsifiers, such as alkylphenol-ethylene oxide adducts.

A particularly stable carbon foam or stable carbon layer is obtained when the compositions of the invention contain reinforcing materials such as mineral wool, glass wool, glass silk, cellulose wool, carbon fibers, boron and boron carbide wires, metal wires and / or springs, whereby mineral and glass wires. use is particularly advantageous. Carbon fibers, boron and boron carbide, wire and / or springs are in themselves very expensive materials, but nevertheless in the production of these reinforcing materials, which are extremely resistant to tension and compression, and which are themselves stable at extremely high temperatures and unchanged even in larger fires. defective batches are formed which cannot be used in air transport and spacecraft and which, such as carbon fibers, are then used as seals and in applications where only cheap reinforcing materials can be used. Such carbon fibers, boron and boron carbide yarns and metal wire doors are well suited for the production of fire retardant laminates and porous materials according to the invention, as they are also heat resistant up to 600 ° C under the influence of fire and keep the fire-formed carbon foam or carbon layer.

Also suitable as additives for the resins used according to the invention, in particular furan resins, are partially carbonized or pre-fired tar and pitch, as described in DE-OS 234102. The preferred furan resins useful for preparing the layering masses and porous materials 1 according to the invention are described by DT-AS. 639 and DT-AS 1,096,522, as well as Ullmann's Enzyklopedie der Technischen Chemie, part 13 (1962) Verlag Urban und Schwarzenberg, pp. 453-478.

Other polymers, such as, for example, polyurethane, acrylic, epoxy and / or alkyd resins, can also be used according to the invention in the production of layer layers and porous materials which have advantageous refractory properties.

Layered masses and porous materials prepared in accordance with the invention may be introduced in the form of sheets, pipe joints, pipes, layers or coverings for the protection of wood, ceramics, plastic or metal by placing them on top of these materials.

The proportion of laid reinforcing materials in the amount of material is about 1-50% compared to the proportion of plastic in the mixture used as a starting material in the production of layered masses and porous materials according to the invention. In the first place, the proportion of reinforcing material compared to the proportion of plastic is between 5 and 35% by weight.

The proportion of substances which, under the action of fire, produce a carbon-rich layer or carbon foam, such as polyacrylic acid, poly vinyl chloride, rock tar, etc., rises to about 5 to 50% by weight of the starting material. compared to the amount of plastic.

For example, a fluorine or furan resin soluble in water or alcohol or forming an emulsion in water, containing 50% by weight of resin, is homogenized with a polyacrylonitrile powder containing 5% by weight, a polyvinyl chloride powder containing 16% by weight and glass glasses having a weight of 4 em. is 10%, with 12,600,7 7 and is used in the preparation of the layering compositions according to the invention, in which inorganic fillers are optionally added. The above-mentioned phenolic resin used for the preparation of the deposition compositions according to the invention is water-soluble and its preparation is described in Ullmann's Enzyklopedie der Technischen Chemie, part 13, in the above-mentioned text, p. 465.

The production of more refractory deposition masses and porous materials according to the invention in various forms, such as sheets, fittings, layers, etc., is followed by mixing, spraying or casting, and the curing of the resin takes place using catalysts, especially acids. Private catalysts and curing conditions are mentioned, for example, in Ullmann's Enzyklopedie der Technischen Chemie.

A prerequisite for the reaction according to the invention to obtain a more fire-retardant fibrous reinforced layer or fibers and to form a carbon foam or carbon layer under the action of fire is a temperature which is between 50 and 1000 ° C. The formation of carbon foam or carbon layers in each case depends on the duration of the effect of temperature and the altitude of the prevailing temperature, for example even at relatively low temperatures, about 70 ° C, under said effect on the deposition mass for several hours or days, a carbonized porous or smooth carbon layer At a temperature of 700 ° C for a period of time ranging from one minute to an hour.

The ability of the deposition compositions and porous materials prepared in accordance with the invention to retain flames during a fire is enhanced by the addition of flame retardants such as antimony trioxide, antimony pentoxide, red phosphorus, melamine, etc.

According to the invention, a phenol-furan resin containing said reinforcing materials and optionally resins which, under the action of fire, form a dense carbon foam or carbon layer such as polyvinyl chloride, polyacrylonitrile, coal tar, etc. is 60% of the resin and 40% is furan resin.

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The advantage of the deposition compositions and porous materials prepared according to the invention is that the fire and heat retention capacity of plastics, in particular furan-resin mixed condensates, is substantially improved, whereby said fire retention capacity results in low smoke generation. With the method according to the invention, it is possible to obtain deposition masses and porous substances which, under the action of fire, form a carbon foam or a carbon layer which is fire-retardant and by means of which the spread of fire is prevented. For example, the formation of a hi il layer also insulates the steel structures of tall houses when the fire is strongly affected.

When foamed polystyrene and soft or hard polyurethane foam are used in the production of layered masses of porous materials by simultaneously using said reinforcing materials and carbon-promoting additives such as polyacrylonitrile, it is possible to reduce the strength of these organic foams, especially polystyrene. .

The deposition mass is prepared, for example, in such a way that a strong, light, porous carbon layer with a thickness of 0.1 to 3 mm or carbon foam containing reinforcing materials, which may be 15 cm thick, is formed under the influence of fire.

Example

To a commercially available aqueous still uncured mixed condensate of furan resin containing 60% furan resin and 40% urea, foamed polystyrene was added in 2 mm spherical bodies, and the aqueous mixture was poured into a mold to which a small amount of phosphoric acid was added as a hardener. The water was allowed to evaporate, leaving 3 plates with a thickness of 80 mm and a weight of about 497 kg / m.

The fire resistance of this plate was tested in accordance with DIN 4102, sheet 2 (published February 1970). After the combustion test, a carbon layer with cracks formed on the fire side of the plate. The thickness of the non-carbonated part of the plate was 5-10 mm.

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A temperature above 1000 ° C was used in the combustion test. The experiment shows that the refractory insulation board made according to the invention prevents fire from spreading very well to the spaces on the other side of the board in the event of a fire.

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