DE3616100A1 - Foam, and the use thereof, process for the preparation thereof, and apparatus for carrying out the process - Google Patents

Abstract

The invention relates to a process for the preparation of a self-supporting, heat-insulating foam which is characterised in that a first mixture (A) of inert, anhydrous fillers comprising from 45 to 35% by weight of obsidian, from 27 to 30% by weight of aluminium silicate, from 19 to 23% by weight of kaolin (china clay) and from 9 to 12% by weight of granulated polytetrafluoroethylene, and a second mixture (B) comprising from 60 to 51% by weight of an unsaturated ortho-phthalic acid polyester resin, from 20 to 25% by weight of an adipic acid-polyester resin, from 9 to 12% by weight of a solvating agent, from 5 to 7% by weight of gylcerol and from 6 to 5% by weight of a polyether resin are mixed to give a mixture (C), during which from 10 to 15% by weight of a crude isocyanate and from 0.8 to 1.2% by weight of a catalyst are simultaneously added under high pressure, and the resultant composition is then poured into moulds. The invention also relates to a foam obtainable by this process, and to an apparatus for carrying out this process. This apparatus has a catalysis chamber in which the crude isocyanate, a catalyst and, if desired, a monomeric styrene are simultaneously injected with the aid of high-pressure pumps, the base of the catalysis chamber containing a vertical outlet under which is arranged a vertical mould comprising two movable, vertically arranged, continuous belts parallel to one another and at a separation of from 10 to 50 mm from one another, which ... Original abstract incomplete.

Description

Foam as well as its use, process

for its production and device for carrying out the process the The invention relates to a foam, a method for its production, its Use and a device for performing this method.

The foam according to the invention is a rigid, Self-supporting foam with filler material based on polyester resins and an isocyanate having good heat insulating properties.

This foam is used for the production of molds and in them Molds cast objects of essentially the same composition are suitable. The device for carrying out the method according to the invention is in particular a continuous casting device.

In the previously known molding technique of dense or cellular Polymers are made from steel, Zama alloys (Zn, Al, Mg) or expensive forms Also used from reinforced polymer materials, on which in any case a release agent and a base coat or "primer" must be applied to ensure good separation to ensure the object from the mold. An object to be painted must also be subjected to a pickling process beforehand, since the presence of Residues of the release agent make it impossible for the paint to adhere.

According to the invention, a rigid foam is provided which is used for Production of forms is suitable, which neither require nor reinforcement Make the use of release agents, primers or the like. Required, so that the Forms and those formed in them Objects easily, quickly and can be produced economically.

It was surprisingly found that PTFE (polytetrafluoroethylene) is an excellent release agent and that a reasonable percentage of PTFE containing object can be easily taken out of the mold and smooth and has shiny surfaces. One therefore achieves a great advantage, the consists in the fact that release agents are not required, which, incidentally, are often due to the reaction heat (1800 C approx) and the strong, through the foam on the Mold walls exerted pressure to be dried out, whereby the removal of the The product becomes difficult to move out of the mold and the production areas are damaged and become uneven. In any case, the one treated with a release agent must be used Form extracted objects are subjected to a pickling process in order to only then to be able to be painted. The application of release agents to the mold walls, the careful removal of the items from the mold and the pickling process represent all work stages, which are due to the loss of time and the resulting Lengthening the manufacturing times significantly increases the cost of the end product.

As is well known in the foam art, these are common compositions used as starting material by the presence of with Isocyanates bound to polyols are labeled up to ten times their original value Expand in volume. The foams obtained in this way have a weight of 100 kg / m³ not excessive density and a resistance that is technical for a satisfactory application as building material is not suitable. Also are the physical ones Properties of these fabrics for the production of large, self-supporting Articles not suitable. In addition, those made from these foams tend to be Items tend to splinter and are unable to hold screws in place.

In particular, it should be noted that the chatty disadvantage, except for the limitation of the area of application of the foam to thermal and acoustically insulating fillers, the use of expensive support elements Made of metal, such as galvanized sheet metal or aluminum, makes it necessary to have a sufficient To ensure the strength of the foam products. All of this requires costly manufacturing stages and generates large amounts of waste.

In the U.S. U.S. Patent 4,206,294 (Halle et al) is a foam resin described, which consists of a liquid, unsaturated polyester, an organic Isocyanate compound, a surface active agent, an accelerator and a Composition of peroxide expansion agents being prepared. Among other things, will in this patent claims that the addition of surfactant agents is essential for expansion.

In any case, this is a sproedes material without Fillers, with low mechanical strength, having a density of 700/800 Kg / m3 and is therefore also expensive.

In the German patent specification 945.479 a method for the production is of foams made of high molecular weight polyurethanes, in which one unsaturated, branched or linear polyesters containing wholly or predominantly carboxyl end groups and polymerizable vinyl or allyl compounds in the presence of polymerization accelerators reacts with polyisotyanates. You get a stiff, fragile one Low specific weight foam, its practical use in not specified in this patent, but entirely intended for those Applications that require high mechanical strength properties are not appropriate is.

In Italian patent application no. 50562 A / 78 is a composition for the production of rigid, self-supporting foams, which 30-40% of an orthophthalic acid polyester resin, 28-19% of an isocyanate, 25.30-34.70% an inert silicate, 0.70 - 1.30% of a catalyst with an accelerator, 10 to 4.00 of a self-dissolving compound, and 6.00-1% of a thinner Contains styrene base.

You get a stiff foam with very good mechanical, chemical and physical properties, which has been successfully used in various fields of application, especially in construction, is needed where good self-supporting, self-extinguishing and insulating properties are required. However, this composition is for the new technological applications on the aerospace and aerospace industries electronic fields are not particularly suitable because of those in these fields the substances to be used are subject to very strict requirements.

It is therefore an object of the present invention to achieve this these new technological requirements and in the preparation of a composition, which has a fluidity suitable for continuous casting and for production of foams is suitable, which by a low specific weight, a high melting point, good stability against even temperature changes of about 2500C, a K-factor lower than 0.080 and a very high mechanical strength is marked.

Another object of the present invention is a method for the production of the substances mentioned and in a device for implementation this procedure.

The composition according to the invention contains an unsaturated one Orthopedic acid polyester resin mixed with an unsaturated adipic acid polyester resin, a solvation agent, glycerine and, with a polyether, inert mineral fillers, Polytetrafluoroethylene (PTFE), epoxidized soybean oil, an isocyanate, a Mesh catalyst and possible additives described below.

In particular, the unsaturated orthophthalic acid polyester resin the following composition: Phthalic anhydride 28 parts by weight maleic anhydride 16 parts by weight of monopropylene glycol 30 parts by weight Trinilzyamide glycol 2 parts by weight of monomer styrene 22 parts by weight of paraffin 2 parts by weight.

This composition is similar to that under the trademark SNIAL 5016/2 manufactured by SAVIO (Como, Italy) is sold in however, for the purposes of the present invention, this is the percentage of styrene decreased to 8% and the hydroquinine acting as an inhibitor was removed.

The unsaturated adipic acid polyester resin consists of the following Ingredients: orthophthalic anhydride 9-11% by weight maleic acid hydride 14-12% by weight % Propylene glycol 10-12% by weight styrene 25-30% by weight adipic acid 38-35% by weight this Resin is sold by the company SNIAL under the trademark SNIAL 5220 and is an excellent plasticizer that improves the impact resistance of adipic acid polyester resin improved.

The filling material consists of a mixture of the following four components: Obsidian 39% by weight kaolin 21% by weight aluminum silicate 29% by weight polytetrafluorenaethylene 11 wt.% The chemical composition in weight of the individual components is The following: Obsidian SiO2 - 72.00% Al 203 - 13.17% Na2O - 3.50 X CO, - 0.10% Fe203 - 2.00% K20 - 4.50% H20 - 3.70% SO - 0.10% CaO - 0.70% MgO - 0.12% TiO2 - 0.11 X kaolin SiO2 - 58.40% Al203 - 39.00% Na2O - 1.00% Fe202 - 0.70% K20 - 0.90% aluminum silicate SiO2 - 62.00% Al 203 - 30.00% Na20 - 4.00 % Fe203 - 4.00% Granular polymer PTFE PTFE 94.50%)) 100% Coke ash 5.50% All these ingredients are sold on the market: Obsidian is made by Cave di Lipari-Pumex (Italy), the kaolin is supplied by the Norwegian company Nepheline Synite is sold, the aluminum silicate is made by the Italian company Pozzi-Arosio while the granular polymer PFTE is sold by the Italian company Montefluos under the trademark Algoflon F2 ".

The technical properties of the individual components of the filling material are given in the following tab: Components granulanetry Density Melting Flamppunkt Terperatur- Warmeleitfaehigin Micron Kg / m point ° C oc G & iet keit K-Factor Obsidian 520 650 1400 5-120 0.09 Kaolin 80 260 1200 14-180 Silicate 300 350 1200 11-120 0.07 PTFE (granular) 35 400 327 -37-280 0.12 Coke ash 360 418 1180 1105 11-204 0.13 PTFE in solution Viscositaet 1500 10D 1090 1 (-190 0.14 800 The inventive addition of the component consisting of polytetrafluoroethylene It also increases the melting point and heat resistance of the end product and brings with it further advantages that result from the following properties of this Constituent parts are: a) optimal application possibilities from -37 to over 280 ° C; b) infinity (tried with flamethrower); c) very high insulation capacity; d) low dielectric constant, dielectric strength (D149-75) KV / mm80; e) Bulk weight 420; Granulometry 35 microns; f) lowest coefficient of friction among the Solids; g) Fractional 350 Kg / cm²; h) high corrosion resistance; i) unsolvable in solvents; k) typical self-lubricating agent.

In addition, the PTFE is used as a release agent against the temperatures 3400C constant and its presence in the product according to the invention allows a exceptionally easy separation from the form.

It should also be noted that when using the granular Polytetrafluoroethylene alone a transformation technique is used that of the Manufacture of ceramic articles is similar. Indeed softened and the PTFE only melts above the crystal phase (3430C), but also has a Viscosity that excludes extrusion and injection molding. Hence must the powder is mechanically pressed with a pressure of 110 kg / cm2 (preforming). It is then heated up to 3800C for 5 hours, whereby the cores are welded together will. The mass is then slowly cooled over 10 hours, so that the whole Processing usually takes 10 or more hours.

In contrast, the PTFE is used as a component of the filling material according to the present invention Invention surprisingly incorporated into the composition very quickly, without exerting any mechanical pressure. This is likely due to the Adding isocyanate to the mixture of all other ingredients is taking place chemical reactions at which temperatures of 185-200 ° C and High pressures are created that give the desired results within 5 minutes allow to receive.

Instead of granular Algoflon F2, a dispersion polymer was also used of PTFE i.e. Algonflon D60G used with good results. A product that still has given better results, but is PTFE Algoflon BN 29/9, manufactured by of the Ausimmont company of the Montedison group. These two products are also on the part sold by the above-mentioned company Montefluos.

Algoflon BN 29/9 with pH 9-10 consists of 60.5% PTFE, 6% Triton and 4% ammonia, finely divided in a non-ionic wetting agent. On this product the epoxidized soybean oil (1.4 wt.%) is added according to the invention, to get a better fluidity and elasticity of the product.

Algoflon BN 29/9, dissolved in epoxidized soybean oil (sold from the company ENGHEL), is in the mixture of polyester resins and other liquid Components incorporated.

To the mixture consisting of two saturated polyester resins, In view of the high viscosities of the resins mentioned, 10.5% by weight of a solvatant added.

An alkylaryl phosphate product was used as the appropriate solvatant, such as is sold by the company MONSANTO under the brand name SANTICIZER 148. This product, which consists of isodecil diphenyl phosphate, has proven itself in excellent Wise proven in the experimental samples and confirmed that the choice was correct was.

This solvatant is a clear, oily, odorless liquid, has a specific gravity of 1.070g / ml at 250C and a viscosity in centistokes of 97.5 at 0 ° C and 22.5 at 250C and is mostly organic Solvents solvable.

Glycerine becomes a mixture of unsaturated polyester resin Amount of 7% by weight at most, preferably 6.30% by weight, added as a vulcanizing agent serves.

To this mixture, an amount of at most 7% by weight is added Polyester resin with a low viscosity is added as a stiffening agent.

A polyether resin, particularly suitable for the invention Composition is under the brand name GLENDIOL 0700, GLENDIOL 0400, GLENDIOL 0222 distributed by the company MONTEPOLIMERI of the Montedison Group.

After the filling material with the above as described above Mixture of polymer resins has been mixed, to this mixture an amount of 1% by weight of an acetyl acetone peroxide catalyst added to which an amount of 0.05% by weight of an accelerator containing 6% by weight of the cobalt octoate was admixed which is usually added at a room temperature lower than 200 ° C. For the composition according to the invention that contains a proportion of monomer styrene contains, an ethyl methyl ketone catalyst is particularly suitable from the company Montedison sold under the PEROXIMON K3 brand.

Excellent results were also achieved with the product PEROXIMON DB " the same company Montedison also get a very good network and quick recovery guaranteed.

The isocyanate is added at the same time as the catalyst, as it z. For example from the company Schell & Co under the trademark CARADATE 30 and is sold by Mantedison under the trademark TEDIMON 31. That The product is liquid, has a dark brown color and has a viscosity at 250C from 160-240 pounds P and a density of 1.23 g / ml. The flash point of these products is 2000C and its hardening point is around 10 ° C.

In some cases, monomer styrene is also added up to 1% by weight, for example if you lower the viscosity of the mass at temperatures below 160C want.

The composition according to the invention is suitable for continuous (Strataggus and discontinuous pouring, as it will be described in more detail below.

Before describing the process for producing the inventive Composition overrides, in order to avoid any misinterpretation, it should still It should be noted that, firstly, each polyester has different properties. For the purposes of the invention, unsaturated polyesters are very strong in setting and high melting point, which are used, for example, for lining rocket projectiles and spaceships are suitable. Second, it should also be uplifted that the various components of the composition play a crucial role in preservation play the desired role in maintaining the desired properties, since In the course of the polymerization reactions take place which build up the individual Change components and probably give rise to the formation of new substances, which in their total time form the product, which is the technical one Resin area never has softened mechanical and physical properties, as has also been confirmed by laboratory tests which will be reproduced later.

The procedure consists of three separate stages, it will be carried out separately the solid mixture A of the fillers and the liquid mixture prepared. the The composition of these mixtures is as follows: MIXTURE A No. Ingredient Weight% granulometry (micron) 1 obsidian 45-35 520 2. aluminum silicate 27-30 300 3. Kaolin 19-23 80 4. Granular resin PTFE 9-12 20 These components of the mixture A have already been described.

MIXTURE B No. Ingredient Weight-X 1. Orthophtalsic acid polyester 53-40 2. Adipic Acid Polyester 20-25 3. Sivatant 9-12 4. Glycerin 6- 7 5. Polyeter Resin 6- 5 6. PTFE in solution 7-11 If PTFE in solution is used, then the Mixture A no granular PTFE added.

In special cases, however, PTFE can be used for mixture A. it can be added to mixture B in the desired proportion.

Mixtures A and B are then mixed together in a centrifuge.

The proportion between these two mixtures depends on the desired density. The preferred ratio of these mixtures is as follows: Mixture A 48% by weight + Mixture B 38% by weight = Mixture C 86% by weight Centrifuged for 3 minutes in a centrifuge at a speed of 1800 t / min and then placed in a catalysis chamber, in which 11-15% by weight of the Isocyanate and 0.8-1.2% by weight of the catalyst are injected. Should also introduce 1% by weight of the styrene into this catalysis chamber, then the isocyanate content becomes decreased by 1% by weight. If possible, however, you should add styrene refrain, as its damping is harmful to the BBDUG staff.

The mixture is due to the high injection pressure of the latter two Bestat'udteile strongly stirred and becomes more fluid and flowable, so that it can be cast continuously or discontinuously in molds, in which it foams and fully hardens within 5-8 minutes, even if it does is poured cold at a room temperature of 22-250C. The foaming that without Addition of additives, such as silicone freon or water, to the conventional ones Polyurethane technology, which takes place, is based on the excretion of hydroquinone, which is always avesend in the unsaturated polyesters, be it due to it, that the OH groups, no: # present in the unsaturated polyesters, and the in the silicates still remaining moisture of about 1.8% are sufficient to keep up with to react to the isocyanate and to release C02 in an amount that is necessary for the desired Expansion from 50 to 150% of the volume of the composition is sufficient.

The following 3 examples of discontinuous and continuous Giessens illustrate the inventive method.

EXAMPLE 1: Manufacture of a 25mm thick um plate with one density of 396 kg / m³.

MIXTURE A No. Ingredient% by weight Granulometry (Micron) 1 Obsidian 39 520 2 aluminum silicate 29 300 3 kaolin 21 80 4 PTFE granular 11 20 total: 100 MIXTURE B No. Ingredient% by weight 1 orthophthalic acid polyester 55.00 2 adipic acid polyester 23.00 3 Solvatant 4 Glycerin 6.30 5 Polyeter resin 5.20 Total: 100.50 That Mixture C is formed from Mixtures A and B which weigh 4.8 and 3.8 kg.

The mixture C is centrifuged at 1800 rpm for 3 minutes, whereby the viscosity is reduced and the flowability of the mass is increased. The mixture C @@ n is pumped and into this chamber is then in a Kata lysis Kaer at the same time 1.3 kg of isocyanate and 100 g of the catalyst of the type indicated above under high pressure (20 atm.) Injected.

The injection pressure of these two components stirs the whole mass during the injection period (10 seconds).

The mass is poured into a 25 liter mold. The mold is closed and ve @ scha @ u @ t the mass very quickly and fills the volume of the in 120 seconds Shape. The expansion is 150% (semi-foaming). The maximum temperature is 190-2200C and is reached in 180 seconds. After 10 minutes the hardened Plate is very easy to remove from the mold thanks to the addition of PTFE.

The weight loss is negligible (approx. 2%) and the density is 388 Kg 3 The panel can be sawed immediately and in machine tools without cracking be processed. With a total weight of 12,500 kg of the same composition you get a plate with a density of 488 kg / m³. A lot of 45 Kg of the same composition was poured into a 3x1x0.03 m mold and the obtained the same density of 488 kg / m.

The 30 mm thick plate with a density of 400 kg / m³ was technological Subjected to laboratory testing and the following results were obtained: Compressive strength: 82 Kg / cm2 Impact strength: a slight dent after the massive one Hit with a 1.5 kg hammer.

Thermal conductivity: 0.056 Kcal / m h ° C Melting point: melts at 7000C not thermal shock resistance: from 400C to 2000C in the oven: unchanged.

Mixtures A and B are intimately mixed in a 1800 T / min stirrer, to form the mixture C (17,200 kg = 86%), which is pumped into a catalise chamber is, in which at the same time under high pressure the isocyanate (2,400 kg = 12%), the Catalyst (0.200 kg = 1%) and the hydrogen peroxide (0.200 kg = 1%) are injected will.

The mixture (20 kg) is poured into a mold with a die 150 x100 x 3 cm (volume of 45 l) poured in until it fills half of the die.

The reaction time for gel formation: 2 minutes, for foaming 3 minutes and curing: 6 minutes, in total 11 minutes. The convex or concave piece is easily removed from the mold after 12 minutes and has a density of 3 of 422 kg / m³, with a wipe shrinkage of about 5%.

The convex and concave pieces of the shape thus obtained become one Mold combined, in which 20 kg of the. Mixture according to Example 1 according to here method described above is poured in order to z. E.g. a solar panel without a release agent of 144 x 94 x13 cm with a density of 468 Kg / M³.

The solar panel can be easily removed from this shape after 15 minutes on shows a smooth and shiny cast skin, without a bubble, which can be painted immediately can. This enables the following three process stages: applying the release agent, picking up and avoiding the use of primer, which was previously necessary before painting.

The possibility of manufacturing a solar panel with only one casting process, which at the same time is self-supporting, has excellent insulating properties and is unchangeable, has obvious advantages over conventional ones The manufacturing method of the solar panels. The # method described above can of course for the production of different items with different Cavities and / or projections are applied.

EXAMPLE 3. Continuous casting.

The mixture prepared as in Example 1 is placed in a catalysis chamber continuously introduced under a pressure of 12 atm., simultaneously and simultaneously continuously the isocyanate and the catalyst in the same percentage as in Example 1 are injected. The mass thus obtained is continuous in a mold cast, which consists of two vertically arranged movable strips.

The distance between the bands depends on the desired thickness the plate to be produced is set. The one at the end of the movable belts perfectly The hardened sheet is cut to the desired length. The plate can be used at the same time on both sides with a laminate made of every plastic, veneer sheets, Paper, cardboard or the like can be covered, depending on the purpose of the plate in the various areas in which it can be applied.

The method according to the invention, in particular the continuous casting method, should be carried out in a device that is primarily one for the Continuous casting installed Catalytic Chamber and second a movable one for the vertical continuous casting has attached rolling mill. One has to find out know that the mixer currently used for foams with the conventional mechanical agitator blades because of the resistance acting on the blades of the viscous catalyzed #composition blocked. It has now been found that this disadvantage can be completely overcome by replacing the mechanical Agitation, in the catalysis chamber at the same time with the mixture C and the isocyanate the catalyst can be injected in the atomized state under high pressure, wherein a perfect homogenization of the mixture to be poured is achieved.

The cleaning of the chamber is carried out very easily with the compressed air.

A preferred embodiment of the device according to the application is shown, for example, in the accompanying drawings, in which: Fig.1 shows schematically the mixing device according to the invention; Fig.2 illustrates the closing device for hermetically closing the mouths for the introduction of the mixture C in the catalysis chamber and FIG. 3 shows this vertical shape Continuous casting.

As can be seen in Figure 1, the mixtures A and B are more well known Way through the dosing containers 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 and pre-mixers known per se 10 and 11 prepared. The mixtures A and B are then introduced into a centrifuge 12, the one by a motor M rotating at a speed of 1800 T / m set agitator 13 has.

At the bottom of the centrifuge 12 are 4 outflow tubes and 4 return tubes 14 provided, through which the mixture C homogenized in the centrifuge by means of two pumps 17 under a pressure of about 12 atm. into a catalysis chamber 15 an eClosing device 16 is introduced.

Immediately in the catalysis chamber 15 a predetermined amount of the mixture C (mixtures A + B) is carried out, the locking device closes automatically 16 and the semicircle C is through the tube 14 of the locking device in the Centrifuge returned to always remain homogeneous.

At the same time pumps 18 and 19 and optionally 20 are in operation ge u t to the isocyanate from a container 21, the catalyst from a container 22 and possibly the styrene (in a container 23) under the pressure of 20 atm.

inject into the catalysis chamber. Already starts after 2 seconds the reaction, the spout is opened and the composition is put into a Poured in the form.

If the device described here above is set for continuous casting then a perpendicular shape is used, consisting of two parallel to each other movable belts 24, which form the side walls of the mold, of course is also closed at the top and bottom. The bands 24 are still 120 and be moved on vertical rollers 25 at a speed of 4 m / min. Of the The distance between the parallel strips 24 is adjustable in a range ç 16Es0 mm, so that in this continuous casting process 1 to 5 cm thick plates are desired Can produce length.

The top and bottom walls of the form are by endless horizontal Caterpillars bands 26 are formed, which move at the same speed of the vertical Moving bands 24. The composition is from the catalysis chamber 15 in this Poured vertical shape up to a height of about 40 cm and foams very quickly on the stretch of 28 m, which corresponds to the length of the bands 24.

The plate comes out of the mold in the fully hardened state and is fed to the cutting devices.

To produce both sides; clad panels with one on a coil wound laminate of any kind, the laminate 27 is in the form introduced and taken from the corresponding belt 24, whereby it is different from his Coil unwinds.

In this way, the mass between the two expands and hardens Laminates and strongly adheres to the same.

The locking device 16 consists of a chamber into which the Mixture C is introduced by pumps 17. This chamber has a bottom with four Outflow openings 31 through which the mixture flows into the catalysis chamber 15.

After the dosed filling of the same, these mouths closed by a clover leaf-shaped closure plate 28 made of self-lubricating Teflon, which is rotated by 450 with every entry and exit.

The locking device 16 also has a plurality of circular arranged thread launder 32, into which screws 30 are screwed, the the flange of the catalysis chamber 15 to the locking device 16 with an insert Clamp the seal.

The catalysis chamber is washed with compressed air without solvents. In the currently used catalysis chambers, in which the mixing is mechanical is carried out by stirring paddles, it is necessary in the event of stopping, Introduce a solvent into the chamber to remove the product residue from the agitator paddles The casting in a vertical form avoids possible disadvantages of continuous pouring into the forms consisting of horizontal strips. These disadvantages are that bubbles form on the surface of the product form, which are created by foaming the reaction gases that are pressed upwards. These gas bubbles form a number of voids in the plate, which form the mechanical Strength of the same be.e ## traecht i gen.

While this phenomenon is neglected in the case of polyurethanes can.

which are consequently poured into the horizontal movable molds can.

On the other hand, they would have the disadvantages mentioned above when pouring horizontally Forms of compositions based on the unsaturated polyester cause.

For this reason, according to the invention in the vertical movable Molds cast in order to completely avoid these disadvantages. You get it Plates perfectly smooth on both sides and the difference in DIohWE between the lower and upper plate part is hardly 3%, a difference that the mechanical strength of the plate absolutely not impaired.

You also get the advantage that the foaming and hardening times can be decreased by 2 seconds, which increases the productivity set.

This is due to the fact that the flowing, self-contained mass develops the heat faster, which causes the reaction becomes livelier and exerts greater upward pressure on the mass. During the reaction, as already said, the heat develops, and when it does If the endothermic reaction has been exhausted, the crosslinking is also complete and all cells are evenly distributed within the plate.

The continuous casting process using the vertical Shaping allows plates with a cellular structure to be obtained. which opposite the structures obtained when pouring into the horizontal molds are much better is. In addition, the pouring head remains fixed when pouring vertically, while when pouring horizontal casting movable casting heads are used, which because of their more complex Structure are less reliable and the evenness of the pouring and the Does not insure the distribution of the mass, which means that the density of the plate is also not guaranteed becomes even.

The present invention has been made with reference to a preferred embodiment described, but it goes without saying that different modifications of the same can be used without departing from the scope of the invention.

Claims (15)

Claims 1. Process for the production of self-supporting, heat-insulating foams, based on unsaturated polyester resins and an isocyanate, indicated by the fact that a first mixture is obtained (A) from inert, anhydrous fillers consisting of 45 to 35 wt .-% obsidian, 27 to 30% by weight aluminum silicate, 19 to 23% by weight kaolin and 9 to 12% by weight granulated Polytetrafluoroethylene and a second mixture (B) of 60 to 51% by weight of an unsaturated ortho-phthalic acid polyester resin, 20 to 25% by weight of an adipic acid polyester resin, 9 to 12% by weight of a solvating agent, 5 to 7% by weight glycerin and 6 to 5% by weight a polyether resin, mixed to form a mixture (C), while at the same time under High pressure 10 to 15% by weight of a crude isocyanate and 0.8 to 1.2% by weight of a catalyst adds, and the mass thus obtained is then poured into molds. 2. The method according to claim 1, characterized in that one is a Mixture (A) is used, which consists of 39% by weight obsidian, 29% by weight aluminum silicate, 21 Wt .-% kaolin and 11 wt .-% polytetrafluoroethylene. 3. The method according to claim 1, characterized in that one is a Mixture (B) is used, which consists of 55% by weight of unsaturated ortho-phthalic acid polyester resin, 23% by weight adipic acid polyester resin, 10.50% by weight solvating agent, 6.30% by weight Glycerin and 5.20% by weight of polyether resin. 4. The method according to any one of claims 1 to 3, characterized in that that 48% by weight of the mixture (A) are mixed with 38% by weight of the mixture (B) and to the 86% by weight of the mixture (C) obtained, 13% by weight of crude isocyanate and 1% by weight Adding catalyst. 5. The method according to claim 4, characterized in that one for Mixture (C) 12% by weight isocyanate, 1% by weight catalyst and 1% by weight monomeric styrene gives. 6. The method according to claim 1, characterized in that the Mixture (C) using high pressure pumps, preferably at a pressure of 12 atm., Introduced into a catalytic chamber, in which the crude isocyanate and the catalyst injected under high pressure in the atomized state. 7. The method according to claim 6, characterized in that the After a catalytic reaction lasting 2 seconds, the mass is poured into a vertical mold. 8. Self-supporting, heat-insulating foam based on unsaturated Polyester resins and an isocyanate obtainable by the process according to any one of Claims 1 to 7. 9. Use of the foam according to claim 8 for molds. 10. Device for performing the method according to one of the claims 1 to 7 with containers and dosing devices for the individual components and with mechanical mixers for the preparation of the mixtures (A) and (B) and with a Centrifuge to mix the mixtures (A) and (B) to prepare the mixture (C), characterized in that two pairs of tubes emerge from the bottom of the centrifuge (12) (14) extend downwards, a pump (17) being provided for each pair of tubes is to the mixture (C) under a high pressure, especially of 12 atm., about to pump a closing and return device (16) into a catalytic chamber (15), and that the catalysis chamber (15) with high pressure pumps (21, 22 and 23) for simultaneous Injection of isocyanate, catalyst and optionally monomeric styrene equipped is and has a vertical pouring mouth at the bottom. 11. The device according to claim 10 for continuous casting of plates, characterized in that a vertical shape is provided below the pouring mouth is made up of two parallel to each other and at a distance of 10 to 50 mm from each other vertically arranged, endless belts (24) that form the vertical walls of the mold form and at a constant speed on a set of vertical rollers (25) are moved, and consists of two endless caterpillar belts (26), which are moved at the same speed on horizontal rollers and which Form upper and lower walls of the mold, with a tube (29) attached to the pouring mouth is connected to the casting compound from the catalytic chamber (15) on the lower wall pour the mold. 12. The device according to claim 11, characterized in that one or both vertical bands (24) a coil (27) made of metal or plastic laminate is assigned to coat the surfaces of the sheet emerging from the mold. 13. Device according to one of claims 10 to 12, characterized in that that the bottom wall of the closing and return device (16) is the upper wall of the catalytic chamber (15) forms and four outflow openings evenly spaced on a circular line (31) and a four-humped closure for the outflow openings that can be rotated by 900 (31). 14. Device according to one of claims 10 to 13, characterized in that that it is automatically controlled in a known manner from a control station. 15. Use of polytetrafluoroethylene for demoulding solid or semi-foamed articles made of a self-supporting thermally insulating foam according to claim 8 when using molds made of the same foam.