DE10130650A1 - Method for introducing liquids into a mold by means of a conveyor - Google Patents

Abstract

The invention relates to a method for introducing fluids into a mould by means of a delivery device which comprises an upper layer (i) and a lower layer (iii), said upper layer (i) comprising at least one opening (iv) through which the liquid passes. The invention is characterized in that the discharge end of the delivery device or a mounting for the discharge end of the delivery device is screwed onto the layer (i) in at least three places.

Description

The invention relates to methods for introducing Liquids by means of a conveyor in a form that a upper layer (i) with at least one opening (iv) through which Liquid is filled, and has a lower layer (iii).

For the construction of ships, for example ship hulls and cargo space covers, bridges, roofs or high-rise buildings Construction parts are used, the significant loads can withstand external forces. such Construction parts usually consist of these requirements Metal plates or metal supports through an appropriate Geometry or suitable struts are reinforced. So exist hulls of tankers due to increased Security standards usually consist of an inner and an inner outer fuselage, each fuselage made of 15 mm thick steel plates, which are connected by approx. 2 m long steel struts are built up. Because these steel plates have significant forces both the outside and the inside are exposed Steel shell stiffened by welded-on reinforcement elements. A disadvantage of these classic construction parts out both the significant amounts of steel that are needed as well as the time and labor-intensive production. In addition, such construction parts have a considerable amount Weight on, resulting in lower tonnage of the ships and results in an increased fuel requirement. In addition are such classic construction elements based on Steel requires a lot of maintenance because both the outer surface, as well as the surfaces of the steel parts between the outer and the inner shell are regularly protected against corrosion have to.

PLC elements are a replacement for the steel structures (Sandwich plate system) known, which is a composite of metal and include plastic. Due to the liability of the Composite elements are created on the two metal layers with extraordinary advantages over known steel Constructions. Such PLC elements are known from the documents US 6 050 208, US 5 778 813, DE-A 198 25 083, DE-A 198 25 085, DE-A 198 25 084, DE-A 198 25 087 and DE-A 198 35 727. These composite elements are usually used manufactured in such a way that the starting materials for production of the polyisocyanate polyadducts in one Work step poured or sprayed between the metal plates become. Because the reactive starting components for manufacturing the plastics in the composite element already when mixing start responding and completely filling the room between the metal plates prerequisite for a flawless Is the process of injecting the product Starting components a crucial and critical step in the process Manufacture of the composite elements. Especially with reactive Liquids that harden cause additional leakages Workload.

The present invention was therefore based on the object improved process for the introduction of liquids by means of to develop a conveyor into a form in which just filling the space between plates (i) and (iii) especially with the starting components for the production of Plastics (ii) between the plates (i) and (iii) optimized becomes. This manufacturing process should in particular share significantly reduce defective elements and a safe one Introducing liquid components between the plates of the Allow composite element.

This object was achieved in that the Outflow end of the conveyor or a holder for the Outflow end of the conveyor at at least three points, preferably three to six digits, particularly preferably four or screwed five places to the layer (i). The is preferred Liquid through at least one opening (iv) in (i) and / or (iii) filled in the space between (i) and (iii).

The expression "outflow" can be common Trade facilities with the help of which liquids are filled are, for example, tank sockets, hose ends, mixing heads Static mixer or the like. It is preferably the Outflow around a mixing head. Such mixing heads are generally known and for example in connection with usual Dosing devices for commercial polyurethane systems available.

The "liquids" are preferably liquid Starting components for the production of plastics, preferably those which adhere to (i) and (iii), particularly preferably it is the one shown later Starting components for the production of Polyisocyanate polyaddition products.

Layers (i) and (iii) usually have no features on that to attach an outflow end for filling can serve with liquids. The attachment can be preferred done in such a way that you have bolts with a thread that are used for Attach the outflow end or the bracket in which Layer (i) shoots. These bolts can preferably on the Taper the thread-facing side to make it easier to insert it into the To be able to introduce layer (i). The bolts preferably have a diameter of 6 mm to 20 mm and a length of 8 mm to 42 mm. The thread after fixing the bolt after is directed outside, d. H. on the side of (i) that of (iii) facing away, preferably has a length of 4 mm to 30 mm. The The bolts are inserted, for example, by shooting with With the help of a bolt feed tool that is commercially available e.g. B. at the Hilti is available. Preferably (i) thus has threads with the help of which the outlet end at the opening (iv) which the liquid is filled with is screwed with (i). One can preferably improve the seal between the Outflow and the layer (i) between the layer (i) and the Attach an O-ring made of an elastic material to the mixing head. Such O-rings are generally known and can in their Dimensions on the diameter of the opening (iv) and the Mixing head can be matched.

It is particularly preferred not to attach the outflow end directly on the layer (i), but fixes the outflow end on one Bracket that is screwed to (i). With this bracket, made of common materials, such as plastics, Wood or preferably common metals can exist prefers a construction with holes, through which the threads fixed on (i) are guided and for example, be fastened by means of appropriate nuts. Moreover the bracket has fasteners for the outflow end on, for example plug connections, screw connections or Edges with which the outflow end with elastic bands with the bracket can be clamped. Is particularly preferred the outflow end at at least three points with the bracket attached to avoid tilting.

One is therefore preferred to mount at least three Screw threads that are attached to (i) and to them Fix the mixer head in place. The bolts can after Completion of the composite elements, for example on the surface sawn off from (i).

Filling the space between (i) and (iii) can be done with usual Conveyors, preferably continuously, carried out with, for example, high and low pressure machines, preferably high pressure machines. Filling is preferred with a high pressure machine over one or more, preferably a mixing head, in which the starting components are mixed, in a single step, preferably injection process. In a single injection process means that the filling of the Space between (i) and (iii) for example with the Starting materials for the production of (ii) before full filling is not interrupted. The raw materials are thus preferably in a single shot under pressure in the space between (i) and (iii) given. This is especially true if it is the liquid is a reactive mixture with the reaction hardens. It is therefore preferred to wear the Starting materials by means of a high pressure apparatus over one or more, preferably a mixing head. Filling the space between (i) and (iii) can be both in the vertical orientation of (i) and (iii), as well as in the horizontal alignment of (i) and (iii) respectively.

Layers (i) and (iii) can preferably be used as conventional ones Plastic, wood or preferably metal plates, for example Iron, steel, copper and / or aluminum plates, with the thicknesses according to the invention are used.

Both (i) and (ii) can be coated, for example primed, primed, painted and / or with usual Plastics coated in the manufacture of the invention Composite elements are used. (I) and (iii) are preferred uncoated and particularly preferably, for example Usual iron shot blasting cleaned used.

Preferably, (i) and / or (iii) in addition to the or Openings (iv) through which the starting components for production of (ii) are entered, at least one further opening (v) on. The amounts of starting materials for the production of (ii) are difficult to measure so that just the space to be filled (R) is filled, but overflow is prevented. Therefore a larger amount of starting components is preferred Production of (ii) given in the space between (i) and (iii), than this can record. The resulting overflow will preferably discharged through openings (v). You can preferably on the or attach overflow vessels to the openings (v). These overflow vessels are preferably in a position above the between (i) and (iii) with the starting materials for the preparation of (ii) filling space. This has the advantage that only after complete filling with the starting materials an increase in still liquid, d. H. raw materials not yet fully reacted be found in the overflow vessels. On the rise the starting components in the overflow vessels can thus the complete filling of the space between (i) and (iii) determine. The openings can be closed, for example with a plastic or metal plug, preferably with a Screw cap that is either in the overflow vessel or is preferably located between the overflow vessel and (i) and / or (iii), respectively. The openings (iv) preferably remain until the end of the Hardening process of the mixture (a) and (b) by the fixed Mixing head closed.

In addition, one or preferably several openings (v) serve to allow air to escape from (R) during the filling process.

The openings (iv) and (v) are preferably Bores in (i) and / or (iii) with a diameter of 0.5 to 5.0 cm in (i) and / or (iii).

The space between (i) and (iii) with the starting materials to produce (ii) does not have to fill the entire room between (i) and (iii). Both (i) and (iii) can protrude beyond the edges of (ii), i. H. only in one Part of (i) and (iii) is bound by (i) via (ii) to (iii). For example, the space between (i) and (iii) before filling with the starting materials in this way be sealed so that the seal is within the range of (i) and (iii) enclosed space and edges of (i) and / or (iii) survive.

The conveying capacity can be dependent on what has to be filled Volume can be varied. To ensure a homogeneous hardening of (ii) to ensure the delivery rate and funding facility preferably chosen such that the space to be filled within from 0.5 to 20 min with the components for the preparation of (ii) can be filled. It is preferably low pressure or particularly preferably high pressure machines, preferably with Piston metering, particularly preferably axial piston metering, wherein preferably the storage container with agitator and preferably heatable is designed and preferably a circuit reservoir Mixing head storage container is present, preferably the Discharge capacity is 0.1 to 3.0 kg / sec.

The starting components for the production of the Polyisocyanate polyadducts are usually made at one temperature from 0 to 100 ° C, preferably from 20 to 60 ° C, mixed and like already described in the space between (i) and (iii) brought in. The mixing can be done mechanically using a stirrer or a stirring screw, but preferably by the High-pressure machines usual counterflow principle take place in which A- and B- Component jet in the mixing head under high pressure hit and mix, taking the beam of each component can also be divided. The reaction temperature, i.e. H. the Temperature at which the reaction takes place is in Depending on the material thickness usually> 20 ° C, preferred 50 to 150 ° C.

In the development of suitable manufacturing processes found that an uncontrolled leakage of liquid Starting components for the manufacture of (ii) hardly become defects fix it. Due to the limited amount per shot introduces uncontrolled loss of raw material for the production of (ii) incomplete filling of the space between (i) and (iii). Because of the quick response and the very good Liability of (ii) to (i) and (iii) arise from a incomplete filling of large areas in the composite element that no (ii) included and also no longer with starting components can be filled. Such composite elements must unfortunately be discarded.

To prevent loss of output components, it has therefore proved to be advantageous, the shape to be filled very precisely check for leaks. Usually the Layers (i) and (iii) in a suitable arrangement, for example parallel to each other, fixed. The distance is usually chosen so that the space (R) between (i) and (iii) is a thickness from 10 to 300 mm. The fixation of (i) and (iii) can for example by spacers z. B. in a form or suitable bracket. The edges of the space are usually sealed such that the space between (i) and (iii) with the liquid or Starting components for the production of (ii) are completely filled can, a flow out of these starting components before the complete filling is prevented. Sealing can with usual plastic, paper or metal foils and / or -Plates that are glued or welded, for example are pressed and, if necessary, also as a spacer can serve. This preferred sealing relates do not refer to the preferred openings (iv) and (v) that were presented at the beginning.

Checking the tightness of (R) before filling with the starting components are preferably carried out by Differential pressure measurement. Under the expression pressure difference measurement is too understand that one is trying to find a pressure difference between the space (R) and the outside environment over a period of time to build up, for example by trying to create a sub- or to achieve overpressure in relation to the external environment. This can be done using conventional vacuum pumps or generally known ones Compressors that pump air or gas into the room (R) have been reached become. Can create a stable positive or negative pressure in (R) this indicates a sufficiently dense cavity with the starting components for the production of (ii) can be filled. It is preferable to note that one the openings (iv) and (v) that are used to fill (R) with the starting components or as ventilation openings or as overflow openings for the discharge of excess Provides starting components, also temporarily seals. there if necessary, at least one of these openings can serve Connect vacuum pump or compressor to (R).

While filling the liquid in the space between (i) and (iii) can preferably a negative pressure in the to be filled Space. This offers the advantage that the liquid "sucked" into the room and also small cavities with the Liquid to be filled. It is therefore preferred that the Starting materials for the production of (ii) in the liquid state in the space between (i) and (iii) and during this Filling a negative pressure in the space to be filled between (i) and (iii). The negative pressure is preferably in the space to be filled 0.2 to 0.8 bar, d. H. the pressure in the form to be filled is 0.8 bar to 0.2 bar lower than that Ambient air pressure. The negative pressure caused, for example, by well-known vacuum pumps can be generated preferably achieved in that (i) and / or (iii) in addition to the one or more openings (iv) in (i) and / or (iii) through which the starting materials for the production of (ii) are registered, have at least one other opening (v) through which the negative pressure is applied.

Preferably, the space to be filled between (i) and (iii) especially dry before filling. This has the advantage that in particular liquid components to be filled, the are reactive towards water, for example isocyanates, not in react unwanted side reaction. The drying that preferably takes place directly before filling, for example using hot air or compressed air. Furthermore you can fill the space between (i) and (iii) heating (i) and / or (iii) to a temperature of Dry at 20 to 150 ° C for 10 to 180 minutes. Prefers you can fill the space between (i) and (iii) with a Blow dry the air through openings (iv) and (v) in (i) and / or (iii) through the space to be filled between (i) and (iii) directs.

• a) 2 mm bis 20 mm, bevorzugt 2 mm bis 10 mm, besonders bevorzugt 5 mm bis 10 mm Metall, Kunststoff oder Holz, bevorzugt Metall,
• b) 10 mm bis 300 mm, bevorzugt 10 mm bis 100 mm eines Kunststoffes, der durch Härtung der in Form gefüllten Flüssigkeit entsteht,
• c) 2 mm bis 20 mm, bevorzugt 2 mm bis 10 mm, besonders bevorzugt 5 mm bis 10 mm Metall, Kunststoff oder Holz, bevorzugt Metall,

wobei sich die Längenangaben auf die Schichtdicken beziehen. Die Breite der Verbundelemente kann üblicherweise 0,5 m bis 10 m, bevorzugt 1 m bis 5 m betragen. Die Länge der Verbundelemente kann im allgemeinen 0,5 m bis 10 m, bevorzugt 1 m bis 5 m betragen. Bevorzugt sind die Schichten (i) und (iii) parallel angeordnet. Die seitlichen Ränder des Raumes zwischen (i) und (iii), der mit (ii) ausgefüllt wird, werden bevorzugt abgedichtet, bevorzugt mit Kunststoff-, Papier- oder Metallfolien oder -platten, besonders bevorzugt Metallplatten, die beispielsweise verklebt, verschweißt oder angepresst, bevorzugt angeschweißt, werden und die gegebenenfalls auch als Abstandshalter dienen können. Composite elements which have the following layer structure are preferably produced using the method according to the invention:

• a) 2 mm to 20 mm, preferably 2 mm to 10 mm, particularly preferably 5 mm to 10 mm metal, plastic or wood, preferably metal,
• b) 10 mm to 300 mm, preferably 10 mm to 100 mm, of a plastic which results from the hardening of the liquid filled in the mold,
• c) 2 mm to 20 mm, preferably 2 mm to 10 mm, particularly preferably 5 mm to 10 mm metal, plastic or wood, preferably metal,

the length specifications refer to the layer thicknesses. The width of the composite elements can usually be 0.5 m to 10 m, preferably 1 m to 5 m. The length of the composite elements can generally be 0.5 m to 10 m, preferably 1 m to 5 m. Layers (i) and (iii) are preferably arranged in parallel. The lateral edges of the space between (i) and (iii), which is filled in with (ii), are preferably sealed, preferably with plastic, paper or metal foils or plates, particularly preferably metal plates, which are glued, welded or pressed, for example , preferably welded, and which can optionally also serve as spacers.

Accordingly, the shape to be filled preferably consists of the indicated layers (i) and (iii), preferably in parallel are arranged, as well as seals between the layers (i) and (iii), which prevent the liquid from flowing out during Prevent filling. Layer (ii) is therefore preferably adhesive arranged between layers (i) and (iii).

The liquid for the preparation of (ii) (a) preferably contains Isocyanates and (b) compounds reactive towards isocyanates. Layer (ii) is therefore preferred Polyisocyanate polyadducts. In this document are among the Expressions "starting materials" or "starting components" in particular (a) isocyanates and (b) reactive towards isocyanates To understand connections, but if necessary, insofar as they Also used are (c) gases, (d) catalysts, (e) auxiliaries and / or (f) blowing agents.

The reaction of (a) with (b) to (ii) in is preferably carried out Presence of 1 to 50% by volume of gases (c). Preferably sets one as (b) polymer polyols. The implementation is preferably carried out of (a) with (b) in the presence of (f) blowing agents.

The polyisocyanate polyadducts (ii) according to the invention Composite elements produced preferably have Elastic modulus of> 275 MPa in the temperature range from -45 to + 50 ° C (after DIN 53 457), an adhesion to (i) and (iii) of> 4 MPa (according to DIN 53 530), an elongation of> 30% in the temperature range of -45 to + 50 ° C (according to DIN 53 504), a tensile strength of> 20 MPa (according to DIN 53 504) and a compressive strength of> 20 MPa (according to DIN 53 421).

The composite elements according to the invention can be produced carry out in such a way that between (i) and (iii) polyisocyanate Polyaddition products (ii), usually polyurethanes, the optionally urea and / or isocyanurate structures can have, by reacting (a) isocyanates with (b) Compounds which are reactive toward isocyanates, if appropriate in Presence of blowing agents (f), 1 to 50% by volume, based on the Volume of the polyisocyanate polyadducts, at least one Gases (c), (d) produces catalysts and / or (e) auxiliaries, preferably (ii) adheres to (i) and (iii). The production Such polyisocyanate polyadducts (ii) are common have been described.

The surfaces of (i) and (iii) can be prepared before the Composite elements for cleaning and increasing the Surface roughness with sand or steel balls, preferably with corundum or Iron grit to be blasted. This blasting can be done according to the usual Processes are carried out in which the blasting material is, for example, high pressure hits the surfaces. Suitable equipment for such treatment are commercially available.

By treating the surfaces of (i) and (iii), the are in contact with (ii) after the implementation of (a) with (b), leads to a significantly improved liability of (ii) to (i) and (Iii). The blasting is preferred directly before the introduction of the Components for the production of (ii) in the space between (i) and (iii) performed. The surfaces of (i) and (iii) to which (ii) should adhere, are preferably free of inorganic and / or organic substances that reduce adhesion, for example Dust, dirt, oils and greases or generally as Mold release agents known substances.

The starting materials (a), (b), (c), (d), (e) and (f) in the process according to the invention are described below by way of example:
Suitable isocyanates (a) are the aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates known per se, preferably diisocyanates, which may have been biuretized and / or isocyanurated by generally known methods. The following may be mentioned as examples: alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyl-tetramethylene diisocyanate-1,4,2-methylpentamethylene diisocyanate-1,5, tetramethylene diisocyanate-1,4, lysine ester diisocyanates (LDI) , 1,6-hexamethylene diisocyanate (HDI), 1,3-cyclohexane and / or 1,4-diisocyanate, 2,4- and 2,6-hexahydrotolylene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,2 '- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), 4 , 4'-, 2,4'- and / or 2,2'-diphenylmethane diisocyanate (MDI), polyphenylpolymethylene polyisocyanates and / or mixtures containing at least two of the isocyanates mentioned. In addition, di- and / or polyisocyanates containing ester, urea, allophanate, carbodiimide, uretdione and / or urethane groups can be used in the process according to the invention. 2,4'-, 2,2'- and / or 4,4'-MDI and / or polyphenylpolymethylene polyisocyanates are preferably used, particularly preferably mixtures containing polyphenylpolymethylene polyisocyanates and at least one of the MDI isomers.

As (b) isocyanate-reactive compounds For example, connections are used that are considered opposite Isocyanate reactive groups hydroxyl, thiol and / or primary and / or have secondary amino groups and usually have a molecular weight of 60 to 10,000 g / mol, for. B. Polyols selected from the group of polymer polyols, Polyether polyalcohols, polyester polyalcohols, polythioether polyols, hydroxyl-containing polyacetates and hydroxyl-containing aliphatic polycarbonates or mixtures of at least two of the polyols mentioned. These connections usually point functionality to isocyanates from 2 to 6 and one Molecular weight of 400 to 8000 and are the expert well known.

For example, the following come as polyether polyalcohols known technology through the addition of alkylene oxides, for example tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and / or 1,2-propylene oxide to customary starter substances are available. Known starting substances can be used, for example aliphatic, araliphatic, cycloaliphatic and / or aromatic compounds are used, at least one, preferably 2 to 4 hydroxyl groups and / or at least contain one, preferably 2 to 4 amino groups. For example can be used as starter substances ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerin, trimethylolpropane, Neopentyl glycol, sugar, for example sucrose, pentaerythritol, Sorbitol, ethylenediamine, propanediamine, neopentanediamine, Hexamethylenediamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2- (ethylamino) ethylamine, 3- (methylamino) propylamine, Diethylenetriamine, dipropylenetriamine and / or N, N'-bis (3-aminopropyl) ethylenediamine can be used.

The alkylene oxides can be individually, alternately in succession or can be used as mixtures. Alkylene oxides are preferred used which lead to primary hydroxyl groups in the polyol. Particularly preferred polyols are those which alkoxylated at the end of the alkoxylation with ethylene oxide were and thus have primary hydroxyl groups.

As polymer polyols, a special class of polyether polyols, can be compounds generally known from polyurethane chemistry are used, preferably styrene-acrylonitrile graft polyols.

Especially the use of polymer polyols can shrink the Polyisocyanate polyaddition product, for example the Significantly reduce polyurethane and thus improve it Liability of (ii) to (i) and (iii). If necessary, you can preferred as further measures to reduce the shrinkage Blowing agents (f) and / or gases (c) are used.

Suitable polyester polyols can, for example, from organic Dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids with 4 to 6 carbon atoms, and polyhydric alcohols, preferably diols, with 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms getting produced. The polyester polyols preferably have a functionality of 2 to 4, in particular 2 to 3, and a Molecular weight from 480 to 3000, preferably 600 to 2000 and especially 600 to 1500.

The composite elements according to the invention are preferred under Use of polyether polyalcohols as component (b) for Reaction with the isocyanates prepared, advantageously those with medium functionality towards isocyanates from 1.5 to 8, preferably 2 to 6, and a molecular weight from 400 to 8000.

The use of polyether polyalcohols offers significant Advantages through improved stability of the Polyisocyanate polyaddition products against hydrolytic cleavage and due to the lower viscosity, in each case in comparison with Polyester polyalcohols. The improved stability against hydrolysis is particularly advantageous when used in shipbuilding. The lower viscosity of the polyether polyalcohols and Reaction mixture for the preparation of (ii) containing the Polyether polyalcoal enables faster and easier filling the space between (i) and (iii) with the reaction mixture for the production of the composite elements. Because of the substantial Dimensions especially of construction parts in shipbuilding low-viscosity liquids are of considerable advantage.

As isocyanate-reactive compounds can further in addition to the connections mentioned with a usual molecular weight of 400 to 8000 if necessary Diols and / or triols with molecular weights from 60 to <400 as a chain extender and / or crosslinking agent in the inventive methods are used. For modification the mechanical properties, e.g. B. the hardness, can however the addition of chain extenders, Crosslinking agents or mixtures thereof, if appropriate, are advantageous prove. The chain extenders and / or crosslinking agents preferably have a molecular weight of 60 to 300. In For example, aliphatic, cycloaliphatic and / or araliphatic diols with 2 to 14, preferably 4 to 10 carbon atoms, e.g. B. ethylene glycol, 1,3-propanediol, Decanediol-2,10, o-, m-, p-dihydroxycyclohexane, diethylene glycol, Dipropylene glycol and preferably 1,4-butanediol, 1,6-hexanediol and bis (2-hydroxyethyl) hydroquinone, triols, such as 1,2,4-, 1,3,5-trihydroxy-cyclohexane, glycerin and trimethylolpropane, low molecular weight hydroxyl-containing polyalkylene oxides Based on ethylene and / or 1,2-propylene oxide and the aforementioned Diols and / or triols as starter molecules and / or diamines such as B. diethyltoluenediamine and / or 3,5-dimethylthio-2,4- toluenediamine.

If so for the preparation of the polyisocyanate polyadducts Chain extenders, crosslinking agents or mixtures of which are used, they are conveniently used in one Amount from 0 to 30% by weight, preferably from 1 to 30% by weight, compared to the weight of the total used Isocyanate-reactive compounds (b) are used.

In addition, as (b) aliphatic, araliphatic, cycloaliphatic and / or aromatic carboxylic acids for optimization of the hardening process used in the production of (ii) become. Examples of such carboxylic acids are formic acid, Acetic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, Adipic acid, citric acid, benzoic acid, salicylic acid, Phenylacetic acid, phthalic acid, toluenesulfonic acid, derivatives of mentioned acids, isomers of the acids mentioned and any Mixtures of the acids mentioned. The weight percentage of this Acids can be 0 to 5% by weight, preferably 0.2 to 2% by weight to the total weight of (b).

With the use of amine-started polyether polyalcohols can also change the hardening behavior of the reaction mixture be improved for the preparation of (ii). To be favoured the compounds (b), as well as the other components for Production of (ii) with the lowest possible water content used to control the formation of carbon dioxide by reaction of the Avoid water with isocyanate groups.

In general, component (c) for the preparation of (ii) known compounds are used which have a boiling point at a pressure of 1 bar less (i.e. at lower Temperatures as) -50 ° C, for example air, Carbon dioxide, nitrogen, helium and / or neon. Air is preferred used. Component (c) is preferred over the Component (a), particularly preferred over component (a) and (b) inert, d. H. reactivity of the gas towards (a) and (b) is hardly, preferably not detectable. The stake of gas (c) differs fundamentally from the application usual blowing agent for the production of foamed Polyurethanes. Used during liquid propellants (f) or in the case of gaseous physical blowing agents up to a small percentage in the polyol component are soluble) and during the implementation either due to the Evaporate heat or in the case of water gaseous due to the reaction with the isocyanate groups Developing carbon dioxide is used in the present invention component (c) is preferably already gaseous as an aerosol used for example in the polyol component.

Well-known compounds can be used as catalysts (d) are used, the reaction of isocyanates with the accelerate compounds reactive towards isocyanates, preferably a total catalyst content of 0.001 to 15 wt .-%, in particular 0.05 to 6 wt .-%, based on the Weight of the total used compared to isocyanates reactive compounds. For example, you can the following compounds are used: triethylamine, Tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, Dimethylcyclohexylamine, N, N, N ', N'-tetramethyl-diamino-diethyl ether, Bis (dimethylaminopropyl) urea, N-methyl or N-ethylmorpholine, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylene diamine, N, N, N', N'-tetramethyl butane diamine, N, N, N ', N'-tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo- (2,2,0) octane, 1,4-diazabicyclo- (2,2,2) octane (Dabco) and Alkanolamine compounds, such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyl-diethanolamine, dimethylaminoethanol, 2- (N, N-dimethylaminoethoxy) ethanol, N, N ', N' '- tris (dialkylaminoalkyl) hexahydrotriazines, e.g. B. N, N ', N' '- tris- (dimethylaminopropyl) -s-hexahydrotriazine, iron (II) chloride, zinc chloride, Lead octoate and preferably tin salts such as tin dioctoate, Tin diethylhexoate, dibutyltin dilaurate and / or Dibutyldilauryltin mercaptide, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, Tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide, Alkali hydroxides, such as sodium hydroxide, alkali alcoholates, such as Sodium methylate and potassium isopropylate, and / or alkali salts of long-chain fatty acids with 10 to 20 carbon atoms and optionally pendant OH groups.

It has proven very advantageous to manufacture of (ii) in the presence of (d) to carry out the reaction to accelerate.

The reaction mixture for the preparation of the Polyisocyanate polyadducts (ii) can optionally (e) assistants be incorporated. Examples include fillers, surface-active substances, dyes, pigments, Flame retardants, hydrolysis protection agents, fungistatic, bacteriostatic acting substances and foam stabilizers.

As surface-active substances such. B. Connections in Consider which to support the homogenization of the Serve as starting materials and are also suitable if necessary, regulate the structure of plastics. Be mentioned for example emulsifiers, such as the sodium salts of Castor oil sulfates or of fatty acids and salts of fatty acids with Amines, e.g. B. oleic acid diethylamine, stearic acid diethanolamine, ricinoleic acid diethanolamine, salts of sulfonic acids, e.g. B. alkali or ammonium salts of dodecylbenzene or Dinaphthylmethane disulfonic acid and ricinoleic acid. The surface-active substances are usually obtained in quantities of 0.01 to 5% by weight to 100% by weight of the total isocyanates used reactive compounds (b) applied.

Suitable flame retardants are, for example Tricresyl phosphate, tris (2-chloroethyl) phosphate, Tris (2-chloropropyl) phosphate, tris (1,3-dichloropropyl) phosphate, Tris (2,3-dibromopropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, dimethylmethanephosphonate, Diethanolaminomethylphosphonsäurediethylester and commercially available halogen-containing Flammschutzpolyole. Except for the halogen-substituted ones already mentioned Phosphates can also be inorganic or organic Flame retardants, such as red phosphorus, aluminum oxide hydrate, antimony trioxide, Arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, such as. B. melamine, or mixtures from at least two flame retardants, such as. B. Ammonium polyphosphates and melamine and optionally corn starch or Ammonium polyphosphate, melamine and expandable graphite and / or optionally aromatic polyester for flame retarding the Polyisocyanate polyaddition products are used. In general it has proven to be expedient, 5 to 50% by weight, preferably 5 to 25% by weight of the flame retardants mentioned on the weight of the total isocyanates used reactive compounds.

As fillers, especially reinforcing ones Fillers are the usual organic and known per se inorganic fillers, reinforcing agents, weighting agents, Agents for improving the abrasion behavior in paints, Understand coating agents, etc. In particular mentioned as examples: inorganic fillers such as silicate Minerals, for example layered silicates such as antigorite, Serpentine, hornblende, amphibole, chrisotile and talc, Metal oxides, such as kaolin, aluminum oxides, titanium oxides and iron oxides, Metal salts such as chalk, heavy spar and inorganic pigments, such as cadmium sulfide and zinc sulfide, and glass and. a .. Preferably Kaolin (China Clay), aluminum silicate and Coprecipitates from barium sulfate and aluminum silicate as well natural and synthetic fibrous minerals like wollastonite, Metal and glass fibers of short length. As organic fillers For example, coal, melamine, rosin, Cyclopentadienyl resins and graft polymers and Cellulose fibers, polyamide, polyacrylonitrile, polyurethane, Polyester fibers based on aromatic and / or aliphatic Dicarboxylic acid esters and especially carbon fibers. The inorganic and organic fillers can be used individually or can be used as mixtures.

Preferably, 10 to 70% by weight is used in the preparation of (ii) Fillers, based on the weight of (ii), as (e) auxiliaries on. Talcum, kaolin, Calcium carbonate, heavy spar, glass fibers and / or micro glass balls. The size of the particles of the fillers should preferably be chosen so that that the registration of the components for the preparation of (ii) in the space between (i) and (iii) is not obstructed. Especially the fillers preferably have particle sizes of <0.5 mm.

The fillers are preferably mixed with the Polyol component in the implementation to produce the polyisocyanate Polyaddition products used.

The fillers can be used in comparison For example, the thermal expansion coefficient of steel is greater To reduce polyisocyanate polyadducts and thus the of the steel. This for a sustainable, firm network between layers (i), (ii) and (iii) especially advantageous because it reduces tensions between the layers occur under thermal stress.

Preferred for the production of (ii) are customary as (e) Foam stabilizers used that are commercially available and are generally known to the person skilled in the art, for example generally known polysiloxane-polyoxyalkylene block copolymers, z. B. Tegostab 2219 from Goldschmidt. The share of this Foam stabilizers in the production of (ii) preferably 0.001 to 10% by weight, particularly preferably 0.01 to 10% by weight, in particular 0.01 to 2 wt .-%, based on the weight of the for the production of (ii) components (b), (e) and optionally (d). The use of these foam stabilizers causes component (c) in the reaction mixture Production of (ii) is stabilized.

The blowing agent (f) can be from polyurethane chemistry well-known blowing agents are used, for example physical and / or chemical blowing agents. such physical blowing agents generally have one Boiling point greater at a pressure of 1 bar (i.e. at higher Temperatures than) -50 ° C. Examples of physical Blowing agents are e.g. B. CFC, HCFC, HFC, aliphatic Hydrocarbons, cycloaliphatic hydrocarbons, each for example with 4 to 6 carbon atoms or mixtures of these substances, for example trichlorofluoromethane (boiling point 24 ° C), Chlorodifluoromethane (boiling point -40.8 ° C), dichlorofluoroethane (boiling point 32 ° C), chlorodifluoroethane (boiling point -9.2 ° C), dichlorotrifluoroethane (Boiling point 27.1 ° C), tetrafluoroethane (boiling point -26.5 ° C), Hexafluorobutane (boiling point 24.6 ° C), iso-pentane (boiling point 28 ° C), n-pentane (boiling point 36 ° C), cyclopentane (boiling point 49 ° C).

As a chemical blowing agent, i. H. Propellant due to a Reaction, for example with isocyanate groups, gaseous Products form, for example, come water, hydrated water containing compounds, carboxylic acids, tertiary alcohols, e.g. B. t-butanol, carbamates, for example those in the document EP-A 1 000 955, in particular on pages 2, lines 5 to 31 and page 3, lines 21 to 42, described carbamates, Carbonates, e.g. B. ammonium carbonate and / or Ammonium hydrogen carbonate and / or guanidine carbamate.

Preferred blowing agents (f) are water and / or carbamates used.

The blowing agents (f) are preferably used in an amount sufficient to obtain the preferred density of (ii) from 350 to 1200 kg / m ³ . This can be determined using simple routine experiments which are generally known to the person skilled in the art. The blowing agents (f) are particularly preferably used in an amount of 0.05 to 10% by weight, in particular 0.1 to 5% by weight, in each case based on the total weight of the polyisocyanate polyadducts.

The weight of (ii) by definition corresponds to the weight of the for the production of (ii) components (a), (b) and optionally (c), (d), (e) and / or (f).

For the production of the invention The polyisocyanate polyaddition products are the isocyanates and the isocyanates implemented reactive compounds in such amounts, that the equivalence ratio of NCO groups of the isocyanates (a) to the sum of the reactive hydrogen atoms opposite Isocyanate-reactive compounds (b) and optionally (f) 0.85 to 1.25: 1, preferably 0.95 to 1.15: 1 and in particular 1 to 1.05: 1. If (ii) at least partially Isocyanurate groups bound, is usually a Ratio of NCO groups to the sum of the reactive Hydrogen atoms from 1.5 to 60: 1, preferably 1.5 to 8: 1, applied.

The polyisocyanate polyadducts are commonly used according to the one shot process or the prepolymer process, for example with the help of high pressure or low pressure technology manufactured.

It has proven to be particularly advantageous after the Two-component process to work and the isocyanates reactive compounds (b), optionally the blowing agents (f) and optionally the catalysts (d) and / or auxiliaries (e) to combine in component (A) (polyol component) and preferably mixed intimately and as component (B) the To use isocyanates (a).

Component (c) can contain the reaction mixture (a), (b) and optionally (f), (d) and / or (e) are fed in, and / or the individual components (a) already described, (b), (A) and / or (B). The component that is mixed with (c) is usually liquid. The components are preferred mixed into component (b).

The mixing of the corresponding component with (c) can be done after generally known methods. For example, (c) by well-known loading devices, for example Air loading devices, preferably under pressure, for example compressed from a pressure vessel or by a compressor, z. B. supplied through a nozzle of the corresponding component become. There is preferably extensive mixing of the corresponding components with (c) so that gas bubbles from (c) in the usually liquid component preferably has a size of 0.0001 to 10, particularly preferably 0.0001 to 1 mm.

The content of (c) in the reaction mixture for the production of (ii) can be in the return line of the high pressure machine well-known measuring devices on the density of the reaction mixture be determined. The content of (c) in the reaction mixture can via a control unit, preferably automatically on the The basis of this density can be regulated. The component density can during the normal circulation of the material in the machine online even at very low circulation speeds be determined and regulated.

Find the composite elements available according to the invention Mainly used in areas where construction elements needed to withstand large forces, for example as construction parts in shipbuilding, e.g. B. in ship hulls, for example ship's double hulls with one outer and one inner wall, and cargo space covers, cargo space partitions, Loading flaps or in structures, such as bridges or as Construction elements in house construction, especially in high-rise buildings.

The composite elements according to the invention are not classic To be confused with sandwich elements that have a polyurethane core and / or contain rigid polyisocyanurate foam and are usually used for thermal insulation. such known sandwich elements would be comparative due to their lower mechanical strength not for the above Suitable areas of application.

Claims (15)

1. A method for introducing liquids by means of a conveyor into a mold which has an upper layer (i) with at least one opening (iv) through which liquid is filled, and a lower layer (iii), characterized in that the Outflow end of the conveying device or a holder for the outflow end of the conveying device is screwed to the layer (i) at at least three points. 2. The method according to claim 1, characterized in that you attach a bracket to at least three threads that are attached to (i) are attached, screwed and the bracket on this Fixed outflow end. 3. The method according to claim 1 or 2, characterized in that that you have bolts with a thread that are used to attach the Outflowing or serve the holder in the layer (i) shoots. 4. The method according to claim 1, characterized in that the Outflowing is a mixing head. 5. The method according to claim 4, characterized in that one an O-ring between the layer (i) and the mixing head fixed with an elastic material. 6. The method according to claim 4, characterized in that one the liquids by means of a high pressure apparatus over the Mixing head brings. 7. The method according to claim 1, characterized in that one the liquid continuously by means of the conveyor in one step without interruption in the filling space between (i) and (iii). 8. The method according to claim 1, characterized in that (i) and / or (iii) in addition to the one or more openings (iv), through which the liquids are entered, via have at least one other opening (v). 9. The method according to claim 8, characterized in that one attaches overflow vessels to the opening (s) the rise of the liquid in the overflow vessels complete filling of the space between (i) and (iii) determined, and then closes the opening (s) (v). 10. The method according to claim 1, characterized in that composite elements are produced by means of the method, which have the following layer structure: a) 2 to 20 mm metal, plastic or wood, b) 10 to 300 mm of a plastic which is formed by hardening the liquid filled in the mold, c) 2 to 20 mm metal, plastic or wood. 11. The method according to claim 10, characterized in that the Liquid for the preparation of (ii) (a) isocyanates and (b) contains compounds reactive towards isocyanates and (ii) Represent polyisocyanate polyadducts. 12. The method according to claim 11, characterized in that one the reaction of (a) with (b) to (ii) in the presence of 1 to 50% by volume of gases (c). 13. The method according to claim 11, characterized in that used as (b) polymer polyols. 14. The method according to claim 11, characterized in that one the reaction of (a) with (b) in the presence of (f) Propellants. 15. Composite elements obtainable by a method according to one of claims 1 to 14.