DD284033B5 - METHOD FOR PRODUCING ORGANOMINERAL PRODUCTS - Google Patents

Description

For this 1 page drawing

Field of application of the invention

The present invention relates to a process for the preparation of organomineral products, which are particularly suitable as Gsbirgsverfestigungsmittol for coal, rock and / or ore in mountain or tunneling, which is why the method is also preferably carried out as a method of rock solidification, in which the organomineral products directly in situ be prepared in a rock formation to be consolidated. Furthermore, according to the method, the material in artificial formation such. As foundations, walls of water retention systems or gas and oil wells for stabilization and / or sealing against water and gas can be used.

The method may also be advantageously applied to the consolidation and / or sealing of natural and / or artificial formations exposed to high-energy radiation.

Characteristic of the prior art

Organomineral products in the context of the present invention are more or less homogeneous substances which are produced from a single reaction mixture and at the same time contain organic and inorganic constituents, preferably in the form of interlocking networks of organic polymers and inorganic silicates, into which further organic and inorganic silicates may be added / or inorganic constituents can be incorporated. Certain organomineral products of this kind are already known from a number of prior art publications, reference being particularly made to FR-A-1362003, GB-A-1186/71, DE-A-2325090, DE-A-2460834, DE -A-3421086, US-A-4042536 and EP-A-0000580.

In all the cases described, the organomineral product (s) are prepared from reaction mixtures comprising a polyisocyanate and an aqueous alkali silicate solution ("waterglass solution") In addition, modifiers, catalysts, stabilizers and various blowing agents are used to achieve particular properties Achieving as homogeneous as possible properties of the solubility or solvation of the organic compounds used by water to produce finely divided emulsions special attention! " donated it. The disclosed uses of the organo-mineral products described range from rigid and insulating foams, via putties and adhesives, to soil improvers and rock solidifiers.

In the context of the present invention, one of the main applications of the method according to the invention is rock consolidation. It also appears appropriate to briefly summarize the technical development in this field in recent years. The term "rock stabilization" is understood to mean any process for solidifying and sealing geological and poured rock, erosion and coal formations, the emphasis being on rock solidification underground in mines or in civil engineering From a practical point of view, the method according to the invention is also similar to the already known rock solidification method, so that the prior art cited below can be referred to ways of carrying out the method to supplement the present disclosure.

Rock solidification is a special case of chemical soil consolidation, where by injection of suitable liquid chemicals, gels, rock, coal and ore deposits are solidified or sealed against stagnant and running water or brine. The first such methods were already described towards the end of the 19th century. At that time, especially water glasses were used in conjunction with hardeners. The hardening of the water glasses takes place

different ways. Thus, around 1925 H. Joosten used waterglass and in a subsequent injection calcium chloride as a hardener component. The process was developed into the "monosol process" using an oinzigon injection of highly diluted water glass and sodium aluminate, while another, the so-called "Monodur process", used an emulsion of water glass and an organic acid as the hardness component.

By the middle of this century, the suitability of synthetic resins for the purpose of rock consolidation began to be explored, first in American hard coal mining. Since then, experiments have been carried out with injections of hardenable plastics based on polyesters, polyacrylates, epoxidone and polyurethanes.

For example, in 1959, injections of epoxy resin with fillers were performed. Further dorartigo processes which have been carried out using synthetic resins based on roin organic, in particular on the basis of polyurethanes, are further described in German patents 17 58185 and 3139395.

Right from the start of the development of organo-mineral products, the principle of such products for soil stabilization or mountain hardening was recognized. An early such process is described in the German Patent 1069878 from the year 1957, where emulsions of water glass and polymerizable unsaturated Estorn are injected for soil consolidation. In GB-A-1186771 the suitability of mixtures of water glass and polyisocyanate for sealing mountain formations in mining is mentioned. In the DE-A-2908746 or the parallel EP-A-0016262 again the use of such mixtures of water glass solutions and polyisocyanates for rock solidification and sealing is disclosed, but it is taught that only the addition of polyols to such mixtures to a real real Solidification leads to the formation of stable formations.

In DE-A-3421085 it is described that mixtures of polyisocyanates and aqueous alkali metal silicate solutions can be advantageously improved in rock solidification, when a certain amount of a trimerization catalyst for the polyisocyanate is added, which is used to build up an organic network purely based on trimerized polyisocyanates leads

However, all previously known rock solidification processes have certain disadvantages that limit their applicability and reliability. In the first injection methods for soil and rock solidification using purely inorganic materials, only unsatisfactory solidifications were obtained. This was probably due primarily to the unfavorable ratio of viscosity to solids content of the water glasses used at that time and the fact that the speed and extent of the curing reaction could only be controlled poorly. The effects of temperature, porosity and lumpiness of the soil or rock formation as well as the presence of stagnant and running water influenced the results so that the effects obtained did not correspond to the intended results. In the experiments of a purely inorganic rock stabilization showed a number of undesirable side effects, such as lack of strength of the formations by highly water-containing gels, brittleness due to incomplete or overcrosslinking curing reaction, leakage of the injection material into larger Hohlraumboreiche or washed away by underground aquifers.

An injection at an angle above the horizontal through drill holes could not be performed at all. The water glass hardeners used, such as, for example, formamide and glyoxal, which were introduced in large quantities into the final formation, are now classified as environmentally hazardous.

Similar concerns also speak against numerous plastic-based injection materials that contain or release harmful substances. Examples include: phenols, formaldehyde, organic solvents and water-soluble foaming agents and chlorofluorocarbons. From the large number of conceivable plastic preparations for rock consolidation and / or sealing by injection, therefore, have gained only a few practical importance. These include primarily polyurethane resins, as described in German Patents 17 58185 and 3139395. Here, also for reasons of material savings, preferably those formulations were used, which foam under the given conditions on site. As an advantage foaming formulations is specified in particular that the expansion pressure occurring during foaming can cause a self-injection of the injection material, which makes it possible to work with lower injection pressure or simply fill the grout in holes that are sealed to the outside. However, it has already been recognized that it is a disadvantage in itself that the strength of the cured resin is reduced by the foaming.

However, despite the widespread use of effervescent formulations, foams must be considered at least unfavorable, if not dangerous. Namely, the swelling pressure can not only lead to an advantageous self-injection of the injection material, but can also have a negative effect, namely when it collects behind larger layers and pushes them off. Due to an inherent elasticity of synthetic resin foams also give such foams at a compressive stress by the mountains after, so that rock movements are possible, leading to a new formation of mountain breaks. In addition, most foam * show a tough-elastic behavior that can not cope with the usual mining equipment.

Another particular source of danger for the use of polyurethane reaction mixtures lies in the inadequate controllability of the heat of reaction developed locally in situ. Injections into larger mountain voids can therefore lead to self-ignition of polyurethane mixtures. Especially in coal mining and / or in mine areas with an inflammatory atmosphere, this is an unsolved problem. It is therefore necessary to help with the formulation so that the unavoidably developing heat of reaction can be released to the environment over a longer period of time. For this purpose, however, the formulations must be adjusted slowly with regard to the reaction behavior. However, this in turn imposes severe processing problems on the user site and impairs the reliability of the process. Injection formulations with long reaction times are in fact susceptible to the occurrence of side reactions, for example by absorption of water, whereby the reaction stoichiometry is shifted, so that the desired reaction product is not obtained. The resulting in the reaction with water larger amounts of CO ₂ build up a gas pressure, which can lead in areal gaps to the pressing of mountainous areas and thus counteracts the aspired mountain protection. Slow-reacting formulations also increase the risk of leaking out of the mountain formation or into cavities with considerable loss of injection material. On the other hand, narrow gaps, which require the penetration of a higher injection pressure, can not be achieved.

From green clay of the type mentioned, the use of intumescent polyurethanes for injection in Kohlenborghau on jo are limited, this use is strictly regulated by regulatory provisions.

Crganomineral products have made significant progress in their use as grout grouts for reinon polyurethanes, but have also created a number of new difficulties.

The organomineral products important to the scope of the present invention are obtained from polyisocyanates and aqueous alkali silicate solutions. In such systems, isocyanate groups react with water unaffected by low molecular weight urea steroids, which, although extremely hard and viable, do not contribute to adhesion to the rock strata. The CO ₂ -GaS liberated during the reaction reacts with the alkali oxides (Me ₂ O, where Me = Na, K) present in the alkali silicate solution to form carbonates, thereby precipitating the silicate residue as hydrous xerogel. In this uncontrolled decomposition of alkali silicate solution whose contribution to the adhesive effect is lost. To improve the adhesion, therefore, polyolantoils are also required in such reaction mixtures, which follows, for example, from a comparison of Example 1 of DE-A-2908746 with the remaining examples. Additions of polyols to a reaction mixture of isocyanates in an aqueous alkaline medium are reaction kinetically - especially under the harsh mining conditions - unmanageable, since in the high excess of water always the water-induced isocyanate reaction is the main reaction. Polyols form in such systems therefore only relatively kurzkettigo separated present organic Molokülsegmente in an inorganic matrix.

It was therefore attempted to increase the contribution of the organic portion at the expense of the inorganic portion in systems of the type mentioned. An increase in the proportion of synthetic resin, however, leads to a deterioration of the economy of the process.

Therefore, according to OE-A-3421086, another approach is taken by attempting to control the isocyanate reaction in alkali silicate solutions by simultaneously using a suitable trimerization catalyst while respecting the amounts of reactants so as to provide an organic network derived from trimerization of the isocyanates is formed. Although this indeed gives the final product an extremely high level of stability, it is again formed by hard organic molecular structures which, owing to the lack of suitable functional end groups, can not produce a bonding off-site, in particular on moist rock.

It is also a disadvantage that the trimerization capacity of the catalyst comes into full effect only within narrow limits of the molar ratio catalyst / isocyanate groups, while at a lower or exceeded the optimum ratio, the usual isocyanate reaction is strongly excited with water, so that an undesirably large nichtklebefähiger Urea content arises. However, this procedural limitation has the procedural disadvantage that, with an occasionally desirable high reaction rate of the formulations, an uncontrolled foaming of the in-product is observed, resulting in a product which can be crushed to a light powder.

Another problem that has not yet been satisfactorily solved is the solidification and / or sealing of natural geological or artificial formations exposed to high-energy radiation.

The er.argisch driven expansion of nuclear energy in the last two decades as well as the use of radioactive isotopes for a variety of technical, medical and scientific research purposes, there was more often the situation that a high-energy radiation, in particular a radioactive radiation stored materials over significant periods or temporarily or permanently stored.

The structural constructions selected for these storage and storage purposes or overground or underground

For safety reasons, locations must have extraordinarily high long-term stability and / or tightness against gas and liquid exchange with the environment.

Apart from these increased safety requirements, however, an additional material problem arises in the attempt to provide additional solidification and / or sealing due to the fact that the high energy or radioactive radiation emanating from the material destroys many materials otherwise suitable for consolidation and / or sealing would. This is especially true for most organic based resins.

As formations that must be sealed, in particular underground or above-ground final or intermediate storage for radioactive material, structural designs of nuclear power plants, transport containers for radioactive material or Abklingbecken and water tanks in which radioactive material is kept apply.

Object of the invention

It is the object of the invention to provide a method in which the described disadvantages of the prior art are completely overcome or at least considerably mitigated.

Explanation of the essence of the invention

It is therefore an object of the present invention to provide a process for the preparation of novel organomineral products based on polyisocyanates and aqueous alkali metal silicate solutions, which reliably provides non-foamed polymeric Organomineralprodukte avoiding the specified procedural disadvantages, on the one hand hard, but on the other hand comparable Products have a greatly improved adhesiveness, and in addition have an over organic resins improved resistance to high-energy radiation.

On the one hand, the isocyanate reaction leading to the formation of the inorganic silicate skeleton should proceed unhindered with water and, on the other hand, foaming should be reliably prevented.

This object is achieved by a method according to claim 1. Advantageous specific embodiments of this method can be found in the dependent claims.

In the following, the invention will be explained in more detail on the basis of the reactions which are important for the composition and the properties of the process product and also with regard to a more precise definition of possible starting materials.

In a reaction mixture according to the present invention polyisocyanates (R-NCO), oino wasserrigo alkali silicate solution (HjO ₁ Me ₂ Ox nSiO ₂ ) andoinEpoxidharz / _D ι λΟ> ,. contains, InufenbeidonierfindungsgoinäßonVorfahrondioindem

from the main formula listed below. It should be noted, however, that the radicals R (isocyanate) and R '(epoxy resin) according to the fact that the isocyanates are predominantly di- and higher-functional polyisocyanates and mixtures thereof and the epoxy resins i. D.R. also contain at least two epoxide groups, have other centers that can react in the sense of the following Formolschomas, üas means, however, that the reaction products obtained, which still have such radicals in the following Formula Schoma, are in fact parts hochpolymeror organic scaffolds

 The product-forming reactions are:

1. R-NCO + H ₂ O -> (R-NH-COOH) -> RNH ₂ + CO ₂ + heat

2. ¹ R-NCO + RNH ₂ -> R-NH-CO-NH-R + heat

3. Me ₂ O + COj, -) Me ₂ CO ₃

JK ^Ks * v ~ ° \

5. -R'-C - ^ - + [r-NH-COOR ¹¹ ] -> Ii

6. T% "- OH + R'-db- -> R ¹ ^ CH ₂ -CR '/ ** ^ 9

Ii ι u

OH ^H

The reactions shown schematically in these formulas interlock in the implementation of the method according to the invention for the production of organomineral products as follows: Reaction 1 is the customary known reaction of isocyanates with Wajser. In the context of the present implementation, this reaction has great importance as CO ₂ and heat-giving reaction. The amine formed in this reaction reacts in known manner in Reaction 2 to form urea structures which provide a first portion of solids later to be found in the reaction product. Outside this reaction gives 2 more heat. For the process according to the invention, the urea units formed at this stage are less important than the heat generated. Because while the CO ₂ in reaction 3 in a known manner to form a silicate skeleton with the alkali metal oxide of alkali metal silicate abreacted, that is bound, the heat generated in the reactions 1 and 2, the reaction not yet reacted with water isocyanate groups with the present in the reaction mixture Epoxy resin with opening of the oxirane ring and formation of Polyoxazolidinone ^ forming a high polymer organic support framework.

It should be noted at this point that in the reactions 1 and 2 to produce 1 mole of CO ₂ 2 moles of R-NCO (= 2 x mol) are consumed. Since this CO _{2 is} to be completely bound by the reaction mixture to prevent foaming, isocyanate groups and Me ₂ O molecules in a molar ratio of 2: 1 must be present in the reaction mixture due to the reaction stoichiometry.

Since in the reaction 4 equimolar amounts of isocyanate and epoxide groups react with each other, a further additional proportion of isocyanate groups (y) is required for this reaction.

However, in addition to the basic reactions forming the network 1 to 4, two further reactions are of paramount importance for the properties of the products prepared in the process according to the invention. Since the epoxy resins or the polymers formed from them in the reaction inevitably contain a certain proportion of functional hydroxyl groups, formed in the reaction mixture as by-products by-products urethane segments, which are represented schematically in formula 5 by the parenthesis. With such Ure'ihansegmenten the epoxy resins can also react under Oxazolidinonbildung, wherein it is important that while organic products with free hydroxyl groups (R "-OH) are produced.

These hydroxyl compounds can also react with epoxide units of the epoxy resins present, wherein also organic structures having free hydroxyl groups are formed (reaction 6).

In the process according to the invention, therefore, it is inevitable that products of side reactions form hydroxyl-containing segments in the polymer chains produced. However, these hydroxyl groups are extremely important to the properties of the products obtained because they cause the organic polymer backbone formed to have adhesive properties as well, in that hydrogen bonds can form to the oxygen functions present on the surface of the rock material, according to the following schematic:

(Mountains) °. J? ~~ Ϋ (OrgaTionvineralprodukt)

In contrast to the known processes in which the organic polymer skeleton unfolded no adhesive effect, the process according to the invention forms an adhesive polymer backbone which, in addition to the inorganic silicate skeleton, contributes to the adhesion improvement between the rock and the synthetic resin. Indians in the recipe according to the invention is taken to ensure that always necessary for binding the developed CO ₂ Alkaüoxidmonge present \ Λ, foaming is avoided. The fact that the excess isocyanate groups actually react with the epoxide and not with excess water is ensured by the heat generated in the basic reactions, and, moreover, suitable catalysts generally still play an important role in controlling. Suitable catalysts may be amine-based catalysts, in particular those based on tertiary amines or quaternary ammonium salts, catalysts in the form of organometallic compounds or catalysts in the form of inorganic salts. It should be noted that in the context of the process according to the invention amine catalysts such as 2,4,6-tris (dimethylaminomethyl) phenol or benzyldimothylamine preferably preferentially catalyze the isocyanate / epoxide reaction, while they act as trimerization catalysts in the absence of epoxides (see. DE-A 3421086). Inorganic salts, in particular FeCl ₃ , AICI ₃ or ZnCl ₂ in particular activate the epoxide groups for reaction with NCO groups, but inhibit the reaction between isocyanate and OH groups. Such compounds are therefore found in effective amounts in technical isocyanates as retarders, which are identified in the specifications as hydrolyzable chlorine or as total chlorine. The fact that such, in the context of the process according to the invention catalytically active salts are anyway contained in technical polyisocyanates, has the additional advantage that can be dispensed with in many cases to the separate addition of another catalyst.

Organonietallische connections, z. B. triisopropylaluminum Al (iC ₃ H ₇ ) ₃ , are suitable catalysts for the process according to the invention, through the targeted selection reaction mixtures are available with the desired properties for the particular application. In addition to the inventively calculable stoichiometry, catalysts help to control the intrinsically very complex reaction system epoxy resin-water glass polyisocyanate safely.

It is the goal of any recipe design for carrying out the method according to the invention, by varying the amount and type of catalyst or catalyst system and the reactants to create the following conditions:

1. The isocyanate-water reaction may only progress as far as the resulting CO ₂ -GaS can be absorbed by the total formulation.

2. The exothermic heat formed in this starting reaction and the oxazolidinone formation catalyst must be coordinated so that even in aqueous alkaline systems polymer scaffolds on organic base? arise. In order to meet requirement No. 1, care must be taken that the ratio of reaction partners as defined in claim 2 is met, namely the condition that the organomineral products be prepared in the form of solid, non-foamed products and reactants, polyisocyanate, aqueous reactants involved in the reaction Alkalisilikatlösung and epoxy resin used in such molar ratios that the following relationship is satisfied:

X (Me ₂ O) + y (Ä) + ( _2κ + _y ) (NCO) -> products,

where X (Me ₂ O) is the amount of substance in moles of sodium and / or potassium oxide in the alkali silicate used, Y (- -)) is the molar amount in moles of the epoxide groups in the epoxy resin used,

(2x + y) (NCO) is the amount of substance of the-NCO groups in moles in the polyisocyanate used, and wherein Me is Na or K and χ and y are the respective relative molar amounts expressing positive numbers having a tolerance range, the take into account the usual quality fluctuations of the individual reactants, if these are used as technical commercial products,

and wherein the epoxy resin is used in an amount of from 0.01 to 60% by weight, based on the weight of the alkali silicate solution used.

The correct ratio of isocyanate groups to epoxide groups in the reaction mixture and, matched thereto, the effectiveness of the reaction 4 activating catalyst ensures compliance with the above requirement no. 2.

Reaction mixtures are preferably prepared from starting materials which fulfill the following conditions:

NCO groups from the polyisocyanate) 0.238-1.19 mol proline

Me ₂ O (from alkali silicate solution) 0.081-0.323 mol per 100 g

Epoxy units (oxirane rings, epoxy resin) 0.020-0.80 mol proline

Preferably, such amounts of alkali silicate solution and epoxy resin are used that the alkali silicate solution and the epoxy resin, which are used in one embodiment in the form of a designated "component A" premix, in a pre-mix containing only these two components in amounts of 70 to 95Gew.- These amounts correspond to a content of Me ₂ O of 0.09 to 0.28 mol per 100 g or of 15 to 10 mmol of epoxy groups per 100 g.

From this information, a preferred range for the ratio x / y of 0.4 to 18.6 can be derived.

Since the process is usually carried out with starting products of technical quality, resulting from conventional

Product fluctuations furthermore natural tolerances for the molar amounts of the above reaction partners within the scope of the stated molar ratio. Based on the currently observed quality fluctuation, the following tolerances gelled approximately:

(NCO) ± 5% (Me ₂ O) ± 2.5%

Taking into account the various possible water glass qualities and epoxy resins which can be used in the process according to the invention, it also results that the epoxy resin is present in a reaction mixture for the process according to the invention in a proportion of 0.01 to 60% by weight, based on the weight of the water glass solution used can. As already indicated, the customary polyisocyanates and aqueous alkali silicate solutions which have hitherto been used in such processes can be used in the process according to the invention.

The polyisocyanates are pure or technical polyisocyanates, in particular solvent-free 4,4'-diphenylmethane diisocyanate in admixture with higher-point isocyanates, as they are marketed by different manufacturers, referred to as raw MOI. However, so-called prepolymers which still have reactive NCO groups can also be used. Such products are obtained by reacting polyisocyanates with organic compounds which have at least one, but preferably two or more, active hydrogen atoms relative to NCO groups. Such prepolymers are known to the polyurethane chemist. However, it is inventively claimed to use a prepolymer which is prepared from a monoisocyanate and a claimed epoxide ring-containing resin. NCO groups are reacted in stoichiometric or excess amount with the OH groups unavoidably formed in the preparation of the epoxide group-containing resin, resulting in a prepolymer which is OH group-free. This prepolymer remains storage stable for months. Furthermore, it can be added (see Example 10) to the technical isocyanate, which usually contains a catalyst which stimulates oxazolidinone formation, while still obtaining sufficient storage stability for this component. As aqueous Alkilisilikatlösungen can sodium and / or potassium water glasses, and their mixtures having a dissolved solids content of IO to 60Gew .-%, in particular from 35 to 55Gew .-%, and a content of alkali metal oxide from 5 to 20Gew .-%, in particular 8 to 18% by weight. With regard to their inventive utilization, the water glasses lying in this range show good process properties, such as flowability, readily applicable reaction kinetic properties such as a specific heat range and general physiological and environmental safety. In addition, they bridge the range which, depending on the recipe, results in a high or low water content end product, the product surprisingly having a low water content, such as n & ch Example 9, being considered gas tight with a value of <1 mD (Milli-Darcy).

Epoxy resins which may be used are per se known epoxy resins which have a content of functional epoxide groups in the broad range from 200 to 8000 μmol / kg, preferably in the range from 300 to 700 μmol / kg. Such resins include in particular epoxy resins based on a modified bisphenol-A, based on dimer fatty acids or conventional bisphenol A epoxy resins. Such resins have at least two epoxide groups, but monoepoxides can also be mixed in with them. However, it is also possible to use higher-functional epoxy resins, for example phenol-novolak-based epoxy resins.

The processes according to the invention can preferably be carried out by two mixing methods. After the first method is an A-Komponec. Made of epoxy-containing material with the alkali metal silicate solution, which is then reacted with the calculated amount of B component to the reaction. When using a technical polyisocyanate as the B component, a catalyst activating the oxazolidinone reaction has already been added. In addition, other catalysts may be added to the inventive type of B component. According to the second method, the A component consists only of an alkali silicate solution according to the invention and optionally a catalyst. The B component consists in this case of the polyisocyanate and the epoxide group-containing material. Preference is given here to using the polyepoxide "inertized" by monoisocyanates described above. With appropriate inertness to the A and B components, further additives can be mixed in to achieve particular properties Silicic acids, diatomaceous earth, natural and artificial fibers of different lengths, electrically conductive carbon blacks, hollow microspheres, fly ash, sand, quartz flour, etc.

When the process according to the invention is carried out as a method for rock solidification, a reaction mixture of the desired viscosity is prepared in a manner known per se by mixing the reactants in the above-mentioned sense, and this reaction mixture is injected immediately under pressure into the rock to be solidified known, recited in the cited prior art techniques can be used. Since the products according to the invention are not foams, self-injection methods (filling into a borehole and simple closing) are excluded.

The materials that can be produced according to this teaching are versatile due to the variation of inorganic to organic polymer content, as important polymer properties, such as Ε-modulus and compressive strength can be adjusted within wide ranges.

Thus, formulations with a high silicate content are stone-like masses, formulations with a high organic content tend to have typical properties of polymeric materials.

Due to their reaction behavior, the components can also be injected into open and / or closed molds, so that impressions or plates, rods, rods, models, machine parts, etc. can be produced therefrom.

Also, spraying over two-component spray guns on dry and / or moist substrates is feasible because of the possibility of chemical anchoring to the substrate. Unprotected steel can be exemplary in this way

be provided with a corrosion protection. Damaged prestressed concrete structures can be improved by injection with the nouen materials not only in their statics, but at the same time receive a corrosion protection, which can also neutralize because of the stored buffer salts acid wastewater.

The organo-mineral products prepared by the process of this invention have the advantages that they do not have a foam structure which hinders or prevents a gas-tight seal, and that initial studies have shown that the organo-mineral products having epoxy-extended chain segments are extremely stable to the action of energy radiation , The good blob strength on the steroids is maintained, and there is no release of gases or vapors.

These properties advantageously distinguish the preferred organo-mineral products from those used in coal mining in accordance with EP-A 0016262 or as described in DE-A 3421085. These publications describe products which are i.d. R. have a foam structure and in their preparation from the reaction mixture of water vapor and Troibmitel (chlorofluorocarbons) release, which prevents a perfect gas-tight seal.

The polyurethane segments present in these materials are susceptible to exposure to high-energy radiation (presumably similar to polyamides) and are decomposed by such radiation. At least for purposes of sealing and / or solidifying long-term storage, such materials are therefore i. d. R. unsuitable The organomineral products produced from the three-component reaction system of the process according to the invention are, on the other hand, outstandingly suitable for the described purposes owing to their massive nature and the organic constituents which are insensitive to high-energy radiation.

For the claimed use, the organomineral products in the form of their starting reaction mixtures, either as known from the applications of such organomineral products z. As in coal mining, injected via holes in the formations to be solidified, or they are applied for the purpose of sealing instead or additionally flat on the sealed surface areas of the formation to be sealed, after which each waits the Abreaktion to form organomineral products or possibly which produces favorable environmental conditions.

The invention will be explained in more detail on the basis of exemplary embodiment which relate to selected reaction mixtures for carrying out the method according to the invention and comparison mixtures. Reference is made to a figure which reproduces a photomicrograph of a product prepared by the process according to the invention (magnification 1: 1000).

embodiments

In the following examples, the alkali silicate solutions, the epoxy resins, the polyisocyanates, the catalysts, the stabilizers and the filler are referred to by short names, behind which hide the products listed below:

Starting Materials:

Wt .-% Me ₂ O wt .-% of Me

Gesamtfeststoffos

Water Glass 1: 12.0 45.0 N / A Water Glass 2: 13.8 47.0 N / A Water Glass 3: 8.8 38.0 N / A Water Glass 4: 18.0 54.5 N / A Water Glass 5: 5.8 28.1 N / A Water glass 6: 13.5 40.5 K Type mMolEpoxid kg

Epoxidi MOD.Bisphenol-A 4650-5130

2 dimer fatty acid base 2130-2560

3 bisphenol A standard 5150-5 550

4 phenol novolac 5260

R-NCO-1 diphenylmethane-4,4'-diisocyanate

Free NCO content 31 + 1% by weight

HydrolysierbaresChlorO, from 1 to 0.45%

R-NCO-2 phenyl isocyanate, technically pure

Catalyst-1 dimethylbenzylamine

Catalyst-2 2,4,6-trisdimethylaminomethylphenol

Catalyst-3 Dioctyltin Merkaptid

Catalyst-4 aluminum isopropylate, purity> 98%

Stabilizer-1 silicone-GLYCOL copolymer, without free OH groups

Stabilizer-2 silicone copolymer having a hydroxyl number of 30 ± 5 (mgKOH / g)

Filler Disperse silica

Examples 1 to

In the following Examples 1 to 10, the starting materials which can be taken from the following Table 1 were used, wherein at the same time it is stated which constituents were added together to prepare the reaction mixture in the form of a component A or component B.

Table 1" example

feedstocks

Water glass-1 water glass-2 water glass-3 water glass-4 water glass-5 water glass-6 epoxy-1 epoxy-2 epoxy-3 epoxy-4 R-NCO-1 R-NCO-2 catalyst-!

Catalyst-2 Catalyst-3 Catalyst-4 Stabilizer-1 Stabilizer-2 Filler

80.0

84,15

84,15

20.0

55,22 0,5

1.0

100 10

2.50

0.5

0.5

0.50 1.0

Water glass-1 water glass-2 water glass-3 water glass-4 water glass-5 water glass-6 epoxide-1 epoxide-2 epoxide-3 epoxide-4 R-NCO-1 R-NCO-2 catalyst ^ catalyst-2 catalyst-4 stabilizer- 1 stabilizer-2 filler

49.25 50.25

70

30

95

36.46 0.5

1.0

76.30 0.5

1.0

0.5

90

10

60.88 0.8

1.6

60.92

1.0 2.0

88

10

54.64 0.5

* Quantities of the starting materials in parts by weight A 7 B A 8th B A 9 B 10 Example 5 6 A B Starting materials AB AB

25.5 0.5

'Quantities of the starting materials in parts by weight

example 1

The A and B components are mixed together in the specified mixing ratio until a

whitish emulsion is formed.

The beginning of the reaction is indicated by viscosity increase and heat release.

-10- 284 The course of the reaction can be followed with a Shoro-Härto test instrument:

Minute Shoro hardness 5 2oD 15 3OD 30 4OD 60 45 D

From the reaction, a pale yellow not foaming, but not shrinking material was created.

Example 1a (comparison)

Reducing the proportion of the B component of Example 1 by 50%, we obtain a water-containing xerogel, which shrinks strongly and has low strength.

Example 2

The A and B components are premixed together in the specified mixing ratio until a whitish emulsion is formed.

The beginning of the reaction is indicated by viscosity increase and heat release.

The course of the reaction can be followed with a Shore hardness tester:

Minute Shore HSrto 5 yield 15 74 Λ 17 9OA 45 4OD

From the reaction, a pale yellow not foaming, but not shrinking material was created.

Example 3

The A and B components are mixed together in the specified mixing ratio until a whitish emulsion is formed.

The beginning of the reaction is indicated by viscosity increase and heat release.

The course of the reaction can be followed with a Shore hardness tester:

Minute Shore hardness 1 yield 2 95 A 3 5OD 4 55 D 5 6OD

From the reaction, a pale yellow not foaming, but not shrinking material was created.

Example 4

The A and B components are mixed together in the specified mixing ratio until a whitish emulsion is formed.

The beginning of the reaction is indicated by viscosity increase and heat release.

The course of the reaction can be demonstrated with a Shore hardness tester:

Minute Shore hardness 4 15A 5 65 A 530 ' 2oD 6 3OD

From the reaction, a pale yellow not foaming, but not shrinking material was created.

Example 4a (comparison)

If the proportion of the polyisocyanate from Example 4 is reduced by about 30% by weight, a strongly shrinking xerogel is formed which cures upon release of water.

Example 5

The A and B components are mixed together in the specified mixing ratio until a whitish emulsion is formed.

The beginning of the reaction is indicated by viscosity increase and heat release.

The course of the reaction can be followed with a Shore hardness tester:

Minute Shore hardness 330 ' Fließgrenzo 10 30D 15 4OD 30 45 D 1d 5OD

From the reaction, a pale yellow not foaming, but not shrinking material was created.

Example Sa (comparison)

If you reduce the ante '! of the polyisocyanate of Example 5 by about 15 wt .-%, so was a little shrinking, but relatively soft material which has a Shore hardness of 10A after 20 minutes and after one day a Shore hardness of 35 D.

Example β

The A and B components are mixed together in the specified mixing ratio until a whitish emulsion is formed.

The beginning of the reaction is indicated by Viskos'tätszunahme and heat release.

The course of the reaction can be followed with a Shore hardness tester.

The result is a very firm light yellow resin with low water content, at the same time high inorganic content. The figu.

Fig. 10 shows a photomicrograph of a fracture surface of the material obtained in this example at a magnification of 1: 10000.

Example 7

In a concrete block holes were drilled with a diameter of 50mm and a depth of 900mm. A hollow steel anchor was inserted into the borehole and centered and secured by means of a borehole closure. About the hollow anchor the well with the injection material according to Example 7 using a Hochdruckinjektionsmasc line was verpreiit. After 30min. The pull-out force of the anchor was tested with a hydraulic puller. The anchor (0 30mm) could not be pulled out. When increasing the hydraulic force, finally tore the anchor head.

Example 8

The A and B components are mixed together in the stated mixing ratio until a whitish emulsion is formed.

The reaction curve is indicated by viscosity increase and heat emission.

The course of the reaction can be followed with a Shore hardness tester:

Minute Shore hardness 45 yield 1 65 D

The result is a very firm light yellow resin that neither shrinks nor foams.

Example 9

The A and B components are mixed together in the specified mixing ratio until a whitish emulsion is formed.

The beginning of the reaction is indicated by viscosity increase and heat release.

The course of the reaction can be monitored with a Shore-Härto test instrument:

Minute Shore hardness 5 yield 20 25 A 25 15D 30 20D 60 55 D

The result is a very firm light yellow resin that neither shrinks nor foams.

Example 10

The A and B components werdon mixed in the specified mixing ratio until a whitish emulsion is formed.

The beginning of the reaction is indicated by viscosity increase and heat release.

After the reaction, a material with a high silica content and high gas permeation is formed.

Subsequently, it is demonstrated on the basis of comparative examples that in procedural conditions which do not correspond to the conditions of the method according to the invention, inferior or νΟΊ g unusable organomineral products are obtained.

Table 2

Comparative Examples

Feedstocks *

Comp-A

Comp-B

Comp-A

Comp-B

Comp-A

Comp-B

Water, Demin, COj-free 53.00 60.30 Water glass 1 0.50 NaOH 1.00 Polyisocyanate 31 Catalyst 1 Polysiloxani

65,50

17.82

25.00 25.00

60,30 0,50 1,00

30.15 0.25 0.50

Quantities of the single-salt substances in weight points Comparative Example 1

In a mixing vessel, the successively introduced components A + B are mixed until an emulsion is formed. After about 1 minute stirring time, the mass begins - recognizable by the heat of reaction - to react. This forms a lighter pale yellow foam without useful strength.

Comparative Example 2

In a mixing vessel, the successively introduced components A + B are mixed until an emulsion is formed. After less than a minute stirring time, the mass begins - recognizable by the heat of reaction - to react. The result is a non-foamed mass, consisting of hydrous granules. The initial pH of the reaction mixer of 14 decreased after the reaction to a value of 9-10.

Comparative control game 3

In a mixing vessel, the successively introduced components A + B are mixed until an emulsion is formed. After stirring for about 1 minute, the mass begins to react, recognizable by the heat of reaction, initially resulting in a non-foaming product, which, however, forms a light yellow foam in the second reaction phase. At the end of the reaction time, the brittle foam becomes partially from the inside due to sudden release of CO ₂ and water vapor

zerrisssen.

Claims (14)

1. A process for the preparation of Organomineralprodukten under reaction of organic polyisocyanates in the presence of aqueous Alkalisikatlösungen, characterized in that one carries out the reaction in the presence of an epoxy resin as a further reactant under the reaction conditions with the polyisocyanate or with this compound intermediately formed under Formation of oxazolidinone ring structures containing organic polymer structures reacts. 2. The method according to claim 1, characterized in that the organomineral products are prepared in i -'orm massive, non-foamed products and the reactants involved in the reaction polyisocyanate, aqueous Alkalisikatlösung and epoxy resin used in such molar ratios that the following relationship is met : + Y (^ ⁰ V) + (2x + y) (NCO)> where X (Me ₂ O) is the molar amount in moles of sodium and / or potassium oxide in the alkali silicate used, Yl c >>) is the molar amount in mol of the epoxide groups in the epoxy resin used, (2x + y) (NCO) is the molar amount of the-NCO groups in the polyisocyanate used, and wherein Me is Na or K and χ and y are the respective relative molar amounts expressing positive numbers that have a tolerance width, the usual quality variations the individual reactants are considered, if they are used as technical commercial products, and wherein the epoxy resin is used in an amount which is from 0.01 to 60Gew .-%, based on the weight of the alkali metal silicate solution used. 3. The method according to claim 2, characterized in that a polyisocyanate is used, whose content of NCO groups in the range of 0.238 to 1.190 mol per 100 g of polyisocyanate is that such an aqueous alkali metal silicate solution is used, that the content of Me ₂ O, wherein Me is Na and / or K, in the range of 0.081 to 0.323 mol per 100 g alkali silicate solution, and that such an epoxy resin is used, the content of epoxy groups in the range of 0.020 to 0.800 mol per 100 g of epoxy resin. 4. The method according to any one of claims 1 to 3, characterized in that a chemically pure or technical polyisocyanate or mixture of such polyisocyanates or a mixture of such polyisocyanates with organic monoisocyanates is used as the polyisocyanate, wherein the content of free NCO groups in the range from 10 to 50% by weight, preferably from 25 to 35% by weight. 5. The method according to any one of claims 1 to 4, characterized in that an aqueous alkali metal silicate solution is used which has a dissolved solids content in the range of 10 to 60 wt .-% and a Me ₂ O content of 5.0 to 20Gew .-%. contains. 6. The method according to any one of claims 1 to 5, characterized in that an epoxy resin is used which has a content of functional epoxy groups of 200 to 8000 mmol / kg. 7. The method according to any one of claims 1 to 6, characterized in that the reaction is carried out in the presence of a catalyst which promotes oxazolidinone formation. 8. The method according to claim 7, characterized in that the catalyst is selected from catalysts based on tertiary amines, catalysts in the form of organometallic compounds or catalysts in the form of inorganic salts. 9. The method according to claim 8, characterized in that the catalyst is selected from benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, tetraethylammonium bromide, Dioctylzinnmerkaptid, aluminum triisopropylate, aluminum trichloride, zinc dichloride or iron trichloride. 10. The method according to any one of claims 1 to 9, characterized in that the reaction mixture additionally stabilizers and / or fillers are incorporated. 11. The method according to any one of claims 1 to 10, characterized in that one prepares a first mixture (component A) from the aqueous alkali silicate solution and the epoxy resin and this mixed to prepare the reaction mixture with a second mixture (component B), which is the polyisocyanate and optionally contains the catalyst. 12. The method according to any one of claims 1 to 10, characterized in that for preparing the reaction mixture, a first component (component A) from the aqueous, optionally containing a catalyst alkali metal silicate solution with a second component (component B), which from the Polyisocyanate and an epoxy resin which is completely free from OH groups and which has been obtained by reacting the epoxy resin in a preliminary reaction with a monoisocyanate, the amount of monoisocyanate used being the stoichiometric amount of the OH group. in the epoxy resin corresponds. 13. The method according to any one of claims 1 to 12, characterized in that one carries out the process as a method for rock solidification by injecting the liquid reaction mixture into the cracks and cavities of a mountain and there to react in sltu formation of the organomineral products. 14. The method according to any one of claims 1 to 12, characterized in that it is carried out as a method for solidification and / or sealing of geological and / or artificial formations which are exposed to high energy radiation, by passing the reaction mixture through holes in the Formation injected or coated the surface of the formation to be sealed with the reaction mixture.