DD284033A5 - METHOD FOR PRODUCING ORGANOMINERAL PRODUCTS - Google Patents

Abstract

The invention relates to a process for the preparation of organomineral products which can be used for rock consolidation, stabilization and / or sealing of civil engineering works and boreholes, as molding and coating compositions. The organometallic products according to the invention are prepared by reacting organic polyisocyanates in the presence of aqueous alkali metal silicate solutions. According to the invention, the reaction is carried out in the presence of an epoxy resin as a further reaction partner, which reacts with the polyisocyanate to form oxazolidinone ring structures containing organic Polymergeruesten carrying adhesion-improving OH groups. According to the invention, the organomineral products are prepared in the form of solid, non-foamed products by using the reactants polyisocyanate, aqueous alkali silicate solution and epoxy resin in a molar ratio corresponding to the relationship. x, y, Me correspond to the meaning given in the description and in the claims. Relationship {organomineral; polyisocyanates; Alkali silicate solutions; epoxy resins; Polymer skeleton containing oxazolidinone ring structures; Stratum consolidation; Waterproofing of civil engineering works; bores; Molding and coating compounds}

Description

For this 1 page drawing

Field of application of the invention

The present invention relates to a process for the production of organomineral products, which are particularly suitable as rock solidification agents for coal, rock and / or ore in mining or tunneling, which is why the process 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 may be formed into artificial formation such as e.g. Foundations, walls of water retention systems or gas and oil wells for stabilization and / or sealing against water and gas are 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 state of the 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 publications in the prior art, reference being particularly made to FR-A-1362003, GB-A-1186771, DE-A-2325090, DE-A-2460834, DE-A -3421086, US-A-4 042536 and EP-A-000580.

In all the cases described, the organomineral products are prepared from reaction mixtures comprising a polyisocyanate and an aqueous alkali silicate solution ("waterglass solution") .Additionally, modifiers, catalysts, stabilizers and various blowing agents are used to achieve particular properties The solubility or solvatability of the organic compounds used by water to produce 'one-part emulsions particular attention.' The disclosed applications of bes inscribed organomineral products ranging from molding compounds and insulating foams over putties and adhesives to Bodenverbesserern and Bergungsverfestigungsrnitteln.

In the context of the present invention, since 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. By the term "rock solidification" wc is meant any process for solidifying and sealing geological and poured rock, earth and coal formations, the emphasis being on rock consolidation underground in mines or in civil engineering. and 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 regarding the possibilities of carrying out the method should be used 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 Hartem. The hardening of the water glasses takes place

different ways. For example, H. Joosten used water glass around 1926 and calcium chloride as the hardener component in a subsequent injection. The process was further developed into a "monosol process" using a single injection of highly dilute 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, epoxies and polyurethanes. For example, in 1959, injections of epoxy resin with fillers were performed. Further such processes, which were carried out using synthetic resins on a purely organic basis, in particular based on polyurethanes, are further described in German patents 1758185 and 3139395.

At the beginning of the development of organomineral products, the basic suitability of such products for soil stabilization or mountain hardening was also recognized. An early such process is described in the German Patent 1069878 from the year 1957, where emulsions of water glass and polymerizable unsaturated esters are injected for soil consolidation. The suitability of mixtures of water glass and polyisocyanate for sealing mountain formations in the form of buildings is mentioned in GB-A-118f 7 "In DE-A-2908746 or in parallel EP-A-0016262 the use of such mixtures is repeated from waterglass solutions and polyisocyanates for rock consolidation and waterproofing, it being taught, however, that only the addition of polyols to such blends results in true solidification in which stable formations are obtained.

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 an organic network based purely 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 purely inorganic rock stabilization showed a number of unwanted Nebeneffektdn, such as lack of strength of the formations by highly hydrous gels, brittleness due to incomplete or overcrosslinking curing reaction, leakage of the injection material into larger void areas or a Wegschwemmen by underground aquifers.

One injection at an angle above the horizontal through holes could not be done 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 the German Pa'enten 1758185 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 foams show a tough-elastic behavior that can not cope with the usual mining machines.

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. Boi injections into larger mountain cavities 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 can cause serious processing problems for the user on site and impairs the reliability of the method. Injection formulations with long reaction times are namely susceptible to the occurrence of side reactions, eg. B. by the absorption of water, whereby the reaction stoichiometry is shifted so that not the desired reaction product is obtained. The resulting in the reaction with water larger amounts of CO ₂ build up a gas pressure, which can lead in Fläcnenhaften columns for printing mountain ranges and thus counteracts the desired 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.

For the sake of the aforementioned type, the use of intumescent polyurethanes for injection in coal mining is close Limits set, whereby this use is strictly regulated by official regulations. The organomineral products, when used as grouting agents, have been found to be mountainous over pure However, polyurethanes have made significant progress, but have also led to a number of new difficulties. The organomineral products important to the scope of the present invention are selected from polyisocyanates and aqueous Alkali silicate solutions obtained. In such systems, isocyanate groups react with the participation of water

low molecular weight urea segments, which are extremely hard and strong, but do not contribute to the adhesion to the rock layers. The simultaneously released in the reaction CO ₂ -GaS reacts with those in the

Alkali silicate existing alkali oxides (Me ₂ O, where Me = Na, K) to carbonates and thereby falls into the silicate radical as

hydrous xerogel. In this uncontrolled decomposition of alkali silicate solution whose contribution to the adhesive effect is lost. To improve the adhesion, therefore, polyol proportions are also required in such reaction mixtures, which follows, for example, from a comparison of Example 1 of DE-A-2 908740 with the remaining examples. Additions of Polyolone to a Reaction Mixture of Isocyanates In an aqueous alkaline medium, reaction kinetics - especially under the harsh mining conditions - are not controllable, since with the high excess of water, always the water-induced

Isocyanate reaction is the main reaction. Polyols form in such systems therefore only relatively short-chain separated

present organic molecule segmento in an inorganic matrix.

It was therefore attempted in systems of the type mentioned, the contribution of organic content at the expense of inorganic Increase share. An increase in the proportion of synthetic resin, however, leads to a deterioration of the economy of Process. According to DE-A-3421086, therefore, another way will be described by trying to control the isocyanate reaction in Alkalisilikatlösungen by the simultaneous use of a suitable Trimerisierungskatalysators with simultaneous Attention to direct the amounts of the reactants so that a per se of the trimerization of the isocyanates derived

organic network is formed. While this does in fact impart extremely high strength to the final product, it is again formed by hard organic molecular structures which, due to the lack of more functional

Endgruppen no bonding effect, especially on wet rock effect. It is also a disadvantage that the trimerization capability of the catalyst is only within narrow limits of the Substance ratio catalyst / Isocyanatgruppon comes to fruition, while at a lower or Exceeding the optimum ratio, the usual isocyanate reaction is strongly excited with water, so that a

undesirable large nichtklebefähiger urea content arises. However, this procedural limitation has the procedural disadvantage that at an occasionally desirable high reaction rate of the formulations an uncontrolled foaming of the liijektionsgutes is observed, which leads to a product which leads to a slight

Powder can be crushed. Another problem that has not yet been satisfactorily solved is in the area of solidification and / or sealing of

natural geological or artificial formations exposed to high-energy radiation.

Through the vigorously driven expansion of nuclear energy in the last two decades as well as the use

radioactive isotopes for a variety of technical, medical and scientific investigation ergabsich ergabsich increasingly the situation that a high-energy radiation, in particular a radioactive radiation emitting

Materials Must be stored for a substantial period of time or stored temporarily or permanently. The structural constructions selected for these storage and storage purposes or overground or underground For safety reasons, locations must have an extraordinarily long-term stability and / or tightness against

have a gas and liquid exchange with the environment.

Apart from these increased safety requirements, however, results in the attempt of additional solidification

and / or sealing an additional material problem due to the fact that the high energy emanating from the material destroys numerous materials that would otherwise be suitable for solidification and / or sealing. This is especially true for most organic based resins.

As formations that must be sealed, in particular subterranean or supernatural end or Intermediate storage for radioactive material, structural designs of nuclear power plants, transport containers for radioactive material Material or sinks and water tanks holding radioactive material are considered. Object of the invention

It is the object of the invention to provide a method in which the described Nacrueile Sta Sta of the art completely overcome or at least significantly mitigated.

Explanation of the essence of the invention It is therefore the object of the present invention to provide a process for the preparation of novel organomineral products on the basis

of polyisocyanates and aqueous alkali metal silicate solutions which, while avoiding the specified disadvantages of the method, reliably provide non-foamed polymeric organo-mineral products which are hard on the one hand but have greatly improved adhesiveness over comparable products and which in addition have improved resistance to high-energy radiation compared to organic resins ,

On the one hand, the isocyanate reaction leading to the formation of the inorganic silicate skeleton should be unhindered with water

On the other hand, a foaming safely prevented.

This object is achieved by a method according to claim 1. Advantageous concrete Embodiments of this method can be found in the dependent claims. Hereinafter, the invention will be more important in terms of the composition and properties of the process product Reactions as well as with a view to a more detailed definition of possible starting materials explained in more detail.

In a reaction mixture according to the present invention, polyisocyanates (R-NCO), an aqueous alkali metal silicate solution (H ₂ O ₁ Me ₂ O x nSIOj) and an epoxy / ι _wQv. contains run in the inventive method in the

in the following formula scheme. Ee should, however, still be pointed out 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 Epoxidgruppnn, have other centers that can react within the meaning of the following formula scheme. However, this means that the reaction products obtained, which still have such radicals in the following equation, are in reality parts of highly polymeric organic frameworks

 The product-forming reactions are:

1. R-MCOI · H ₂ O -> (R-NH-COOII) -> RNIh ι CU ^ ι Wilrmo

2. R-NCO. ► RNH ₂ -> R-NH-CO-NIi-R ι · Wünuü

3. Mg _? 0 t CO ₀ -> Me ₀ CO _n

* 4 Λ J Q

4. R-NCO t R'-C'-C-> / ^S _O

iir S

Arn

5. R'-CC- + (R-NH-COOR ¹¹ J -> R "-OH +

it

Q,

6. R "-OH + R'-dC- ->R" -CH ₂ -C-R '

Il

OH ⁿ

The Schematically illustrated in these formulas reactions intervene in the practice of the inventive method for producing Organomineralprodukten as follows: Reaction 1 is the usual known reaction of isocyanates with water. 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. In addition, this reaction provides 2 more heat. For the process according to the invention, the urea units formed at this stage are more 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 polyoxazolidinones, which form 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 moles verb) are consumed. Since this CO _{2 is} to be completely bound by the reaction mixture to prevent foaming, for reasons of the reaction stoichiometry, isocyanate groups and Me ₂ O molecules must be present in a ratio of 2: 1 in the reaction mixture.

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 hydroxyl functional groups, formed in the reaction mixture as intermediates by-products urethane segments, which are represented in formula 5 schematically by the parenthesis. With such Urethansegmenten the epoxy resins can also react under Oxazolidino.ibildung, wherein it is important that while organic products with free hydroxyl groups (FT-OH) are produced.

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

Thus, in the process of the invention, hydroxyl-containing segments are inevitably formed as products of side reactions 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:

* "^" 'W ^ noiulnora Lprocluk U)

In contrast to the known methods, bi>! where the organic polymer skeleton unfolded no adhesive effect, in the method according to the invention a lifting polymer skeleton is formed, which contributes to HaftungsverhöSbSrung between rock and synthetic resin in addition to the inorganic silicate framework. By taking care in the formulation according to the invention that there is always the amount of alkali oxide necessary for the binding of the developed CO ₂ , 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, which also usually suitable catalysts still take an important control function. 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-Trls (dimethylaminomethyl) phenol or benzyldimethylamine clearly 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 , AICIa ° ZnCl] activate in particular the epoxide groups to react 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.

Also organometallic compounds, eg. For example, triisopropylaluminum AKi-C ₃ H ₇ I 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 stoichiometry, which can be calculated according to the invention, catalysts help to reliably control the intrinsically very complex reaction system epoxy resin-water glass polyisocyanate.

It is the goal of any recipe classification 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 proceed as far as the resulting CO ₂ gas can be absorbed by the overall formulation.

2. The exothermic heat formed in this initial reaction and the oxazolidinone formation catalyst must be coordinated so that even in aqueous alkaline systems polymer scaffolds are formed on an organic basis. To meet requirement No. 1, care must be taken to maintain the ratio of the reactants as defined in claim 2, namely the condition that the organo-mineral products be prepared in the form of solid, non-foamed products and the reactants involved in the reaction Polyisocyanate, aqueous alkali metal silicate solution and epoxy resin used in such molar ratios that the following relationship is satisfied:

X (Me ₂ O) + y (-) + (2x + y) (NCO) - »Products,

where X (Me ₂ O) is the molar amount in moles of sodium and / or potassium oxide in the alkali silicate used,

O Y () is the amount of fabric in moles of epoxide groups in the epoxy resin used,

(2x + y) (NCO) the amount of NCO-groups in mol in the used. Polyisocyanate is, and wherein

Me stands for Na or K and χ and y are the respective relative molar numbers expressing positive numbers, the one Have tolerance width, which take into account the usual quality fluctuations of the individual reactants, if this

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 employed

Alkalisilikatlösung, is. The correct ratio of isocyanate groups to epoxide groups in the reaction mixture and, matched to that Effectiveness of the reaction 4 activating catalyst ensures compliance with the above requirement No. 2. Preferably, reaction mixtures are prepared from feedstocks 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 Epoxide units (oxirane rings, excluding epoxy resin) 0.020-0.80 mol proline Preferably, such amounts of alkali metal silicate solution and epoxy resin are used that the alkali metal silicate solution and the Epoxy resin used according to one embodiment in the form of a premix referred to as "component A"

are present in a premix containing only these two components in quantities of 70 to 95% by weight of alkali silicate solution and 5 to 30% by weight of epoxy resin. These amounts correspond to a content of Me ₂ O of 0.09 to 0.28 mol per 100gbzw. from 15 to 210mmol epoxide groups per 100g.

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 amounts of substance of the above reactants within the specified molar ratio. On the basis of currently observable quality fluctuations, the following tolerances apply approximately:

(NCO) ± 5% (Me ₂ O) ± 2.5%

(-) ± 7.6%

Taking into account the various possible water glass qualities and epoxy resins which can be used in the process according to the invention, it is further evident 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 waterglass solution used can. As already indicated, in the process according to the invention the usual polyisocyanates and aqueous alkali metal silicate solutions which have hitherto been used in such processes can be used.

The polyisocyanates cyanate are pure or technical polyisocyanates, in particular solvent-free 4,4'-diphenylmethane diisocyanate in admixture with higher-functional isocyanates, as they are marketed by different manufacturers, called crude MDI. However, it is also possible to use so-called prepolymers which still have reactive NCO groups. 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, the use of a prepolymer which is produced from a mcnoisocyanate and a claimed epoxide ring-containing resin is claimed in an inventor. In this case, in stoichiometric amount of excess NCO groups, the OH groups unavoidably formed in the preparation of the epoxide group-containing resin are reacted to form 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 the formation of oxazolidinone, and sufficient storage stability is also obtained for this component. As aqueous alkali metal silicate solutions, sodium and / or potassium waterglasses, and mixtures thereof having a dissolved solids content of 10 to 60% by weight, in particular 35 to 55% by weight, and an alkali metal oxide content of 5 to 20% by weight, in particular 8 to 18% by weight. In terms of their inventive utilization, the water glasses lying in this range have good process properties, such as fluidity, easily replaceable 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 formulation, yields a high or low water content end product, the product surprisingly having a low water content, as in Example 9, being gas tight with a value of <1 mD (Milli-Darcy).

As epoxide resins, per se known epoxy resins can be twisted, which have a content of functional epoxy groups in the broad range of 200 to 8000mMol / kg, preferably in the range of 300 to 700mMol / 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 can also be used more highly functional epoxy resins, such as epoxy resins on phenol novolac Bp us.

The process according to the invention may preferably be carried out by two mixing methods. According to the first method, a Α component of epoxy-containing material is prepared with the alkali silicate solution, which is then reacted with the calculated amount of B component. When using a technical polyisocyanate as the B component, a catalyst activating the oxazolidinone reaction has already been added. In addition, other catalysts of the type of B component according to the invention may be added. According to the second method, the Α-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 process 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 immediately injected under pressure into the rock to be solidified, in the cited prior art described techniques can be used. Since the products according to the invention are not foams, self-injection methods (filling in a borehole and simple closing) are excluded.

The materials that can be produced according to this teaching are due to the variation of inorganic to organic polymer content

versatile because important polymer properties, such as Ε-modulus and compressive strength are adjustable over a wide range.

Thus, formulations with a high silicate content are stone-like masses, formulations with a high organic content are more likely

typical properties of polymeric materials.

Due to their reaction behavior, the components can also be injected into open and / or closed molds, see above

that from this impressions or plates, rods, frames, models, machine parts, etc. can be made.

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

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

The Organomineralprodukte prepared by the process according to the invention have the advantages / cf that they no Have foam structure that complicates or prevents a gas-tight seal, and that first investigations shown

have said that the organo-mineral products having epoxide group extended chain segments are extremely stable to the action of high energy radiation. The good adhesion to stone is maintained, and there is no release of

Gases or vapors. These properties advantageously distinguish the preferred organo-mineral products from those as described in U.S. Pat EP-A 0016262 used in coal mining or as described in DE-A 3421085. In these Publications describe products that have i.d.R. have a foam structure and in their preparation from the Drafting of water vapor as well as Treibmitel (Chlorfluorkohlonwasserstoffe) give off what a perfect gastight Seal prevented. The Polyurethansegrnente present in these materials are against exposure to high-energy radiation

(presumably similar to polyamides) sensitive and are decomposed by such radiation. At least for the purpose of sealing \ / or solidifying long-life ligaments, such materials are therefore i.d.R. not suitable.

The organo-mineral products produced from the three-component reaction system of the process of the invention are

On the other hand, due to their massive nature as well as the organic components which are insensitive to high-energy radiation, they are outstandingly suitable for the purposes described.

For the claimed use, the organo-mineral products are either in the form of their starting reaction mixtures

as known from the applications of such Organomineralprodukte z. B. In coal mining, injected over holes in diezu consolidating formations, or they are applied for the purpose of sealing instead or in addition flat on the surface to be sealed surfaces of the formation to be sealed, after which the Abreaktion below

Waiting for organometallic products training or possibly produces the favorable environmental conditions. In the following, dl *) invention will be described on the basis of exemplary embodiments which include selected reaction mixtures for the Implementation of erfim'ungsgemäßen method and comparison mixtures relate, explained in more detail. It is on a 1, which is a photomicrograph of a method prepared by the method of the invention

(Magnification 1 1000) product.

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 abbreviations, behind which hi h hide the products listed below:

Starting Materials:

R-NCO 1

R-NCO 2

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

filler

Wt .-% Me, 0

Wt .-% of the total solids

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 ! Was8erg as-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 mmol of epoxide kg

MOD. Bisphenol-A Dimer fatty acid base Bisphenol-A Standard Phenol novolac

4650-5130 2130-2560 5150-5550 5260

Diphenylmethane-4,4'-diisocyanate FreeNCO content3l ± 1 wt% Hydrolysable chlorine 0,1-0,45% Phenyl isocyanate, technically pure dimethylbenzylamine

2,4,6-trisdimethylaminomethylphenol

Dioktylzinnmerkaptid Aluminum isopropylate, purity> 98% Siucon-GLYCOL copolymer, without free OH groups Silicone copolymer having a hydroxyl value of 30 ± 5 (mgKOH / g) Disperse silica Examples 1 to

In the following Examples 1 to 10, the starting materials which can be taken from the following Table 1 are 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 Was.serglas-3 Water Glass 4 Water Glass 5 Water Glass 6

Epoxy-1Epoxid 2Epoxid-3Epoxid-4R NCO-1R NCO 2

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

filler

80.0

84,15

84,15

20.0

55,22 0,0

1.0

100 10

2.50

0.5

0.5

0.50 .1.0

Water glass! Water Glass 2 Water Glass 3 Water Glass 4 Water Glass 5 Water Glass 6

Epoxy-1Epoxid 2Epoxid-3Epoxid-4R NCO-1R NCO 2

Catalyst-1 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

54.64 0.5

* Quantities of the monosubstituted substances In weight points Table 1 · A 7 B A 8th B A 9 B 10 Example 5 6 A B Substitutes AB AB

88

10

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, his one

whitish emulsion is formed.

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

-ί-- 284 The course of the reaction can be followed with a Shore hardness tester:

Minute Shore hardness 5 2oD 15 3OD 30 4OD 60 4OD

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

Example 1a (comparison)

Reducing the proportion of the B component from Example 1 by 60%, we obtain a water-containing xerogel, which shrinks strongly and has low strength.

Example 2

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 5 yield 15 74A 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 an increase in viscosity and heat release.

Dor reaction history can be followed with a Shore hardness tester:

Minute Shore Shepherd 1 yield 2 95A 3 5OD 4 55 D 5 COD

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

Example 4

The A and B components are mixed with each other 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 flow course can be followed with a Shore hardness tester:

Minute Shore hardness 4 15A 5 65A 530 ' 20D 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 Hürie 330 ' yield 10 3OD 16 4OD 30 45 D 1d SOD

From the reaction, a pale yellow not foaming, but not shrinking material was created. Example 5a (comparison)

If the proportion of the polyisocyanate from Example 15 is reduced by about 16% by weight, a somewhat shrinking but relatively soft material is formed, which after 20 minutes has a Shore hardness of 10A and, after one day, a Shore hardness of 35 D has.

Example β

Di 3 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 an increase in viscosity and heat release cn. 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 figure

Fig. 10 shows a photomicrograph of a fracture surface of the material obtained in this example at a magnification of 1000.

Example 7

In a concrete block holes were drilled with a diameter of 50mm and a depth of 900mm. In the drill hole, a hollow steel anchor was inserted and centered and secured by means of a Borlochverschlussss. About the hollow anchor, the well was pressed with the injection material according to Example 7 using a high-pressure injection machine. 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 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 Htrte 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 Reaktionsvsrlauf can be followed with a Shore hardness tester:

Minute iShore-Hlrte 5 said border 20 2i> 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 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. After the reaction, a material with a high silica content and high gas permeation is formed. Subsequently, it is demonstrated by means of comparative examples that under process conditions which do not meet the conditions

correspond to the inventive method, inferior or completely unusable organomineral products are obtained.

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 scaffolds reacts. 2. The method according to claim 1, characterized in that the organomineral products are prepared in the form of solid, non-foamed products and reactants involved in the reaction polyisocyanate, aqueous Alkalisikatlösung and epoxy resin used in such Stoftmengenverhältnissen that the following relationship is satisfied: X (Me ₂ O) + y ( ^ ⁰ X ) + (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, V ( <C - k) 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 numbers expressing positive numbers t ufweisen a tolerance breadth, the usual Quality variations of the individual reactants are taken into account when d'ese 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 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 is in the range of 0.081 to 0.323 moles per 100 g of alkali silicate solution, and that such an epoxy resin is used, the content of epoxy groups in the range of 0.020 to 0.800mol 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 contains a dissolved solids 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 d6r 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 a completely free of OH groups epoxy resin, which has been obtained by reacting the epoxy resin in a pre-reaction with a monoisocyanate, wherein the amount of monoisocyanate used the stoichiometric amount of OH groups 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 formation in the cracks and cavities of a mountain and there to react with in situ formation of the organo-mineral 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.