JPH0386758A - Manufacture of organic mineral product - Google Patents

Abstract

PURPOSE: To obtain an organic mineral product which is excellent in adhesion etc., and suitable for a stratum reinforcing agent, radioactive material storing container sealing, etc., by adding an organic polyisocyanate and an epoxy resin to an alkali metal silicate aqueous solution and reacting the mixture.

CONSTITUTION: An organic polyisocyanate (example: diphenylmethane-4,4'- diisocyanate) and an epoxy resin (example: a bisphenol A type epoxy resin) are added to the aqueous solution of an alkali metal silicate (example: sodium silicate), and the mixture is reacted. An organic mineral product is produced, and an adhesive organic polymer structure containing oxazolidinone ring structure is produced by the reaction between the epoxy resin and polyisocyanate or a compound formed in an intermediate stage. In this way, the obtained organic mineral product has a property of bonding a rock to a synthetic resin with high adhesive strength.

COPYRIGHT: (C)1991,JPO

Description

[Detailed description of the invention] (Industrial application field) -knnn l+ L -/ + ++,
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! 74A4 A process for producing an organo-mineral product which is particularly suitable as a formation strengthening agent for rocks and/or ores.

The reason for this is that the method is carried out as a strata strengthening method in which the organo-mineral product is produced directly in situ within the strata structure to be strengthened. Furthermore, according to the method, the material can be used in man-made structures such as walls, foundations of tank structures, for example in gas and oil drilling for stabilization and/or sealing against water and gas. The invention can further be used as an advantageous method of exposing natural and/or man-made structures to abundant high radiant energy for reinforcement and/or sealing.

PRIOR ART Within the scope of the present invention, an internal composition of an organic polymer and an inorganic silicate which simultaneously contains organic and inorganic components and which is prepared from a single reaction mixture and which can additionally contain organic and/or inorganic components is used. More or less homogeneous materials suitable for network formation bonded to are described as organo-mineral products.

Such organo-mineral products are already known from numerous prior art publications, in particular from French Patent Publication (P.
R-A)l, 362.003, British Patent Publication (C
B-A)l, 186.771. German patent publication (D
E-A) 2, 325.090, German Patent Publication (DB-
A) 2.460.834, German Patent Publication (DE-A
) 3,421,086, United States Patent Publication (US-A
) 4.042.536 and European Patent Publication (EP
-A) 0.000.580 is referenced.

The organo-mineral products in all the cases described are prepared from reaction mixtures containing polyisocyanates and aqueous alkali metal silicate solutions (water glass solutions). Furthermore, modifiers, catalysts, stabilizers and various blowing agents are used in each case to obtain special properties. Particular attention is paid to the solubility or solvation of the organic compounds used as this results in finely dispersed emulsions with water in order to achieve as homogeneous properties as possible.

The description of organo-mineral products for the disclosed applications extends from cement and adhesive compounds, to molding compounds and insulating foams, to soil amendments and formation strengthening agents.

Since one of the main applications of the method according to the invention is the strengthening of geological formations within the scope of the invention, it is appropriate to summarize and describe in general terms the more recent technical advances in this special field. This seems to be the case.

In connection with this, “stratum reinforcement”
onsolidation) J is a term used in geology.
It is understood to mean a method consisting of the strengthening and sealing of loose rock, soil and coal structures. The main emphasis is on the reinforcement of subsurface formations in mining or in construction technology. Such methods are known per se and in practical terms, and the method according to the invention is similar to already known formation strengthening methods. The results of the prior art cited below should be considered with regard to the possibility of following the method for the purpose of supplementing the present invention.

Formation reinforcement is the process of chemical, soil reinforcement when coarse gravel, rock, coal or ore deposits are strengthened or sealed against non-flowing and flowing water or seawater by injection of suitable liquid chemicals. Special Limited Moops 7z L Harefuu Nanatsuji is written at the end of the Hatakekanshinshi/10th period. At that time water glass was used along with hardeners. Water glass can be hardened in a variety of ways. Thus 1925
In 2002, HlJoos2OH used water glass and then injected calcium chloride as a hardener component. The process was further developed into a monosol process, in which a single injection of highly diluted water glass and sodium aluminate was used. Another method, the so-called Monodur J method, used an emulsion of water glass and an organic acid as a hardener component.

In the middle of the 20th century, the suitability of synthetic resins for the purpose of strengthening strata was investigated, and this was first done particularly in the mining of American hardwood and coal. Experiments were therefore carried out with the injection of curable plastics based on polyesters, polyacrylates, epoxides and polyurethanes.

In 1959, for example, epoxy resin and filler injections were carried out. Moreover, such a method actually uses pure organic bases and synthetic resins based on polyurethane.
It is published in 139.395 in 139.395.

The development of organo-mineral products has begun and it has been recognized that such products are fundamentally suitable for strengthening soils and strata. An early method of this kind was described in German patent specification 19
1.069.878 of 1957, in which water glass and polymerizable unsaturated ester emulsions were injected for the purpose of soil reinforcement. German Patent Publication 1.186.77i mentions the suitability of mixtures of water glass and polyincyanate for the sealing of geological formations in mining. German Patent Publication 2,908.746 or parallel European Patent Publication 0.016.262 again discloses the use of such mixtures of water glass solutions and polyisocyanates for strengthening and sealing formations. ing. however,
They teach that only by adding polyols to such mixtures can stable structures be obtained and true reinforcement result.

German Pat. It is stated that any mixture of aqueous metal silicate solutions can advantageously improve formation strengthening.

However, all previously known methods of strengthening geological formations have the disadvantage of limited applicability and reliability.

In the case of the first injection methods, the most satisfactory reinforcement was not achieved due to the reinforcement of soils and strata using purely inorganic materials. This was probably due primarily to the fact that the ratio of viscosity to solids content in the water glass used was not then favorable, and also to the fact that control over the rate and extent of the curing reaction was not optimal. Ta. The effects of soil or strata structure bonding and temperature, porosity, or the occurrence of stagnant and running water may have affected the results in such a way that the effects obtained do not correspond to the planned results.

Attempts at purely inorganic formation reinforcement may result in insufficient strength of the structure due to extreme water-containing gels, brittleness due to incomplete or overly cross-linked hardening reactions, runoff from groundwater-supported river beds, or no A number of undesirable side effects appear, such as leakage of injection material into large recessed areas.

It was completely impossible to inject through a hollowed-out hole at an angle above the horizon. The water glass hardening agents used, such as formamide and glyoxal, have been introduced into ground construction in large quantities and today must be classified as environmentally hazardous.

Similar limitations have been discussed for many plastic-based injection materials that emit or contain hazardous substances. Mention may be made, by way of example, of phenol, formaldehyde, organic solvents and water-soluble blowing agents, and chlorinated and fluorinated hydrocarbons. Of the large number of imaginable plastic preparations for strengthening and/or sealing formations by injection, only a few have achieved practical significance. These include German Patent Publications 1.758.185 and 3.13.
The polyurethane synthetic resin described in 9.395 is included.

Again for material economic reasons, the formula is that white 8
! It was preferable to use it when foaming under 5i conditions. In this case, the advantage of foam formulations is that, in particular, the expansion pressure is generated during foaming, creating the effect that the injection material injects itself, and injecting the injection material inside the hollowed-out hole that seals the outside. This makes it easier to operate or requires lower injection pressures. However, it has been recognized that foaming itself has the disadvantage that the strength of the hardened synthetic resin is reduced.

Despite the expanded application of foam formulations, however,
Foams would at least not be considered desirable, if not dangerous. Expansion pressures in fact not only create an advantage for the injected material to inject by itself, but can also be counterproductive, primarily if the expansion pressures accumulate behind-the-scenes in large formations and displace the formations. Due to the inherent elasticity of synthetic resin foams, such foams also lead to new formation of cracks in the formation during stress in the formation, with the result that movement of the formation becomes possible.

Furthermore, most foams handle well against conventional mining equipment.
．． The theory of elastic single action 2 is shown below.

A further particular source of danger when using polyurethane reaction mixtures is the inadequate control of the heat of reaction generated itself at the work surface. When completely injected into large formation depressions, spontaneous ignition of the polyurethane mixture occurs. In particular in coal mines and/or in mines containing flammable atmospheres, this remains an unresolved problem.

Therefore, it is necessary to adopt remedies that allow the heat of reaction that is unavoidably generated in such formulations to be released into the surroundings over a prolonged period of time. However, for this purpose the formulation needs to slow down solidification in terms of reaction behavior. However, this imposes severe manufacturing process technical problems on the user and impairs the reliability of the manufacturing process. Injection formulations with long reaction times are in fact susceptible to the occurrence of side reactions, for example due to absorption of water, resulting in a stoichiometric shift of the reaction and failure to obtain the desired reaction products. The large amount of carbon dioxide generated in reaction with water creates a gas pressure that causes the movement of the mineral deposits within the stratified cracks, thus working against the immobilization of the strata that it is trying to reach. Additionally, slower-reacting formulations increase the risk of drainage from seepage into depressions or reinforcement of formations;
Increases the substantial extraction of injected material. The narrow groove edges require high injection pressures for penetration, which the injection material cannot reach on the other hand.

For reasons of the type mentioned, the use of foamed polyurethane for injection in coal mining narrows the limits. Its use is also strictly regulated by requirements of the Pharmacy Act.

Compared to pure polyurethanes, organo-mineral products have yielded substantial benefits for use as injectants for formation reinforcement, but have resulted in many new difficulties.

Important organo-mineral products within the scope of the invention are obtained from polyisocyanates and aqueous solutions of alkali metal silicates. In such systems, the isocyanate groups react with water to form low-molecular urea segments, which are extremely stiff and can withstand loads, but do not contribute to the adhesive action with respect to rock formations.

At the same time, the carbon dioxide gas released during the reaction is absorbed by the alkali metal oxide (Me2) present in the alkali metal silicate solution.
Ol (where Me is N8, K) to form carbonates and precipitate silicate residues to the same extent as dry gels containing water. In this uncontrolled decomposition of the alkali salt silicate solution its contribution to the adhesive action is lost. A polyol component is therefore necessary in such reaction mixtures in order to improve their adhesion, for example in comparison with the remaining examples of Example 1 of German Patent Publication 2,908,746. The addition of polyols to the reaction mixture of incyanate in an alkaline aqueous medium cannot be controlled from the point of view of reaction kinetics, especially under the harsh conditions of mining, since the water-induced incyanate reaction is the main reaction due to excess water. . In such systems, the polyols therefore form relatively short chain organic molecular segments that exist in isolated form within an inorganic matrix.

Attempts have therefore been made to increase the contribution of organic compounds in the mentioned systems with the presence of inorganic compounds.

However, the increase in the synthetic resin component makes the method less efficient.

According to German Patent Publication 3.421.086, another method therefore attempts to control the reaction of isocyanates in alkali metal silicate solutions by likewise using suitable trimerization catalysts. has been followed, while simultaneously considering the amounts of reactants in such a way as to form a network derived from the trimerization of incyanates. Although this gives an especially high strength to the final product, especially for moist rocks, the structure of hard organic molecules cannot provide any adhesive effect due to the lack of suitable functional end groups. It is composed of

A further disadvantage is that the trimerization capacity of the catalyst is only fully exploited within a narrow range of the substance ratio catalyst/amount of isocyanate groups. If the ratio is decreased or exceeds the optimum, the normal incyanate-water reaction is strongly activated, resulting in the production of undesirable non-adhesive urea components. This formulation limitation, however, is a disadvantage in process technology, and sometimes in the case of high reaction rates of the desired formulation, uncontrolled foaming of the injection material leading to a product that crumbles into a light powder has been observed.

The structural facilities or above-ground or underground sites chosen for these storage and storage purposes must at the same time have long-term stability and/or impermeability to gases and liquids in exchange for environmental conditions for safety reasons. must have.

Apart from these increasing safety demands, however,
The use of additional materials due to the fact that the high energy or radiation generated from the materials when attempting additional reinforcement and/or sealing destroys many materials that are suitable for reinforcement and/or sealing. A problem arises. In particular, this applies to most resins with organic bases.

In this connection, in particular underground or above-ground final or intermediate storage locations for radioactive materials, transport containers for radioactive materials, structural equipment of nuclear power plants or cooling oil and water containers for storing radioactive materials must be sealed. It is considered to be a structure that cannot be built. It is therefore an object of the present invention to provide a new process for the production of organo-mineral products based on polyisocyanates and aqueous alkali metal silicate solutions, which process has been described in a reproducible manner. Avoiding the disadvantages of the process technology produces a non-foamed polymeric organo-mineral product, which on the one hand, but also on the other hand, has improved formable adhesion compared to comparable products and even compared to organic resins. improved resistance to high-energy radiation. In this connection, it is necessary, on the one hand, to develop inorganic silicate structures and, on the other hand, to reliably avoid foaming.

This object is achieved by the method defined in claim 1 of the invention. That is, the method involves reacting an organic polyisocyanate with an epoxy resin as a co-reactant in the presence of an aqueous alkali metal silicate solution. This is a method for producing an organo-mineral product having a polymer structure. Advantageous special developments of this method can be found in the dependent patent claims.

The present invention will be explained in more detail below, in connection with a more precise definition of the possible starting products, the reactions of the main parts which are important for the nature and composition of the products according to the process.

According to the present invention, in the polyisocyanate (R-NCO) mixture, the main reaction proceeds as described in the following reaction formula. However, in this connection, incyanates are mainly difunctional, higher functionality polyisocyanates and mixtures thereof, and epoxy resins usually have at least two epoxy groups, R
It is pointed out that the group and the R' group of the epoxy resin further have centers capable of reacting in the sense of the following reaction scheme. However, in the reaction scheme below, the reaction product obtained with such a group is in fact part of the organic structure of the polymer.

The reaction that produces the product is expressed as:

1, RWCO+ H*O→(R-NH-C00H
)→RNHt+CO*10 heat 2, R-NCO+ R-NH,-◆R-N11-
CO-NH-R ten heat 3, MevO+ COt→Me*C05R'-0C
R, -C-R' H The method for producing an organo-mineral product according to the present invention is carried out by the reactions shown in the above reaction formula, which are interrelated as follows. Reaction formula 1 is a reaction between incyanate and water.

This reaction is well known and very important; it is exothermic and produces carbon dioxide. The amine produced in this reaction reacts with the incyanate in Scheme 2 to form a urea bond, the urea structure forming the first solid portion as known in the subsequent reaction product. On the other hand, carbon dioxide gas reacts with the alkali metal oxide component of the alkali metal silicate to form carbonate in Reaction Formula 3. The heat generated in Reactions 1 and 2 allows the reaction of the water and the still unreacted incyanate groups with the epoxy resin present in the reaction mixture, opening the oxirane ring and forming a polymeric organic framework. Produces oxazolidinone.

In this relationship, it must be pointed out that in equations 1 and 2, 2 moles of RNCO (= 2 X mol) are used to produce 1 mole of CO. This CO2 should be completely combined with the reaction mixture to prevent foaming, and the isocyanate groups and MetO molecules should be present in a 2:1 ratio of amounts of substances.

Since equal amounts of inocyanate and epoxy groups react with each other according to Scheme 4, an additional portion of isocyanate groups (Y) is required for this reaction.

In addition to basic reaction formulas 1 to 4 for network structure formation,
Two reaction equations are very important for the properties of the products produced in the process according to the invention.

It is inevitable that the polymer or epoxy resin produced therefrom in the reaction contains a proportion of functional hydroxyl, urethane segments. The R -1fH-C0OR'carbamate ester shown in parentheses in Reaction Scheme 5 is produced as an intermediate. It has a free hydroxyl group (R
'-0R) and on the other hand react with the epoxy resin to form the urethane segment oxazolidinone.

These hydroxy compounds can react with the epoxy groups of the epoxy resin still present, and according to Reaction Scheme 6, organic structures containing hydroxyl groups of ilM are obtained.

In the reaction according to the present invention, the segment containing a hydroxyl group results in inevitable side reaction products in the resulting polymer chain. The hydroxyl groups in particular are important for the properties of the exceptionally obtained products, since the organic polymer structure formed also has an adhesive effect. It can form hydrogen bonds with oxygen located on the surface of rock materials. In particular, it can be expressed as follows.

In sharp contrast to the known methods, in which the organic polymer structure does not produce any adhesive effect, in the method according to the invention an adhesive polymer structure is produced which, in addition to the inorganic silicate structure, forms a bond between the rock and the synthetic resin. contributes to improving the adhesion of Foaming can be avoided in the formula according to the invention if care is taken that the amount of alkali metal oxide necessary to bind the carbon dioxide gas generated is always present.

The heat generated in the basic reaction ensures that excess incyanato groups actually react with epoxy groups and not with excess water. Furthermore, in the reaction, a suitable catalyst assumes an important control function. Suitable catalysts are amine base catalysts, especially tertiary amines or quaternary ammonium salts, in the form of organometallic compounds or in the form of inorganic salts. In this connection, 2.4.6 Tris(
Amine catalysts such as dimethylaminomethyl)phenol or benzyldimethylamine catalysts are preferred for isocyanate/epoxide reactions, which act as trimerization catalysts in the absence of epoxy groups. (See German Patent Publication 3.421. (186). Inorganic salts, in particular FeCQs, kQCQ- or ZnCQt, in particular activate epoxy groups to react with NCO groups and inhibit the reaction between isocyanate and OH groups. inhibit.

Therefore, such compounds, specifically identified as total chlorine or hydrolyzable chlorine, are included in effective amounts in industrial incyanates as inhibitors. The fact that such catalytically active salts within the scope of the process according to the invention are included in the technical polyisocyanate in many cases makes it possible to dispense with the separate addition of further catalysts. Adds additional benefits.

Organometallic compounds, such as triisobrobylaluminum A(2(tCs1lyL), are advantageous catalysts for the process according to the invention and, as a result of their specific selectivity, reaction mixtures with desirable properties for particular applications can be obtained. I can do it,
In addition to the stoichiometry that can be calculated according to the invention, the catalyst itself contributes to the reliable control of the highly complex epoxy resin/water glass/polyisocyanate reaction system.

In this connection, the aim of the development of the formulation for carrying out the process according to the invention is to create the following preconditions by varying the amount and type of catalyst or catalyst system and also the amount and type of reactants: .

(2) The incyanate/water reaction must proceed to the limit that the carbon dioxide gas generated in the process can be absorbed by the entire formulation.

2. The heat of the exothermic reaction generated in this starting reaction and the catalyst activating the oxazolidinone formation must match each other in such a way that the polymer structure together with the organic base is formed in the alkaline aqueous system.

In order to fulfill the precondition No. 1, care should be taken that the proportions of the reactants defined in more detail in claim 2 are maintained. Mainly, the organic mineral product produces a solid, non-foamed product, and the reactants polyisocyanate, aqueous alkali metal silicate solution, and epoxy resin are included in the reaction, and the following relationship is satisfied: used in such proportions of substances.

X (Me2O) 10Y (Otsu x ) + (2X +
Y )(NCO)-> product where X (Me2O) is the amount of substance in moles of sodium and/or potassium oxide in the alkali metal silicate used.

Y (,2) is the amount of epoxy groups in moles in the epoxy resin used.

(2X + Y)(NCO) is the amount of one MCO group in moles in the polyisocyanate used, where Me represents Na or K, and X and Y are the relative molar amounts of each. It is a positive number that, for polyisocyanates used as industrial commercial products, has a margin of error that allows for normal amount variations in the individual reactants. The epoxy resin is then 0.01% based on the weight of the alkali metal silicate solution used.
60% by weight is used.

The correct ratio of incyanato groups to epoxy groups in the reaction mixture and the corresponding effectiveness of the catalyst to activate Reaction Scheme 4 are to ensure the maintenance of the preconditions No. 2 above.

Preferably, the reaction mixture is prepared from the starting materials so that the following conditions are met:

NCO group (from polyisocyanate) 0 per 100y
, 23g - 1,19mol 1Aeto (from alkali metal silicate solution) 100g
02O81-0.323 mole epoxy units per epoxy unit (0.020-0.80 per 100g from epoxy resin
moles of oxirane rings) such amounts of alkali metal silicate solution and epoxy resin are 1
According to one embodiment, it is used in the form of a preliminary mixture described as "component A", consisting of two components: 70 to 95% by weight of alkali metal silicate solution and 5 to 30% by weight of epoxy resin. Only those present in the premix are used. These amounts corresponding to the content of Me2O are 0.09 to 0.28 mol/100 g, and the epoxy groups correspond to 15 to 210 mmol/100 g, respectively.

From these data, a preferred range of the X/Y ratio is derived from 0.4 to 18.6.

Since the process is normally carried out with starting materials of technical quality, natural tolerances also result in the amounts of the reactants being within specific amounts of material ratios due to normal product variations. In practice, on the basis of currently known quality variations, approximately the following tolerances are reasonable in this relationship:

(NCO) ± 5% (Me2O) ± 2.5% (Otsu) ± 7.5% Given the various possible water glass and epoxy resin qualities that can be used in the method according to the invention, the method according to the invention It is clear that the epoxy resin in the reaction mixture for is present in a proportion of 0.01 to 60% by weight, based on the weight of the water glass solution used.

The customary aqueous polyisocyanate and alkali metal silicate solutions conventionally used in the processes described above can also be used in the process according to the invention.

In this connection, the polyisocyanates are pure or technical polyisocyanates. In particular, solvent-free 4,4'-diphenylmethane diisocyanate is mixed with what is described as crude MDI on the market by various methods of preparing higher functionality incyanates. However, so-called prepolymers can still be used although they contain reactive NCO groups. Such products are obtained by the reaction of polyisocyanates with organic compounds containing at least one or more hydrogen atoms, and such prepolymers are well known among polyurethane chemists. According to the invention, the use of a prepolymer is claimed, which is produced from one resin containing epoxy rings and a monoisocyanate. In this case the NCO group is stoichiometric or in excess of O
It reacts with H groups and is inevitably produced in the production of resins containing epoxy groups. Prepolymers are produced without OH groups. This prepolymer is stable in storage for several months. Additionally, technical isocyanates, which normally contain catalysts to activate oxazolidinone formation, can be added as shown in the examples. Adequate storage stability has also been obtained for this component.

The aqueous alkali metal silicate solution used is a sodium and/or potassium water glass or a mixture thereof, the content of dissolved solid substances being from 10 to 60% by weight, preferably from 35 to 55% by weight. . The content of alkali metal oxides is from 5 to 20% by weight, especially 8
to 18% by weight is preferred.

In connection with the use according to the invention, the water glasses in this range exhibit excellent process-technical properties of fluidity, special thermal range and general physiological and environmental safety, such as reaction-kinetics. The properties are fully usable.

Additionally, aqueous alkali metal silicate solutions yield final products with high or low water content depending on the formulation, with products with low water content having values of <1 mD (a+1llidarcy) as shown in Example 9. It is surprising that it is considered impermeable to gases.

The epoxy resin used is a well-known epoxy resin, and the content of epoxy groups as functional groups is 200
It lies in a wide range from 300 to 700 mmol/kg, preferably from 300 to 700 mmol/kg. Such resins are in particular epoxy resins based on modified bisphenol A or trimerized fatty acids or standard bisphenol/
- is an epoxy resin based on epoxy resins. However, such resins contain at least two epoxy groups and monoepoxides can also be added. Phenol/as a highly functional epoxy resin
Epoxy resins with a novolak base can be used.

〇 + + + + + + 2 + + I = To + Rehaha Lord A Shitsuji Kudaden\ can be done. According to a first mixing method, component A is prepared from a material containing epoxy groups together with an alkali metal silicate solution. This is then reacted with the calculation amount of the B component. If technical incyanate is used as the Bli fraction, a catalyst is already added to activate the oxazolidinone reaction. Furthermore, other catalysts according to the invention are also added to the B component.

According to a second mixing method, component A is separated from the catalyst, which is considered to be an alkali metal silicate solution according to the invention. Component B consists in this case of a material containing epoxy groups and a polyisocyanate.

In the case of the above-mentioned polyepoxide, it is preferable to use it after inactivating it with a monoisocyanate.

In addition to the specific deactivation of components A and B, additives can be added to achieve special properties. In this connection, examples include dispersed silicic acid, diatomaceous earth, natural and synthetic fibers of various lengths, conductive soot, dyes, hollow spheres, ash in fuel exhaust gases.

When the method according to the invention is carried out as a method for strengthening strata, the reaction mixture with the desired viscosity is itself prepared in a known manner, mixing the reactants in the specific sense mentioned above and injecting the reaction mixture under pressure directly into the formation to be strengthened, according to the techniques described in the known art cited in the introduction. You can rely on it. Since the products according to the invention are non-foaming, self-injection methods (punching, pouring and simple sealing) are ignored.

Materials produced according to this teaching can be used in a wide variety of applications, for example by varying the ratio of inorganic to organic polymer, since important polymer properties such as modulus of elasticity and compressive strength can be adjusted over a wide range.

Thus, formulations that retain a high proportion of silicate are stone-like materials, while formulations that retain a high proportion of organic polymers, on the other hand, have properties typical of polymeric materials.

Due to the reactive behavior of the components, they can be injected in open and/or closed molds, cast or manufactured into panels, ronds, frames, models, machine elements, etc.

Blowout of dry and/or moist subsoil using a two-component squirt gun is possible with the potential for chemical anchorage to the substrate. In this way, for example, unprotected steel can be treated for corrosion protection.

Damaged and stressed concrete structures can be improved by injection with new materials that are not only static, but also require corrosion protection, and acidic effluents can be neutralized by inserted buffer salts. .

The organo-mineral product produced by the method according to the invention has the advantage that it does not have a foam structure which makes gas-tight sealing difficult or impedes sealing, and the organo-mineral product is enlarged by epoxy groups. It contains long chain segments and is very stable when exposed to high energy radiation. The bond strength to stone is excellent and remains intact and does not release gases or vapors.

These properties advantageously distinguish organo-mineral products used in coal mining by European patent 0.0+6.262 and from those described by German patent 3.421.085. These publications generally describe products that exhibit foamed structures, emit water vapor, or whose blowing agents (chlorofluorocarbons) prevent a completely gas-tight seal during their manufacture. ing. The presence of polyurethane segments in these materials is sensitive to exposure to high energy radiation and is degraded by such radiation (perhaps in a similar manner to polyamides). Such materials are therefore generally unsuitable, at least for the purpose of sealing and/or reinforcing long-term storage locations.

Owing to the hard nature and the organic component being insensitive to the previously known high-energy radiation, on the other hand, the organo-mineral products produced from the ternary reaction system of the process according to the invention have already been described. very suitable for the purpose.

For the claimed application, the organo-mineral product in the form of the starting reaction mixture is injected through a hollow hole into the structure to be reinforced, e.g. in coal mining. As known from known applications, or they can alternatively or additionally be applied in a layer to the surface area to be sealed of the structure and then reacted with respect to the structure of the organo-mineral product. The completion of the process is desired in each case or represents favorable environmental conditions if it is to be applied.

The invention will be explained in more detail below with reference to examples relating to selected reaction mixtures and comparative mixtures to provide what is needed to realize the process according to the invention.

In this connection, reference is made to a photomicrograph (magnification 1:1000) of a product produced by the method of the invention.

The components used in the following examples, alkali metal silicate solution, epoxy resin, polyisocyanate, catalyst, stabilizer, and filler, are summarized and shown below.

Starting materials: Water glass-1 Water glass-2 Water glass-3 Water glass-4 Water glass-5 Water glass-〇122O 13,8 8,8 18,0 5,8 13,5 45,0 47,0 38 ,0 54,5 28,1 40,5 Epoxide 1 Epoxide 2 Epoxide 3 Epoxide 4 Modified bisphenol A zN-fatty acid basis bisph↓Nol A standard product phenol novolak 4, 650-5.130 2.130-2.560 5.150 5.550 5,260 R-NCO-i Diphenylmethane 4.4' to diisocyanato #NC
O content 1i31±IM amount% Hydrolyzable chlorine 0.1-0.45% R-NCO-2 Phenyl isocyanate industrial purity catalyst-1 Catalyst-2 Catalyst-3 Catalyst-4 Dimethylbenzylamine 2, 4.6 -Dorisdimethylaminomethylphenoldioctyltinmercaptideisopropylaluminum, pure f>98% Stabilizer-1 Stabilizer-2 Free@Silicone/glycol copolymer without OII group OH value 3G±5 (+11g 1 <oz' g ) Dispersed Silicic Acid Examples 1-1O In Examples 1 to 1O, the starting materials shown in Table 1 below are used and at the same time are used to prepare the reaction mixture. The reaction mixtures in which each component is indicated are mixed together in the form of component A or component B.

The amounts of starting materials are given in parts by weight.

Example 1 Component A and component B are mixed together in the specified mixing ratio until a white emulsion results.

The onset of the reaction is indicated by the generation of heat and an increase in viscosity.

The progress of the reaction can be tracked using a Shore hardness tester.

Min Shore Hardness 0 D 0 D 0 D 5 D The reaction yields a bright yellow, non-foamed, non-shrinking material.

Example 1a (Comparative) When the proportion of component B is reduced by 50% from Example 1, a hydrous dry gel is obtained, which undergoes severe shrinkage and has low strength.

Example 2 Component Δ and component B are mixed with each other in the specified mixing ratio until a white emulsion is obtained.

The onset of the reaction is indicated by the evolution of heat and an increase in viscosity.

The progress of the reaction can be tracked using a Shore hardness tester.

Shore Hardness Yield Point 4 A Q A 0 D The reaction produces a bright yellow, unfoamed but unshrinkable material.

Example 3 Component A and component B are mixed in the specified mixing ratio until a white emulsion results.

The onset of the reaction is indicated by the evolution of heat and an increase in viscosity.

The progress of the reaction can be followed using a Shore hardness tester.

Shore Hardness Yield Point 5 A 0 D 5 D 0 D The reaction produces a bright yellow, non-foamed but non-shrinkable material.

Example 4 Component A and component B are mixed in the specified mixing ratio until a white emulsion results.

The onset of the reaction is indicated by the evolution of heat and an increase in viscosity.

The progress of the reaction can be tracked using a Shore hardness meter.

Min Shore Hardness 4 15 A 65 A 530 seconds 20 D 20D The reaction produces a bright yellow, non-foamed, non-shrinkable material.

Example 4a (comparison) The proportion of polyisocyanate is about 30% by weight from Example 4.
When reduced, a dry gel forms which shrinks severely and hardens after water is removed.

Component A and component B are mixed in the specified mixing ratio with each other until a white emulsion results.

The onset of the reaction is indicated by the release of heat and an increase in viscosity.

The progress of the reaction can be followed using a Shore hardness tester.

minutes shore hardness 330 seconds Yield point 10 30 D 15 40 D 30 45 D 1 day 50D The reaction is bright yellow, non-foaming, non-shrinkable material occurs.

Example 5a (Comparative) When the proportion of polyisocyanate is reduced by about 15% by weight compared to Example 5, the resulting material is relatively soft, albeit with less shrinkage, and the Shore hardness is less than IOA when measured after 20 minutes. Shore hardness was 35D after one day.

Component A and component B are mixed together in the specified mixing ratio until a white emulsion is produced.

The onset of the reaction is indicated by the generation of heat and an increase in viscosity.

The progress of the reaction can be tracked using a Shore hardness tester.

A very hard, bright yellow resin is produced, containing at the same time a high inorganic proportion and a low proportion of water.

The figure shows a micrograph of the fracture surface of the material obtained in this example at 1000x magnification.

Example 7 A hole with a diameter of 50 mm and a depth of 900 mm was cut into a concrete block. A hollow steel anchor was pushed into the cutout and centered by sealing and fixing the cutout. The hollow hole was compression molded with the injection material according to Example 7 through the hollow anchor using a high pressure injection machine.

After 30 minutes, the anchor extraction force was tested using a hydraulic tension device. Anchors with a diameter of 30 mm could not be pulled out. As the water pressure increased, the anchor head eventually broke off.

EXAMPLE Component A and B were mixed together in the specified reaction ratio until a white emulsion formed.

The onset of the reaction is indicated by the evolution of heat and an increase in viscosity.

The progress of the reaction can be tracked using a Shore hardness tester.

Shore Hardness Yield Point: 5 D Produces a very hard, bright yellow resin with no shrinkage or foaming.

Example 9 Component A and component B were mixed together in the specified mixing ratio until a white emulsion formed.

The onset of the reaction is indicated by the evolution of heat and an increase in viscosity.

The progress of the reaction can be tracked using a Shore hardness tester.

Yield Point 5 A 5 D 0 D 5 D A very hard, bright yellow resin was produced, with no shrinkage or foaming.

Example 1O Component A and component B were mixed together in the specified mixing ratio until a white emulsion formed.

The onset of the reaction is indicated by the evolution of heat and an increase in viscosity.

After the reaction, a material with a high proportion of silicic acid and high gas permeation results.

Comparative examples with process conditions that do not meet the requirements of the process according to the invention are then carried out, giving completely unstable and substandard organo-mineral products.

Table 2 Polyisocyanate 31 has an incyanate content of 31% by weight Comparative Example 1 In a stirred vessel, components A+B are added successively and mixed until an emulsion is formed. After approximately 1 minute of stirring, heat generation is observed and the materials begin to react. At the same time it produces a bright shiny yellow, unusable foam.

In a mixing vessel, components A+B are added sequentially and mixed until an emulsion is formed. After 1 minute of stirring, heat generation is observed and the materials begin to react. A non-foamed material is produced, which consists of water-containing granules.

From the initial pH of the reaction mixture of 14 to the post-reaction pH of 9-10
decreases to the value of

Comparative Example 3 In a stirred vessel, components A+B are added successively and mixed until an emulsion is formed. After approximately 1 minute of stirring time, heat generation is observed and the materials begin to react. Initially, a non-foamed product is produced, but in the second reaction phase a bright yellow foam is produced.

At the end of the reaction time, the brittle foam partially ruptures due to the rapid escape of carbon dioxide and water vapor from the interior.

[Brief explanation of drawings]

Claims (1)

[Claims] 1. A method for producing an organic mineral product by reacting an organic polyisocyanate in the presence of an aqueous alkali metal silicate solution, further reacting in the presence of an epoxy resin as a co-reactant, The epoxy resin is an organic mineral characterized in that it reacts with polyisocyanate or a compound formed in an intermediate step to form an organic polymer structure containing an oxazolidinoone ring structure under the reaction conditions. Method for producing sex products. 2. The organic mineral product is produced in the form of a solid non-foamed product, and the co-reactants polyisocyanate, aqueous alkali metal silicate solution and epoxy resin included in the reaction satisfy the following relationship. Used in the substance amount ratio, X (Me_2O) + Y (■) + (2X + Y) (NCO)
→Product where X(Me_2O) is the amount of sodium oxide and/or potassium oxide in the alkali metal silicate used, expressed in moles, and Y(■) is the amount of sodium oxide and/or potassium oxide in the epoxy resin used. It is the amount of substance expressed in moles of epoxy groups, (2X+Y)(NCO
) is the substance amount in moles of -NCO groups in the polyisocyanate used, where Me stands for Na or K, X and Y are the respective relevant molar amounts,
The number has a tolerance range that allows for normal quality variations in the individual co-reactants if these are used as industrial commercial products, and the epoxy resin is 2. Process for the preparation of organo-mineral products according to claim 1, characterized in that an amount is used ranging from 0.01 to 60% by weight, based on weight. 3. The polyisocyanate has an NCO group content of 0.238 to 1.1 per 100g of polyisocyanate.
The alkali metal silicate solution has a Me_2O content in the range of 0.081 to 0.323 mol per 100 g of alkali metal silicate solution, with Me containing Na and/or K. Process for the production of organo-mineral products according to claim 2, characterized in that: 4. Chemically pure or technical polyisocyanates or mixtures of such polyisocyanates or mixtures of such polyisocyanates with organic monoisocyanates are used as polyisocyanates, and free NCO groups are The content ranges from 10 to 50% by weight,
Process for the production of organo-mineral products according to any one of claims 1 to 3, characterized in that the content is preferably in the range from 25 to 35% by weight. 5. The alkali metal silicate aqueous solution has a dissolved solid substance content in the range of 10 to 60% by weight, and a Me_2O content in the range of 5.0 to 20% by weight. A method for producing an organo-mineral product according to any one of paragraphs 1 to 4. 6. Epoxy resin is 200 to 8000mMol/kg
6. A process for producing an organo-mineral product according to claim 1, characterized in that a content of epoxy functional groups of . 7. A method for producing an organo-mineral product according to any one of claims 1 to 6, characterized in that the reaction is carried out in the presence of a catalyst that promotes the formation of oxazolidinone. 8. An organo-mineral product 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. Production method. 9. The catalyst is benzyldimethylamine, 2,4,6-
The organic compound according to claim 8, characterized in that it is selected from tris(dimethylaminomethyl)phenol, tetraethylammonium bromide, dioctyltin mercaptide, aluminum triisopropylate, aluminum trichloride, zinc dichloride, iron trichloride. Method of manufacturing mineral products. 10. Process for the production of organo-mineral products according to any one of claims 1 to 9, characterized in that stabilizers and/or fillers are additionally added to the reaction mixture. 11. Component A of the first mixture is prepared from an aqueous alkali metal silicate solution and an epoxy resin, which is mixed with component B of the second mixture, the second mixture comprising polyisocyanate and optionally Claim 1, characterized in that it comprises a catalyst for producing the reaction mixture.
A method for producing an organo-mineral product according to any one of paragraphs 1 to 10. 12. To produce the reaction mixture, the first component (component A) of the aqueous alkali metal silicate solution, containing a catalyst if necessary, is mixed with the second component (component B), The two components consist of an epoxy resin with completely free OH groups obtained by reacting the epoxy resin with a polyisocyanate and a monoisocyanate in a preliminary reaction, the amount of said monoisocyanate being determined by the OH groups of the epoxy resin. 11. A process for the production of an organo-mineral product according to claim 1, characterized in that the stoichiometric amount of . 13. The method is characterized in that it is carried out as a method for strengthening geological formations by injecting the liquid reaction mixture into the cracks and depressions of the formation, allowing the formation of organo-mineral products to react in situ. A method for producing an organo-mineral product according to any one of claims 1 to 12. 14. carried out as a method for strengthening and/or sealing geological and/or man-made structures, in which a hole is made into the structure, a reaction mixture is injected, and the structure is sealed with the reaction mixture; 13. Process for producing an organo-mineral product according to claim 1, characterized in that the surface is coated in order to prevent the production of organic mineral products and is exposed to high radiant energy.