SK24995A3 - Process for using a synthetic resin system - Google Patents

Abstract

A process for using a polyurethane-based synthetic resin system in which the system consists of an isocyanate component a) and a polyol component b) and auxiliaries and additives c) can be added to the components a) and/or b) and the polyol component b) contains an insufficient proportion of primary or secondary di or polyamines. The system is used to insert and secure roof bolts in boreholes and to that end is preformulated as a two-part system with components a) and b), possibly including auxiliaries and additives c), the components a) and b), possibly including auxiliaries and additives c), the components a) and b) are mixed together shortly before introduction into the boreholes and the mixture spontaneously undergoes an increase in its viscosity to form a gel-like substance which secures the roof bolts in the boreholes and then slowly hardens.

Description

Technical field

The present invention relates to a method of using a synthetic resin system based on polyurethane, wherein the system consists of an isocyanate component and / or a polyol component b) as well as excipients and additives which can be added to the components and / or b / a a polyol component and / contains a deficient proportion of primary or secondary diamines or polyamines.

BACKGROUND OF THE INVENTION

Such synthetic resin systems are known, for example, from DE-OS 36 10 729. They are used for the production of coating or sealing agents which are cured by the action of air humidity.

It is already known for the mounting of climbing irons in the mountains that so-called glued climbing irons are used, in which the gluing is carried out by means of two-component synthetic resin systems. In this case, the resin components can be introduced into the bores either in separate cartridges, into which the soap irons are driven by destruction of the cartridges, and a curable mixture is produced by rotating which, after curing, holds the soaring iron firmly by gluing to the mountains.

However, the curable composition can also be forced into the bore by means of a pump before or after the introduction of the iron.

Most often with overhead bores, the problem is that part of the resin mixture flows back partially into the bore, so that the adhesion of the rising iron is imperfect.

2. Summary of the Invention

The present invention has as its primary object to avoid this drawback when fixing the glued iron.

This object is solved according to the invention by the features set forth in the characterizing part of claim 1. Surprisingly, experiments have shown that the two-component synthetic resin composition according to the invention, which has a gel-like consistency, can be well pumped and can also be easily introduced into the bores facing upwards. without leaking again when it reaches the maximum bore depths before hardening due to the force of gravity. It is also most surprising that the two-component mixture exhibits sufficient load-bearing capacity to hold the bonded lead iron in the bore until hard.

Further embodiments are provided in the subclaims.

The polyisocyanate component and / or used in the process according to the invention are preferably polyphenylene polymethyl polyisocyanates which are produced by condensation of aniline and formaldehyde and subsequent phosgenation (polylyeses MDI) or derivatives of these polyisocyanates, liquid at room temperature and having carbodiimide. biurethane, urethane and / or allophanate groups, as well as prepolymers thereof, i.e. excess products of the reaction of polyisocyanates with polyols. Suitable polyols for the preparation of prepolymers are compounds generally known from polyurethane chemistry, preferably long-chain polyols with hydroxyl numbers below 150 mg KOH / g of substance. Preferred are

- a mixture of polyisocyanates (polymeres MDI), obtained by phosgenation of condensates of aniline with formaldehyde, liquid at room temperature, as well as their liquid reaction products with an excess of polyhydric alcohols having a molecular weight range of 62 to 3,000, having NCO / NCO molar ratio OH = 1: 0.005 to 1: 0.3), in particular polyols having a molecular weight range of 106 to 3000. Mixtures of 2,4'-diisocyanatodiphenylmethane and 4,4'-diisocyanatodiphenylmethane, liquid at room temperature, are also suitable as polyisocyanate and / or components. Basically, other polyisocyanates are also suitable according to the invention, for example known from DE-OS 28 32 253, pages 10 and 11. Most preferably, mixtures of polyisocyanates of the diphenylmethane series with a viscosity at 25 [deg.] C. of 50 to 500 mPa.s with an NCO content of about 30 to 32% by weight.

The polyol component b) is a mixture of organic polyhydroxyl compounds with hydroxyl numbers between 30 and 2000, the hydroxyl number of the mixture being between

200-500 mg KOH / g substance.

The polyhydroxyl compounds are preferably polyether polyols known per se from polyurethane chemistry or mixtures of various such polyether polyols. Polyether polyols which can be used well are, for example, the propoxylation products of divalent to eight-valent aging molecules such as water, 1,2-dihydroxypropane, trimethylopropane, pentaerythtir, glycerin, sorbitol, ethylenediamine and optionally cane sugar. Generally, component (i) has a mean hydroxyl functionality of 2.0 to 5.0, preferably 2.0 to 3.0.

Such suitable mixtures can be obtained, for example, by subjecting the corresponding mixtures of starter molecules of, for example, said type to a propoxylation reaction. However, it is also possible for the separately produced polyhydroxy polyether to be mixed with the component (i) used according to the invention after its manufacture.

As amines according to the invention, primary and secondary amines and polyamines and mixtures thereof are used.

Suitable aromatic amines are, for example, 4,4-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 1,3,5-triisopropyl-2,4 -diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,4-diaminobenzene and technical grade mixtures with the three last-mentioned compounds, 3,5-di (methylthio) -2,4-toulenediamine, 3,5-di (methylthio) -2,6-toulenediamine and technical mixtures thereof, 1,2ethylene-di- / 4- amino / thiophenyl ether, 1,3-propanediol di (p-amino) benzoate, 3,5-diamino-4-chlorobenzoic acid isobutyl ester, 1,3-propylene di [4-amino] benzoate.

Suitable cycloaliphatic amines are:

isophorone diamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl -4,4'-diaminodicyclohexylmethane,

N-cyclohexyl-1,3-diaminopropane, N- (5-aminoethylpiperazine).

Suitable aliphatic amines are, for example, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, diisopropyltriamine.

-5 As auxiliary agents and additives c /, common in polyurethane chemistry, the following can be used:

catalysts for accelerating various isocyanate addition reactions, such as, in particular, organic compounds of bismuth and tin, for example dibutyltin dilaurate, organic alkali metal salts, for example potassium acetate or tertiary amines, triethylene diamine, dimethylethanolamine or N-ethylenmorpholine. These catalysts are generally used in an amount of up to 2% by weight, preferably in an amount of 0.1 to 1% by weight, based on the total mixture. Water scavengers for the production of unfoamed or low foaming products, for example zeolite pastes, used in an amount of between 1 and 5% by weight.

Foam regulators, i.e. foam stabilizers or foam destabilizers, preferably based on polysiloxane. They are added in an amount of up to 2% by weight, preferably between 1ppm and 1000 ppm, based on the entire mixture.

Optionally, water may be added as an expanding agent, which may be added in an amount of up to 5% by weight, preferably 0.5% to 2% by weight.

Alternatively, physical expanding agents, for example partially halogenated hydrocarbons or other volatile compounds, for example dichlorofluoromethane or pentane, can be added, which can be added in amounts up to 20%.

Or also organic or inorganic flame retardants, for example phosphoric acid esters or aluminum hydroxide derivatives in amounts of up to 20% by weight, in the case of liquid compositions and 50% by weight. in the case of solid funds.

Or also fillers, for example urea, silica meal or talc in amounts up to 50% by weight.

In the reaction mixtures used in the process according to the invention, the individual components are generally present in amounts corresponding to isocyanate characteristic numbers of from 90 to 150, preferably 120 to 140. The isocyanate number is understood to mean the proportion of the number of isocyanate groups present in the reaction mixture. multiplied by 100, with water entering the calculation as a difunctional compound.

Before carrying out the process according to the invention, in general the auxiliaries and additives c) which are optionally used are combined with the polyol component b), followed by treatment according to the two-component principle. That is, the polyisocyanate components and / with the polyol component b) and / or the mixture of polyols b) and the auxiliaries and additives c) are mixed to produce the reaction mixture. Mixing units known in the art can be used for this purpose.

Examples

It is known from the anchoring technique that the higher viscous two-component plastics of the synthetic resins are processed by means of

-Ί metering pumps with integrated pressure pattern.

These pumps are not self-sucking, which is due to the viscosity of the two-component plastic resin and a higher injection pressure is necessary for the introduction process. Due to the use of two-component plastics resins can be used.

dosing pumps already in place Low-viscosity individual components of the resin are sucked in by dosing mixing, eg static

The PUR for the reinforcement of rock, a two-component mass of a plastic pump and reacted by the method to a higher viscous product, which can then be transported only by pressure. These mixed two-component plastics resins will then adhere, after curing, to the commercially available injection-anchored climbing mountaineering iron in the borehole, or they may adhere to the climbing iron in the borehole as a mortar.

Examples of the invention j

The following examples according to Tables 1 to 4 serve to further illustrate the process. All percentages refer to weight percent.

Examples

In the examples of Tables 3 and 4, the starting components used in Tables 1 and 2 are used for components b / and c /.

table 1 component b default components OH value viscosity system / mg KOH / g at 25 ° C / mPa.s/ primary glycerin and 380 450 polyol I propylene oxide glaciation sucrose, 1,2- 380 580 polyol II propanediol, propylene oxide bases polyol III trimethylopropane propylene oxide 380 600 polyol I 1,2-propanediol 56 324 causing propylene oxide flexibility polyol II ditto 260 73 causing flexibility polyol III butanediol causing tetrahydrofuran 176 277 flexibility polyol IV triethanolamine 27 870 causing propylene oxide flexibility ethylene glycol 1808 16 diethylene glycol - 1,057 26 glycerin - 1827 750 castor oil - 160 680

diamine I diamine II diamine III diamine IV (N- (ε-aminoethyl) piperazine) (N-cyclohexyl-1,2-diaminopropane) (3,3'-dimethyl-4,4'-diaminocyclohexylmethane) technical mixture of 1,3 , 5-triethyl-2,4-diaminobenzene

c / system components default components Catalyst I dimethylethanolamine catalyst II triethylenediamine, 33% ethylene glycol Catalyst III dibutyltin Catalyst IV potassium acetate Catalyst V 2,4,6-tris (dimethylaminomethyl) phenol zeolite paste type of zeolite ... 50% in castor oil From tables 1 to 4 shows that for two-component

The polyurethane system according to the invention has a wide variety of starting components, in particular for component b / system (Table 1), also for component c / system (Table 2).

Of course, in addition to the above-mentioned starting materials, other components are also suitable, since the components mentioned in 1 and 2 are only those components which, in the variable compositions or formulations in the tables, are listed in Tables and 4, and / which are shown in Tables 3 and 4 to suitable two-component polyurethane compositions which gel in gel-like consistency in fractions of a second and are capable, in this quasi-thixotropic state, to hold the rising iron in the bore upwards reliably until it reaches a time of solidification, measured in minutes, of a glue fastening effect which renders the pitch iron suitable for receiving the load.

-10 Table 3 polyol components b / a.c / 1 2 3 4 system

b / base polyol about. about 50 I 50 I 40.8 II 73 III II polyol causing flexibility o, 0 39 I 38 IV 50 II 10.9 castor oil II sieúovadlo % 2 DEG 2 MEG 1 DEG 5 glycerin H diamine % 6 I 6 II 6 III 10 IV c / catalyst Q, 'o 1 I 1 II 0.2 III 0.1 IV 1! zeolite 0, O 2 z .p. . 2 z.p. 2 z.p. 2 z.p.

paste

OH number / incl

ekv.aminov / mg KOH / g 305 317 328 401 viscosity cP. with 378 510 197 517 density g / cm ³ 1,032 1,032 1,028 1,044 isocyanate component and / system Type MDI MDI prepolymer MDI NCO content o, o 30.5 30.5 18 30.5 viscosity cP. with 220 220 250 220 density g / cm ³ 1.23 1.23 1.16 1.23 reaction 100g of polyol with isocyanate - g 87.7 92.5 164 128.5 gel time min 0.02 0.02 0.06 0.08 setting time min 1.25 0.30 1.50 12,30 characterizing 117 119 120 130

number

NCO

-11polyol 5 6 components b / a c / system

b) a base polyol % 76 III 40 I tt polyol causing flexibility about 0 10 III 43 IV n sietzovadlo % 5 MEG 5 DEG tl diamine % 6 I 8 II c / catalyst % 1 IN 2 II 11 zeolite paste 0, 0 2 z.p. 2 Z .p. OH number mg KOH / g 453 310

/ including amine equivalents /

viscosity cP. with 499 495 density g / cm ³ 1,030 1.031 isocyanate component and / system Type MDI prepolymer NCO content % 30.5 18 viscosity cP. with 220 250 density g / cm ³ 1.23 1.16 reaction 100g of polyol with isocyanate g 133 146 gel time min 0.10 0, 05 solidification time min 2.15 1.00 characteristic NCO number 120 113

-12Table 4

polyol with components b / a system 7 l c / 8 9 10 11 b / base polyol % 57 II 40 III 30 II 70 I 80 III II polyol % 36 III 47 III 57.9 III 15 IV 12.1 RI spôsopujúci tin flexibility oil II crosslinking after % 2 MEG 2 Gly 2 DEG 2 DEG 5.6 Gly Glycerine Glycerine II diamine % 8 I 8 III 8 III 10 IV - - c / catalyst % 1 IN 1 IN 0.2 III 1 I 0.1 IV II zeolite % 2 z.p. . 2 z.p. . 2 z.p. . 2 z .p. 2.2 z.p.

paste

OH number mgKOH / g / incl. 379 434 1,041 312 477 1,011 278 372 1,013 328 341 1.054 444 510 1,045 viscosity density cP. with g / cm ³ isocyanate component and / system Type MDI inter- inter- inter- MDI Lymer Lymer Lymer NCO content o o 30.5 13 13 13 30.5 viscosity cP. with 220 4060 4080 4060 220 density g / cm ³ 1.23 1,011 1,013 1,054 1.23 polyol 7 8 9 10 11 components b / a c / system reaction

100g polyol g 111 213 192 215 128.5 with isocyanate doba zgélo- min 0.08 0.10 0.10 0.20 Dear setting time min 13,00 11,30 7.30 8.00 13,00 characteristic NCO number 119 119 120 114 110

Tables 3 and 4 list 10 examples which contain corresponding formulation instructions to guarantee the above reaction results.

Example 12 shows the opposite case in which the component b / system was assembled without diamines, with a composition similar to that of Examples 1 to 10. The use of such a mixture did not achieve a special gelation effect in which a gel-like or quasi-thixotropic a condition capable of holding the iron in the bore inclined upwards.

FIG. 1, it can be found that a steep increase in viscosity in fractions of minutes is only achieved with the compositions in which the diamine crosslinker is used, as shown in the compositions of Example 4a, whereas, on the other hand, without the diamine crosslinker as demonstrated in Example 11, only occurs. a slow increase in viscosity so that this mixture is unable to hold the rising iron in the bore inclined upwards.

Injection resins based on two-stage polyurethane resins, which do not form a gel-like consistency after mixing the components, leak due to gravity when used in heavily ground rock. In the polyurethane resin system according to the invention based on a two-component polyurethane, this varies after mixing low viscous individual components in a volume ratio of 1; 1 after 12 seconds to a cuddly product which cures after 4 to 5 minutes.

The system should be treated by the known injection technique of two-component polyurethane mixtures so that no special metering pumps are required.

Example 12 (experimental grouting) The grouting anchoring device was plugged into a borehole in wet artificial rock (anhydride). The gel-like resin mixture stood out at the deepest bore to be filled at its greatest depth from the injection anchoring device and had to be evenly pushed back from the deepest bore to the borehole because of its gel / quasi thixotr / quasi / consistency did not flow automatically under the force of gravity down. In FIG. 2 is a load diagram obtained in an injection attempt. It shows the capture of the strength of the grouting device. At a bonding length of 50 cm, the rising iron was loaded after 1 hour curing. The climbing iron could not be pulled out of the bore, but was pulled out by a force of 250 kN.

Application example 13

Strength tests were carried out in the laboratory on slightly foamed specimen bodies. The following values were found:

compressive strength 20.4 N / mm ' bending strength limit 5.2 N / mm ' Module E 1.1 N / mm ^: density 695 kg / m

Since the two-component polyurethane system does not stretch so strongly with respect to the higher creep pressure in the annular gap, it may start from strengths that are still above the above values.

Example of use 14 with anchor rope

Flexible anchoring ropes or multi-strand ropes are often used for difficult anchoring. Adhesion between these ascending irons and the rock is achieved by injecting an anchoring mortar on the basis of the prior art by hand.

In a comparative example, a 4 m long anchor rope having a squeezable bond that can hold the anchor plate to anchor the seam lining at the edge of the wall was used, a cement-based anchor mortar that was mixed in a simple mixer and pump water. The consistency of the mortar was so thick that it did not flow out of the steeply rising holes. The anchoring ropes can be plugged, by hand, into a borehole filled with mortar.

The disadvantage of this anchoring mortar lies in the comparatively costly preparation of a suitable mortar consistency, followed by the necessary careful cleaning of the routing routes of mortar residues by rinsing with water, but also in comparison with the fast-setting synthetic resin adhesive mixture with the relatively late action of the cement mortar.

-16Example of use 15 with anchor rope

The anchoring experiment was carried out with a two-component polyurethane system in a 4 m long single-sided closed and transparent Plexiglas tube. The tube was erected vertically and mounted on a block of rock. In the experiment, a long anchor cable was inserted up to the deepest point of the tube. On the anchor line with a radius of 6 mm.

A plastic hose with an inner hose was attached. During the injection, a pressure drop of 35 bar occurred in the injection hose. After 30 seconds, the annular space between the anchor line and the tube wall was completely filled with the polyurethane mixture. The resin composition had a pasty consistency that only a very small portion of the gelled (quasi-thixotropic) resin mixture leaked out, as shown in FIG. 3, from the opening of the tube. This experiment confirmed the excellent holding properties of the newly developed two-component polyurethane system during the initial gel (quasi-thixotropic) consistency state. In contrast to cementitious mortar, however, the curing process terminated disproportionately faster, so that the load-bearing effect of the anchor rope adhered to by the synthetic resin was much earlier.

Claims (22)

PATENT CLAIMS A method of using a polyurethane-based synthetic resin system, wherein the system consists of an isocyanate component and / or a polyol component b) as well as excipients and additives c) which can be added to the components a / and / or b / a The polyol (b) contains a deficient proportion of primary or secondary diamines or polyamines, characterized in that the system serves to introduce and adhere the glued pitch glands to the bores and to this end is formulated as a two-component system with components a / ab /, optionally including excipients and The ingredients c), the components a / ab) are mixed shortly before being introduced into the bore and the mixture spontaneously increases its viscosity to a gel-like consistency which keeps the glued pitch iron in the bores and then cures without delay. Method according to claim 1, characterized in that polyphenylene polymethylene polyisocyanates which are produced by condensation of aniline with formaldehyde and subsequent phosgenation (polymeres MDI) are used as the polyisocyanate component a. Method according to claim 1, characterized in that polyisocyanate derivatives, liquid at room temperature, having carbodiimide, biurethane, urethane and / or alpohanate groups, as well as their prepolymers, i.e. reaction products of polyisocyanates with polyisocyanates with / polyolymes in excess. The process according to claim 2, characterized in that the compounds generally known from polyurethane chemistry are suitable as polyols for the preparation of prepolymers. Method according to claim 4, characterized in that long-chain polyols with OH numbers below 150 mg KOH / g of substance are used. Method according to claim 5, characterized in that mixtures of polyisocyanates (polymeres MDT) obtained by phosgenation of aniline-formaldehyde condensate liquid at room temperature are used. Process according to claim 6, characterized in that liquid NCO groups having reaction products of mixtures of polyisocyanates with excess amounts (NCO / OH molar ratio = 1: 0.005 to 1: 0.3) of polyhydric alcohols from the molecular weight range 62 are used. up to 3,000. Process according to claim 7, characterized in that polyols from the molecular weights of 106 to 3 000 having ether groups are used. Process according to claim 6, characterized in that mixtures of 2,4'-diisocyanatodiphenylmethane and 4,4'-diisocyanatodiphenylmethane, liquid at room temperature, are used. Process according to claim 1, characterized in that mixtures of polyisocyanates of the diphenylmethane series with a viscosity at 25 ° C of 50 to 500 mPa · s having an NCO content of about 30 to 32% by weight are used. Process according to claim 1, characterized in that mixtures of organic polyhydroxyl compounds with OH numbers between 30 and 2000 are used as the component of the polyols b /, wherein the OH number of the mixture is between 200 and 500 mg KOH / g of substance. Process according to claim 11, characterized in that mixtures of different polyether polyols are used as polyhydroxyl compounds. Method according to claim 12, characterized in that the polyoxypolyols used are the propoxylation products of divalent to eight-valent starter molecules such as water, 1,2-dihydroxypropane, trimethylpropane, pentaerythrin, glycerine, sorbitol, ethylenediamine and optionally cane sugar. Method according to claim 12 or 13, characterized in that the polyhydroxyl compound has a mean hydroxyl functionality of 2.0 to 5.0, preferably 2.0 to 3. The process according to claim 14, characterized in that the starting molecule mixtures are subjected to a propoxylation reaction. Method according to claim 15, characterized in that the polyhydroxypolyethers produced separately are mixed together after their manufacture. Process according to claim 1, characterized in that primary or secondary diamines or polyamines and mixtures thereof are used as amines. Process according to claim 17, characterized in that 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'- are used as aromatic amines. diaminodiphenylmethane, 1,3,5-triisopropyl-2,4-diaminobenzene. 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl -2,4-diaminobenzene and technical mixtures with two the latter, 3,5-di (methylthio) -2,4-toluenediamine, 3,5-di (methylthio) -2,6-toluenediamine and their technical mixtures, 1,2-ethylene- (4-amino) -thiophenyl ether, 1,3-propanediol-di (p-amino) -benzoate, isobutyl-3,5-diamino-4-chlorobenzoic acid, 1,3-propylene di- (4-amino) benzoate. Process according to claim 17, characterized in that isophorone diamine, 4,4'-diaminodicyclohexylamine, 3,3'-dimethyl-4,4'-diamino-cyclohexylamine, N-cyclohexyl-1,3- diaminopropane, N- (S-aminoethyl) piperazine. Process according to Claim 17, characterized in that the aliphatic amines used are diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, di-isopropyltriamine. Process according to claim 1, characterized in that in the reaction mixtures to be used the individual components are present in an amount corresponding to a characteristic isocyanate number of 90 to 150, preferably 120 to 140. The method according to claim 1, characterized in that the auxiliaries and additives c), which are optionally used, are combined with the polyol component b), followed by treatment of the two-component system.