AU744113B2

AU744113B2 - A method for the manufacture of elastic, thixotropic organo-mineral systems, the products obtained therewith and their application

Info

Publication number: AU744113B2
Application number: AU82262/98A
Authority: AU
Inventors: Harald Bode
Original assignee: Fosroc International Ltd
Current assignee: Fosroc International Ltd
Priority date: 1997-07-02
Filing date: 1998-06-30
Publication date: 2002-02-14
Anticipated expiration: 2018-06-30
Also published as: DE19728252A1; ZA985770B; EP0993480A1; WO1999001492A1; PL337853A1; AU8226298A

Description

WO 99/01492 PCT/GB98/01907 method fi, the manufacture of elastic, thixotropic organo-mineral systems, the products obtained therewith and their application In the field of mining and particularly for application underground, anchoring and fastening systemls plhy a sq ccial part. The present invention therefore concerns a method for the manulacture ol .n organo-mineral system with which bore holes can be filled and anchors can be agglutinated. The substances according to the invention which may be used for this purpose possess advantageous properties.

Inflammnability i of importance, especially for underground applications for anchoring and agglutinating s\ stems. PU systems, polyurethane systems as well as the known polyester resin systems arc flammable and during hardening develop a strong smell and gases which may be damaging to health. Epoxy resin systems which are in use at the present time are not sufficient to meet these requirements. The synthetic resins named above do however find application because until now it has not been possible to prepare a rapid setting anchor fastening system for overhead application, which can be injected into an overhead bore hole by means of a two component processing plant, without the material flowing out again. Also, apart from high strength, elasticity is also desirable so that the resin can accomodate possible roof movement.

WO A-94/04588 and/or DE-A-42 28 178 disclose primary and secondary amines as polymerising agents for the manufacture of polyurethane synthetic resins. Furthermore it is known that'organo-mineral systems do not burn well and harden to form brittle-hard resins.

Such an organo-mineral system, namely a water-glass/isocyanate system is described in EP-A-0 167 002. It is known that only a few m-iaerials dissolve in water-glass and/or can be emulsified therein. These are primarily short chained dioles and trioles. If one now adds to the A component, dioles and/or trioles according to EP-A-0 167 002, then the elasticity of the product is not increased to any measurable extent On the..contrary an heterogeneous product is obtained because the reaction rate between water-glass and isocyanate and diole/triole is variable. A multi phase resin is obtained. If one uses on the isocyanate side a pre-polymer then an elastic resin will form at first but which will however become brittle after a few days.

It is an objective of the present invention to overcome the disadvatages to which the substances tend which are described in the state of the art and to prepare a material which is not flammnable, which hardens rapidly, possesses thixotropic properties and can be WO 99/01492 -2- PCT/GB98/01907 processed in a machine as a two component system. After hardening, the material should exhibit a residual elasticity, which should be ecologically and toxicologically unobjectionable and if possible should be capable of being manufactured in a cost effective manner.

This objective is achieved by the following invention as it is defined in the claims.

In order to obtain a durable, elastic material, a reactive monomer dissolved or dispersed in water-glass is desirable, which is reactive with respect to isocyanate. In order to obtain thixotropic properties it is necessary to increase the rate of reaction to such an extent that if possible a gel-like -condition is reached instantaneously, which prevents the reaction mixture from running out of a bore hole in overhead working. Surprisingly, it has now been found :,othat in contrast to the ususal polyoles, primary and secondary di and preferably trifunctional poly-oxy-alkylene amine can be dispersed in water-glass without swelling up (gelatinization).

If, as is defined in the claims, one reacts this water-glass mixed with poly-oxy-alkylene amine with isocyanate and/or prepolymers then one will obtain homogeneous substances which will gelatinize instantaneously so that within the space of about 2 minutes a pudding like product is obtained into which an anchor can be set. It is assumed that the rates of reaction of the poly-oxy-alkylene amine on the one hand and of the water-glass on the other hand with the poly-isocyanate component are almost the same. The hardening which follows thereupon leads to a high strength elastic inflammable product.

The raw materials which are necessary for the manufacture of the substances according to the i invention are described in detail in the following.

The compounds employed in the invention having terminal amino groups in which at least one free hydrogen atom on at least one amino group and at least one alkylene group interrupted by one oxygen, nitrogen and/or sulphur atom are present are for example poly-oxy-alkylene amine or polyalkylene polyamine. These materals in addition to the oxygen and/or sulphur atoms which interrupt the alkylene groups may also contain nitrogen atoms.

The poly-oxy-alkylene amines which are employed in the invention have at their disposal a poly-oxy-alkylene chain and one or more terminal amino groups which exhibit at least one free hydrogen atom in the amino group. Poly-oxy-alkylene amines are preferred selected 3 from compounds having the formula WO 99/01492 WO 9901492PCT/GB98/01907 -3-

H

2

NCHCH

2

[OCH

2 OH] e -NH 2 II (I)

OH

3

OH

3

(OCH

2 CH) x-NH 2

OH

3

A(OCH

2 CH) y-NH: (11) (OCH4 2 CH) Z-NH:

CH-

H

2

NCHCH

2

[OCHOH

2 a [00H 2

CH

2 b- [OOH 2 CH] c-NH 2

(I)

II I

OH

3 H 3 0

H

2

NCHCH

2

(OCH

2 OH] n-NH-O-NH- [CHCH 2 O] h-OH 2 OHN1{ 2 I I I OH H 3 I3 OH' 3 11 1?

H

2

N--HCC

2

[OCH

2 CH] n-NH-C-N1{ 2

(V)

I I

OH

3

OH

3 R- (CH 2 CHO) n-CH 2

CHNH

1 I I (VI)

OH

3 in which P, signifies CH 3 0CH 2

CH

2 O, R~Signifies hydrogen or an alkyl residue with 1. to 4 carbon atoms, A signifies the residue of a trivalent alcohol, preferably trimethylol propane or glycerine, xe signifies a number from 2 to 70, b signifies a number from 5 to 160, the sum 'of the numbers a c represents a value of from 2 to 4, n represents a value of from 4 to 80, x, y or z represent a value of from I to 100 or mixtures thereof.

Formula 11 compounds are preferred in particular.

WO 99/01492 WO 9901492PCT/GB98/01907 -4- The poly-oxy-alkylene amities quoted above are known commercially by the trade name Jeffaniineqt'.

Products -which can be used accordingc to formula I are Jeffamine® D-230, D-400, D-2000 or D-4000. Products accordine to formula 11 are Jeffamine® T-403, T-3000 and T-5000.

Products according: to f'orimula III are .leffamnine® ED-600, ED.900, ED-2001, ED-4000 or ED-6000. Pi-oducts according! to formula IV are Jeffamine® DU-700 or DU-3000.

Products according~ to formula V are for example Jetfaniine® BuD-2000 and similar.

P~roducts accordiune to formula VI are .Ieffamnine®V M-600, M-1000, M-2005 or M-2070.

Secondary pok\ -o.x\v-alk\vlene aities for example are compounds in the Nov'amine® SerieS, Molecular wveightus ol from 100 to 10 000 g/Mol are usable, the range from 400 to 6000 is prefe~rred, particularly preferred are 200 to 5000, e.g. about 400 to 1000 or 4000 to 5000 or 1000 to'3001 -/Mol.

F~or the above an the follovving comipounds with terminal amino groups -which are used according to the Invention it holds good that for a shorter length of chain and/or a lower miolecular wxeight thie catalytic properties are increased and the elasticity is reduced.

Poly-oxy-alkylenes where at least one amino group exhibiting a free hydrogen atom forms a part of an urea. guanidi, basic hetero cyclus such as Imidazol, Piperidin etc. may also be used. An example for this is the Jeffamine® BuD-2000 mentioned above.

Accordingly b\ the expression compounds having terminal amino groups all those compounds are to be understood in wvhich at least one group containing nitrogen is linked to the end of the molecule in which at least one reactive i.e. free hydrogen atom is linked to a nitrogen atom.

Examples for polyalkylene amines are compounds having the formula HN- (R-NH)elNH 2 in wvhich R signifies anx alkylene residue having 2 to 5 carbon atoms and n signifies a number of I to 50 or having the formiula A[(NH-R)dNH2j in which R and ni have the above meanings, A signifies a hydrocarbon residue and m signifies; a number of 3 to 20. Diethylene triamine, triethylene tetramine and tetraethylene pentamine are preferred. Diethylene triamine is particularly preferred.

,T

The alkali silicate solutions which are commonly used in this sector of the trade can be employed for the manufacture of the organo-mineral system according to the invention Aqueous solutions of sodium and potassium water-glasses may be used from 28 to 600 Be, having a Mol ratio of Na 2 O to SiO, or K20 to SiO 2 of 1 4 and a dry solids content of 35 to wt%. The densities of water-glass solutions are reported in B. Henceforth Na 2 O or K 2 0 are designated generally as MeO.

The employed water-glass solutions which are preferred according to the invention are colourless, clear as water and more or less viscous aqueous solutions of sodium and/or potassium silicates-with a ratio of SiO 2 to Me2012.

Apart from I-LSiO 4 molecules, the presence of Me-OH and H 3 SiO'ions is to be assumed in the water-glass solutions. The catalysis of the ILSiO, molecules into linear chains three dimensional networks is accompanied by the expulsion of water and is responsible for the viscosity of the water-glass solution.

The sodium and potassium silicate solutions which are shown in the table below and which are available commercially belong inter alia to the water-glass solutions employed according to the invention.

S

°B6 Weight.-% Na20 and/or K20 Weight-% SiO 2 High silica glass "Water-glass" 37 to 40 B6 (German) "Water-glass" 41 0 B6 (American) Alkai soda glass 58 60 B6 Glass having a ratio of 1.6 American Potassiuni glass 28 30 B6 Potassium glass 41 0 B6 35 7.0 26.1 38 7.7 25.8 10.8 11.2 11.3 12.2 18.0 19.7 28.7 36.0 31.4 21.2 26.9 Viscosity 20* cp -200 -200 -60000 -7000 -1000 11.3 11.6 12.8 Sodium water-glasses viscosity.

are preferred because they are more easily available and have a lower The emploment is preferred of sodium water-glasses with a relatively high solids content, which lies advantageously in the range of about 40 to 60 and in particular about 42 to 52 wt.% of inorganic solids. Potassium water-glasses however are also advantageous with a solids content of 25 to 40 More highly concentrated water-glass solutions are also feasible and can be employed within the meaning of the invention. In this case however P:\OPER\Mal2247184 speci.doc-20/1 I/I1 -6high viscosities must be taken into account. Furthermore, mixtures of sodium and potassium water-glasses may be employed.

The Mol ratio of SiO 2 to Me2O in the water-glass solutions which are employed is preferably relatively high and lies advantageously in the range of about 2 to about Particulalry preferred is a range of about 2.48 to 4.45, in particular 2.70 to 2.95 but also to 4.30.

The formation of three dimensional inorganic silica structures is promoted by a Me2O content within the ranges reported above. The composition and the quantity of water-glass to be used must be taken into account when determining the quantity of catalyst in order to achieve a product with optimum strength. Organo-mineral products with excellent flexural tensile strength are achieved according to the invention in particular if the polyisocyanate and the water-glass solution are employed in a Mol ratio NCO to SiO 2 of 0.8 to 1.4, preferably from 0.85 to 1.15. Especially preferred is a Mol ratio NCO to SiO 2 of about 1.0. The use of concentrated water-glass solutions is preferred in order to avoid products 15 of high water content which would affect their long term strength properties in a negative manner. The lower limit of the water-glass fraction is given by the fact that its amount *o must be sufficient to build up the inorganic structure. For this purpose there are most preferably at least 0.2 and preferably at least about 0.5 parts by weight of water-glass Snecessary per one part by weight of polyisocyanate. Just as in the case of a water content 20 which is too high a complete hardening is then no longer possible. The upper limit of water-glass content is for example about 1.6 to about 1.7 parts by weight of water-glass per one part by weight of polyisocyanate when sodium water-glass 48/15 having a Mol ratio of SiO 2 /Me20 of about 2.85 is used.

For the manufacture of organo-mineral systems according to the invention, polyisocyanates can be employed which are commonly used in the specialised sector of polyurethane manufacture. To this group belong such isocyanate compounds which have at least two isocyanate groups. Preferably, mixtures of isocyanates are employed which predominantly include quantities of polyisocyanate compounds having at least three Rr I P\OPER\MaI2247184 spcci.doc-21/11/A1 -6Aisocyanate groups. Examples thereof are the commercially obtainable products Desmodur 44V and Papi. Mixtures of polyisocyanate in which almost no diisocyanates and monoisocyanates are contained belong to those mixtures of polyisocyanate which are especially preferred. An organic polyisocyanate mixture which is obtained by the phosgenation of raw aniline formaldehyde resins which contains predominant amounts of the diphenyl methane diisocyanate isomers and higher functional polyisocyanates with more than 2 benzole rings in the molecule are separated in this method into the diphenyl methane diisocyanate isomer and the higher functional polyisocyanates.

To suitable organic diisocyanates there belong for example aliphatic diisocyanates, aromatic diisocyanates, alicyclic diisocyanates and heterocyclic diisocyanates, for example methylene diisocyanate, ethylene diisocyanate, propylene diisocynate, butylene diisocyanate cyclo-hexylene-1,4-diisocyanate, cyclo-hexylene-1,2-diisocyanate, tetra and hexa-methylene diisocyanate, arylene diisocyanates or their alkylisation products such as WO 99/01492 PCT/GB98/01907 the plienylenie di isocyanates. naphthylene diisocyanates. diphenyl-methane diisocyanates, toluy'lene diisocvanates, di or triisopropyl-benzole diisocyanates, aralkyl diisocyanates such as dixylykene diisocvanates, fluorine substituted isocyanates, ethylene glycol diphenyl etlier-2.2-diisocvanate, naphthialine- 1 .4-diisocyanate, naphthalene- 1. I'-diisocyanate, biphenyl 1-24- i scaae b~ienvl4 .4'diisocyanate. benzophenon-3 .3'-diisocyanate, iluor-eie-2.7-dii koev%.aniate. anthra,-chlinon-2 .6-diisocN'anate. pyrene-3 .8-diisocyanate, clir\vs.cu-2 .8-di s.cvsaniate. 3'-miet hoxvyhexanec-di isocvaniate. octane-diisocyanate, co .cdiisoevanate- I 4f-d iethvl betizole. isocx'anate- 1 .4 -dinietlivlnaphithaline, cyclohexane- I .3-diisocyanai c. I -isopr-opvl--benizolc-2 .4 -di isoc\,ania e. 1 -chllorobenizole-2 .4 -dii socvanate.

S-iluoriobeiw/.oki-2 .4 -di isoev*anate- I -tilt robenzole-2 .4-diisocyanlatc. I -chiloro-4-nethioxybecuzotlc-2 .5-di sis. vaalc. benz7oleaizo-inaphithal ine-4.4'-diisoc\'anateC. diphecnylether-2.4diisocyanate. .Iiphil-elicr-4.4-diisoc\aiiale and Isocvanuirate groups containing Ut. thcse. crudc MIl \\:ilti an NCO cotetnt of about 3 10o and m1odified crude MDI with a proportlin of :0 of'about 30%*O are preferred.

According to the invention. NCO pre-adducts such as are used in the manufacture of polyuirethanie canU also be employed. In the case of NCO pre-adducts it is a question of hieli nolecular compounds having at least twvo terminal NCO groups wvhich preferably exhibit a miolecuilar w~eiogh1 of 500 to 10,000, especially 800 to 2,500. These pre-adducts preferably exhibit an NCO group content of 1.5 to about 30%, whereby 17 to 25% is preferred. The manufacture of these NCO pre-adducts takes place in kcnown manner by the decomposition of compounds containing high molecular OH groups with an excess of polyisocyanate.

Amongst suitable compounds containing high molecular OH groups which are suitable for the mianufacture of NCO pre-adducts there are mentioned polyester, polyether, polyester amide. polythioether, and polyacetale. For example, linear hydroxyl polyesters which contain terminal hydroxyl groups and which have been obtained either by the pdly condensation o1f c--caprolacton or 6-hydroxycapronic acid or by the co-polymerisatioti of re-caprola~ton w~ith divalent alcohols or by the poly condensation of dicarbanic acid with divalent alcohols may be employed as polyoles for the manufacture of NCO pre-adducts.

The hydroxypolvyesters which are employed for the manufacture of the NCO pre-adducts may also be ma~nufactured from dicarbonic acids or mixtures of dicarbonic acids with divalent alcohols. As an example, adipin acid, bernstein acid, cork acid, sebacin acid, oxalic acid, niethyladipin acid, glutar acid, pimelin acid, azelain acid, phthalic, acid, terephithalic acid,isophthalic acid, maleic acid, fumar acid, citracon acid, itacon acid belong to the suitable dicarbonic acids. For example ethylene glycol, propylene glycol, butylene glycol. for example 1.4-butane diole; buten diole, butin diole, Bis-(hydroxy methyl cyclohexane), diethylene glycol, 2.2 dimethylpropylene glycol, 1.3-propylene glycol belong it) the suitable divalent alcohols or their mixtures which are decomposed with~ the dicarboinic acids or with re-caprolacton into the desired hydroxy polyesters.

-8- To the preferred polyoles which are employed for the manufacture of the NCO pre-adducts belong the polyesters based on adipin acid, 1.6-hexane diole and neopentyl glycol with an average molecular weight of 2,000 and polyether, in particular poly-ether diole with an average molecular weight of 2,000.

Furthermore high molecular compounds with terminal carboxyl, amino and mercapto groups are also suitable. Polysiloxane which exhibit groups capable of reaction with respect to isocyanates are also mentioned.

Polyether dioles are preferred whereby in particular polyether dioles with an OH number of about 56 are preferred.

Polymerisers can also be employed in the substances according to the invention. These are multi-functional reactive compounds against isocyanate. In particular they are a sugar such as sorbit or saccharose or a branched polyole such as trimethylole propane, glycerin or pentaerythrite.

A special example is 4.4'-diphenylnethane diisocyanate (also known in the form of the phosgenated product of aniline formaldehyde concentrates, crude MDI). A decomposition product of crude MDI with glycol started polysiloxane having an OH number of 40 to 200 is suitable as a pre-polymeride Polyisocyanates which are employed according to the invention preferably have a content of NCO groups of about 10 to 55% based on the weight of the polyisocyanates Especially preferred are polyisocyanates with an NCO group content of 24 to 36, in particular 28 to 32 wt.%.

A further optional component in the manufacture of the substances according to the invention is a catalyst which has the capacity to catalyse the trimerisation of the polyisocyanate.components. Trimerisation catalysts known from polyurethane chemistry are Ssuitable which are preferably tertiary amines and amino-alcohols. Special examples for suitable trimerisation catalysts are 2,4,6-tris (dimethyl- aminomethly)-phenol as well as other mannich base products having the element of structure.

t a.i. in which R signifies a residue, n has a value of I to 3 and the residues R are located in the o or the p position. The residues R 4 and R 2 can be the same or different and signify, C .4 alkyl residues preferably methly groups or C, 4 hydroxy-alkly residues, preferably hydroxy-methly groups.

Mixtures of the above named catalysts can of course also be employed. Additional suitable catalysts are catalysts chosen from methyl-diethanolamine, N-methly-dipropyldiamine, N-butyl-aminoethanol, dimethyl-amino-2-propanol, diethyl-aminoethozy ethanol and o-tolyl-propanolamine. Further suitable catalysts include 1.4-diaza bicyclo-octane.

iT R BCO, also described as triethylenediamine), N,N'-Bis-dimethyl-diethyl-piperazine, (T he methyl-triethylene-tetramine, dimethyl-benzyl-amine, dimethyl-accetylamine.

WO 99/01492 T^^ff JA« AAT WO 99/0/1492 9 rL- I/AiffDa/UIYU 1.8-diazo-bicyclo[5,4,0] undecen tetramethyl-1.3-butane-diamine.

Preferably how ever, one employs the catalysts having the tertiary amine groups, preferably the compounds mentioned above 2,4,6-tris(dimethyl-amino-methyl)phenol or dimethyl-benz\l-amine.The Mol ratio of catalyst to NCO groups in the reaction mixture is important for the manufacture of the substances according to the invention and must be adjusted taking :!ccount of the following points of view.

a) The quantity of catalyst must be sufficient in order to catalyse the reaction which is necessary Ior building up the organic framework.

b) The quanill of catalyst muist not be so great that an uncontrolled strongly exothermic reaction is set off. because with lle heavy evolution of CO, and without the evapot ation of water this would lead to foaming of the reaction mixture and to products h:iving insufficient strength.

For the usual piferred composition according to the invention and the quantity of waterglass solution used. the relationship of catalyst to NCO group in the reaction mixture amounts to 6.0 to 14.5. preferably 8.5 to 13.8 and in particular 10.2 to 13.3 mMol of catalyst per Mol of NCO group.

A co-catalyst may be employed in order further to control the ?trimerisation? reaction.

This may consist for example of a trivalent iron compound such as FeCI, which, because of production requirements, is frequently to be found in the various commercial polyisocyanates. Of course the other co-catalysts which are known as such may also be used for example trialkyl-phosphanes, such as trimethyl-phospholine, the alkali metal salts of carbonic acids such as sodium acetate or sodium maleate or metal decomposition compounds such as SbO 3 ZrOC 2 l, SbCI 2 or CuCI. Furthermore in addition one may use organo-metal compounds such as for example dibutyl-tin-dilaurate, dibutyl-tin diacetate, tin-2-octoate, dibutyl-tin-dioctoate and di-n-butyl-tin-carboxylate.

Substances having particularly advantageous physical properties are obtained according to the invention if polyisocyanate and water-glass are employed in such amounts and having such compositions, that the preferred relationship which has been explained is formed between the quantity of catalyst to NCO groups, together with the preferred relationship between NCO/SiO 2 which has also been explained and in addition that the catalyst is present in such an amount that the quantity of C02 which is developed is just sufficient for the complete precipitation of the Me2O portion of the water-glass.

The preferred conditions for the manufacture of the substances are a quantity of catalyst of preferably 6.0 to 14.5, more preferably 8.5 to 13.8 and in particular 10.2 to 13.3 mMol per Mol NCO groups, the employment of the polyisocyanate and of the alkali silicate solution in a Mol relationship ofNCO/SiO 2 of 0.8 to 1.4, preferably 0.85 to 1.15, a Mol quantity of reaction masses all compounds which exhibit the groups -OH, -NH 2 -NRH and/or 1H20) of preferably 2.0 to 4.0, more preferably 2.5 to 3.8 but also 2.9 to 3.8, a Mol WO 99/01492 IirlCPnO /G nm WO 99/1492 0-0r ITD/l 0 -10- 1/U70U17U relationship of amino groups of for example poly-oxy-alkylene-amine to an alkali oxide Me 2 O of 0.01 to 1, preferably 0.01 to 0.4, but also 0.01 to 0.3 and/or 0.2 to 0.4, an index defined as Index 100 NCO/OH, in the range of 10 to 30, preferably 11 to 25, but also to 20'or 14 to 22, a portion of-NCO (absolute) in the range of 0.1 to 2.0 preferably 0.3 to 1.0 Mol. more preferably 0.4 to 0.7 Mol but also 0.1 to 0.7 Mol, as well as 0.6 to 1.8 Mol. a portion of an alkali oxide Me:O (whereby apart from Na and K, Me may also comprise Li. C; alnd Rb). in the range 0.01 to 2, preferably 0.05 to 0.2 but also 0.01 to 0.1 or 0.2 to 0.5 of 0:1 to I. a portion of amine from polyamine (absolute) of 0.001 to 0.1, preferably 0.00 to 0.05. but also 0.001 to 0.02 or 0.01 to 0.08 Mol, a Mol relationship NCO to MeO in the range I to 15. preferably 2 to 9 but also I to 6 or 5 to 12 and a Mol relationship of-NCO to amine of 5 to 500. especially 10 to 300. but also 11 to 80 or 100 lo 400.

The \\ater-glass shall exhibit the normal preferred composition i.e. a Mol relationship Si()OMeO() as has previously been defined.

For the decomposition of the polycyanate and the water-glass solution, the uniform distribution of the catalyst in the reaction mixture is desirable for the manufacture of high grade substances according to the invention. The catalyst is most usefully added to the water-glass solution.

Fundamentally. the addition of a blowing agent to the reaction mixture is not necessary, for the manufacture of the preferred substances of the invention. However, according to the exact recipe formulation and the other reaction conditions an exactly metered small quantity of a blowing agent may be added which however is not sufficient to cause the expansion of the product during polymerisation.

Volatile substances which are liquid at room temperature are suitable for this purpose; they volatilise during the decomposition of the water-glass with the polycyanate as the result of the heat which is then liberated. Examples of suitable volatile substances are the known FCKW free blowing agents that is not halogenated blowing agents which dam'age the ozone layer The added quantity of volatile substance amounts preferably to a maximum of 3.5 wt.% based on the total quantity of the reaction mixture. Preferred particularly is a content in the reaction mixture of 1 to 2.8 wt.% of volatile material. Such a small addition does not cause any expansion (foaming) of the product during decomposition. Rather, the volatile material escapes from the reaction mixture almost completely during the beginning phase of the decomposition and as a result leaves behind individual cavities and channels which remain in the reaction mixture and which can absorb alkali carbonate solution. This mechanism contributes to the mechanical strength of the resulting product.

Nucleus formers and stabilising materials can also be added to the reaction mixture.

Suitable materials which form nuclei for example are finely divided solids such as silica and alumina if necessary together with zinc stearate or amorphous silica or metal silicates.

WO 99/01492 PC'T/IGB/l 97 -11- Of these the silica which is precipitated from the colloidal water-glass solution is preferred as a nucleus former.

Suitable stabilisers are silicone oils based on polysiloxanes. They may be added in an amount of about 0.5 to 2. especially 0.8 to 1.4 wt.% based on the total weight of the reaction mixturc.

According t to li desired properties of the organo-mineral systems. yet further additions may be incorpoi :ted into the reaction mixture. For example organic compounds belong to these which posess residues capable of reacting with respect to the isocyanate groups.

lxamples are lolyoles such as polyester and polyether-polyoles as well as phosphonate esters. e.g. Ili-1--chlorethyl- or -isopropyl-phosphonate. which are known in polyurethane cheiistiy. The quantity of the polvoles should be limited so that their addition does not interfere \\ith the formation of a three dimensional organic frame work and the inorganic framework \\lich is interwoveni therewith. Advantageously the addition of polyole or phosphonat-esier is limited to at most 2 to 45, preferably 10 to 20 wt.% based on the isocyanate component.

To reduce the inflammability of the organo-mineral products of the invention, flame inhibiting materials may be added to the reaction mixture. Suitable for this purpose are those flame inhibiting or flame retarding materials such as phosphates and borates which are known from the chemistry of synthetic resins. The quantity of flame inhibiting materials can lie in the range of 2 to 30 based on the isocyanate components.

Preferred flame inhibiting means are halogenated phosphoric acid esters. Especially preferred is a trichlor-propyl-phosphate.

Other additioning and filler materials may be added to the reaction mixture, which have a further effect on strengthening the product. Examples for such fillers are diatomaceous earth, aluminium oxy-hydrate, magnesium silicate, chalk and glass fibres. The quantity of added fillers is determined first of all by the viscosity of the mixture. The quantity lies preferably within the range of 0.1 to 30 wt.% based on the weight of the water-glass solution which has been employed.

To manufacture the substances according to the invention preferably two components A and B are produced first of all. Component A comprises the water-glass solution and contains in addition the compound with the terminal amino groups, as well as the catalyst and, if appropriate a compound which contains the catalyst in a dispersed form.

Component B comprises the polyisocyanate or pre-adduct and/or prepolymerisate and contains if appropriate the cokatalysator as well as if appropriate the volatile material and the stabiliser as well as flame inhibiting additions. Fillers and colouring agents may be employed in an\ desired manner just as well in component A as in component B.

To manufacture the substances according to the invention components A and B are carefully mixed together. Preferably this takes place with a two component mixing device, with which subsequently the resulting mixture can be filled into the cavities which have WO 99/01492 PCT/GB98/01907 -12been provided. In general the setting time of the mixture which is obtained lies between and more than 100 seconds and may be controlled according to wish. If appropriate, the components or the mixture may be warmed or cooled in order to make the setting time fit the requirements.

As has been mentioned in the above, first of all a gel-like product is obtained which hardens after 2 minutes.

The decomposllmon of the mixture starts with the reaction of the NCO groups with the water of the ater-glass solution and with the amino groups of the compound containing the terminal anino groups. An organo-mineral system and gaseous CO: result thereby. The translormation i-s exothermic. The liberated heat leads on the one hand to the volatilisation of the volatile material and on the other hand to the ?trimerisalion? of residual NCO groups under thc effect of the catalyst. The liberated CO, in its turn reacts with the MeO of the water-gl:ss to form alkali metal carbonate. As a result the Me 2 O component is extracted from tihe water-glass. During the course of the decomposition, the remaining silica components form a three dimensional inorganic framework which combines with the organic polymci ide. which is formed at the same tome. to produce a mutually penetrating netork of grea strength. The residual alkali carbonate solution in the channels left by the evaporated volatile material contributes to increasing the strength.

Because of their outstanding properties especially because of their high strength, elastic and fire resistant properties and because of their quasi thixotropic properties during processing, the substances according to the invention are outstandingly suited for filling in bore holes, especially when working overhead, as well as for fixing anchors.

The examples \\ill illustrate the invention.

Example 1 A reaction component A is produced which contains the following materials with the amounts reported in wt.%: Sodium Water-glass 48/50 88.7 Water 4.3 2.4,6-Tris-(dimethyl-amino-methyl)-phenol Jelfamine T-403 Separately therefrom reaction component B is produced with the following constituents: WOl 99/014927 1DC'TM'dDflQ IA Il'? 1~ C rude MDI NCO 3 250 mPas 98 Poilyether-siloxane-block co-polymer 2 The relationship of grams A component to gramns B component is 100 87.

lDurine, the inixin of the two reaction components, the substance reacts spontaneously and is transformed il once into a gel-like quasi thixotropic condition. The substance remains mouldable for tip to 3 miinutes. It is possible to spray this suibstance overhead N-Vithout it i'allinu, down. It *V thuLS suitable for filling in bore holes and for the agglutination of anchors.

Alkera:botit 5 to 10 minuites a solid material arises.

EBanpk 2 TFhe saine procedur-e is followed as in example Iwith the difference that instead of .lelhmie *V403the samec quan1titYV of.leffaniine T-5000 is used.

A suibstance ha\ ing similar processing properties and similar finished product properties as in examiple I is btamned.

Example 3 The same proccdure is followed as in example 2 with the difference that instead of Jeffamine T-50(10 the same quantity of Jeffamine D-2000 is used. Apart from this 0.3 parts by w\eight 4 diniethv'l-benzy'l-anmine are added additionally as catalyst A substance ha\ ing similar processing properties and similar finished product properties as in example 2 is obtained.

Example 4 The same procedure as was followed in example 3 is repeated with the difference that in place of .Jeffamine D-2000, secondary poly-oxy-alkylene amine having a molecular weight of 6000 is employ'ed A substance ha\ ing similar processing properties and similar finished product properties is obtained.

Example Example I is repeated with the difference that the following B component is employed: WCl OQ/01AoQ -14- rLIIL/YI/UIYU7 Crude MDI NCO 31% 250 mPas 40.3 modified crude MDI NCO 30%, 170 mPas 40.3 poly-ether-siloxane-block co-polymer 1.7 pol-y-ether-diole OHZ 56 17.7 To 100 g A component are added 79 g B component.

The substance exhibits similar processing properties as in example I and similar properties for the finished product.

Example 6 Example 2 is repeated \ilhl the difTerence that as the B component the B component described in example 5 and the relationship of component A to component B which is also described there ts employed.

A substance ha\iing similar processing properties and similar properties for the finished product is obtained.

Example 7 Example 3 is repeated with the difference that as the B component the B component described in example 5 is used and the relationship of component A to component B which is also described there is employed.

A substance having similar processing properties and similar properties for the finished product as in example 3 is obtained.

Example 8 Example 4 is repeated with the difference that as the B component the B component described in example 5 is used and the relationship of component A to component B which is also described there is employed.

A substance having similar processing properties and similar properties for the finished product as in example 4 is obtained.

Example 9 A reaction component A is produced which contains the following materials with the amounts reported in wt.%: Potassium Water-glass 28/30 88.7 Water 4.3 Di methyl-benzyl-amine 0.3 WOl 99/0l1492r'~'non -15- lr. It 2.-4 6-Tn s-(diiniethvl-amiino-miethiyl)-phenol Jelfamine T-403 Separately ther l'in reaction component B Is produced with the followingy constituents: Crude MI)I NCO 31Po- 250 milas 98 R dv\-ethier-siloxanie-blo-ck co-polymer 2 The relationship tofgrams A component to 2rams B component Is 100 :87.

Astibstance Iiavin! similar processing properties and similar properties for the finished product as has beeni previously described is obtained.

Example Example 9 is iepeated "ith the difference that as component B the composition of comnponent 13 fr 'an example 5 is used and the corresponding relationship of A component to 13 componenti is employed.

A substance having similar processing- properties and similar properties for the finished product as has previously been described, is obtained.

Example 11 A reaction comiponent A is produced wvhich contains the following materials with the amounts reported in wt.%: Sodiumn Water-glass 88.7 Water 4.3 Dii methyl-benzyl-amine 0.3 2.4 .6-Tris-(dimethiyl-aniiino-methiyl)-phenol .1e ffarnine T-403 Separately therefrom reaction component B is produced with the following constituents: C rude MDI NCO 31%. 250 mPas 98 P 'lyether-siloxane-block co-polymer 2 The relationship of grains A component to grams B com ponent is 100 87 WA QQIA1AQt A substance having similar processing properties and similar properties for the finished product as has been previously described is obtained.

Example 12 Example I I is iepeated with thle difference that to component B additionaIl' 10 parts by NveIL-ht of Ir-ichh'r~-proLpvl-pliospliate -ire added.

A substance ha\Ing, similar processiig properties and similar properties for the finished product as has been previouisly. described is obtained.

Example 13 Ex-ample I I is icpieamed Ith the difference that the follow~ing composition is employed as conlipomieni 13; Crude MI~l NCO 3 10o. 250 tnPas 40.3 modified cnide MDI NCO 30% O. 170 niPas 40.3 1I ilyd-ether-slioxane-block co-polymecr 1.7 propyleile carbonate P, lv-ether-diole 0HZ 56 17.7 The relationship of grains A component to grams B component is 100 8 7.

A substance ia~ \Ing similar processing properties and similar proper-ties for the finished product as has been previously described is obtained.

Example 14 A reaction component A is produced which contains the following materials with the amiounts reported in S&)diuni Water-glass 48/50 88.7 Water 4.3 2.4,6-Tris-(dimethyl-amino-methyl)-phenoI Diethylene-triamnine Separately therefrom reaction component B is produced with the following constituents: Crude MDI NCO 31%. 250 mPas 98 P4 Iyet her-siloxkane-block co-polynier 2 P:\OPERa\MWll2247184 spcidoc-20/11/01 -17- The relationship of grams A component to grams B component amounts to 100:87 Comparative Example 1 A reaction component A is produced which contains the following materials with the amounts reported in wt. Sodium Water-glass 48/50 88.7 Water 4.3 Dimethyl-benzyl-amine 0.3 2,4,6-Tris-(dimethyl-amino-methyl)-phenol 03 Separately therefrom as the B component the B component described for example 5 is produced.

So For 100g of component A 79g of component B were employed.

The substance hardened so quickly that the insertion of anchors after 1 to 3 minutes is no S: longer possible in contrast to the examples according to the invention.

The reference to any prior art in this specification is not, and should not be taken as, an 15 acknowledgement or any form of suggestion that that prior art forms part of the common general knowledge in Australia.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

Claims

1. A method for the manufacture of elastic, fire resistant organo-mineral systems based on waterglass which method comprises: providing component A which comprises waterglass and a compound containing terminal amino groups which compound has at least one free hydrogen atom on at least one amino group and at least one alkylene group interrupted by one oxygen, nitrogen and/or sulphur atom and component B which comprises a polyisocyanate or a polyisocyanate prepolymer and mixing component A with component B and allowing the mixture to react.

2. A method according to claim 1 wherein the ratio by weight of component A to component B is from 1:2 to 2:1

3. A method according to claim 1 or claim 2 wherein the compound having terminal amino groups is a polyoxyalkylene amine or a mixture of different polyoxyalkylene Samines. compounds having the formula: H 2 NCHCH 2 [OCH 2 CH] -NHI II S. CH 3 CH, S(OCH 2 CH x-NH2 **CH Z (OCH 2 H) Y-NH2 CH 3 (OCH 2 CH) z-NH2 CH HNCHCH, [OCHCH 2 a [OCHCH 2 b- [OCH 2 CH] -NHI (I) CH, I H CH CH 3 CH 3 C 3 -19- O II H,NCHCH,- [OCHCH] n-NH-C-NH- [CHCHO] CH 2 CHNH 2 (IV) I I I I CH 3 CH3 CH 3 CH, O O HN-C-NHCHCHr- [OCH 2 CH] n-NH-C-NH 2 CH 3 CH3 R- (CH 2 CHO) n-CHICHNH 2 I I (VI) R CH 3 in which R signifies CH 2 0CH 2 CH20, R' signifies hydrogen or an alkyl residue with 1 to 4 carbon atoms, A signifies the residue of a trivalent alcohol, preferably trimethylol propane or glycerine, x' signifies a number from 2 to 20, b signifies a number from to 160, the sum of a+c represents a value from 2 to 4, n represents a value of from 4 to 80, x, y or z represents a value of from 1 to 100 or mixtures thereof. g A method according to claim 1 or 2 wherein the compound having terminal amino groups is a polyalkylene polyamine.

6. A method according to any one of claims 1 to 5 wherein the compound having terminal amino groups has a molecular mass of from 800 to 10,000g/Mol.

7. A method according to any one of claims 1 to 5 wherein the ratio of NCO/OH is less than 2.

8. A method according to any one of the preceding claims wherein component A is mixed with component B in the presence of a trimerisation catalyst for the ~ZLIsaolyisocyanate.

9. A method according to claim 8 wherein the trimerisation catalyst is dispersed in component A. A method according to claim 8 or 9 wherein a mixture of two or more trimerisation catalysts is present.

11. A method according to any one of claims 8 to 10 wherein the quantity of catalyst is sufficient to catalyse the reaction to build up an organic framework but not so great that foaming of the reaction mixture is caused to occur.

12. A method according to any one of claims 8 to 11 wherein the trimerization catalyst is a tertiary amine or aminoalcohol.

13. A method as claimed in claim 13 wherein the catalyst is 2,4,6- tris(dimethylaminomethyl)phenol.

14. Organo-mineral systems produced by a method according to any one of the I* preceding claims. A method according to claim 1 substantially as hereinbefore described with reference to the examples. DATED this 30th day of November, 2001 Fosroc International Limited by DAVIES COLLISON CAVE Patent Attorneys for the Applicant c -7 1-