GB2088394A - Material for Making Walls - Google Patents

Abstract

A material having good resistance to mechanical stresses and heat, and in particular having substantial resistance to the penetration of a directed flame such as the pointed flame of a blowpipe, comprises per 100 pbw of material, 30 to 70 pbw of a polymerizable substance such as a polyurethane, 10 to 60 pbw of divided sulphur, and various optional ingredients, viz. halogenated compounds, phosphorus-bearing compounds, phosphohalogenated compounds, trivalent antimony oxide, solid or liquid fillers and pigments. The material may be used for the production of strong walls, in particular by filling internal cavities of armoured doors, walls of strong rooms or safes.

Description

SPECIFICATION Material for Making Walls The invention concerns materials that can be used for the formation of strong walls, in particular by filling internal cavities of armoured doors, walls of strong rooms or safes.

It is known that doors or walls of strong-rooms or safes can be reinforced by means of armoured plates made of an elastomeric material. Such plates do not intimately adhere to the door or wall and do not provide sufficient resistance to burglary.

The present invention provides a material having good resistance to mechanical stressses and to heat, in particular having substantial resistance to the penetration of a directed flame such as the pointed flame of a blowpipe, comprising, per 100 parts by weight of the material, from 30 to 70 parts by weight of a polymerizable substance such as a cast resin or a thermosetting resin; from 10 to 60 parts by weight (preferably from 20 to 30 parts by weight) of divided sulphur; from 0 to 15 parts by weight (preferably from 5 to 10 parts by weight) of halogenated compounds, phosphorus-bearing compounds and/or phosphohalogenated compounds; from 0 to 5 parts by weight of trivalent antimony oxide, and from 0 to 50 parts by weight (preferably from 5 to 25 parts by weight) of solid powdery fillers and/or liquid fillers and/or pigments.

Material in accordance with the present invention can have good resistance to house-breakers, burgiars and other miscreants. The polymerizable substance can be constituted by one component or it can be formed from two or more components; the substance is preferably a polyurethane, which is produced by the reaction of one or more organic poiyisocyanates with one or more compounds containing from 3 to 8 atoms of labile hydrogen per molecule, the mean equivalent weight of which is from 100 to 400 and preferably from 200 to 300, such compounds being reacted with the polyisocyanates in amounts such that the isocyanate number is from 1 to 1.5.

The compounds containing from 3 to 8 labile hydrogen atoms per molecule are preferably polyetherpolyols, which are prepared in known manner by the polyaddition of propylene oxide and possibly ethylene oxide on compounds such as polyols, glucosides, alkanolamines or polyamines, such compounds having from 3 to 8 hydrogen atoms capable of reacting with the alkylene oxides. The polyaddition is most frequently performed in the presence of an alkaline compound such as potassium hydroxide until the required amount of the alkylene oxide or oxides has reacted. The alkaline compound is then removed, for example by neutralisation with acid and then filtration of the salt formed.When the polyetherpolyols are prepared from ethylene oxide and propylene oxide, such alkylene oxides may be fixed separately or in admixture on the compounds having the labile hydrogen atoms, or by alternating the two fixing methods referred to above.

The compounds containing from 3 to 8 labile hydrogen atoms per molecule may also comprise a mixture of polyether-polyols as defined above with amino compounds such as diethanolamine, ethylenediamine, diethylenetriamlne, tolylenediamines and diphenylmethanediamines.

The organic polyisocyanates are preferably aromatic polyisocyanates, such as tolylene diisocyanate, which is generally referred to as 'TDI', or 4,4'-diphenyimethane diisocyanate, which is generally referred to as 'MDI'. The organic polyisocyanates may also comprise crude TDI, which is produced by the reaction of phosgene on a crude tolylenediamine containing various condensed amines and isomers, or crude MDI, which results from the condensation of phosgene on the unpurified product of the reaction between aniline and formaldehyde.Such polyisocyanates may be used directly or in the form of prepolymers produced by the reaction of the organic polyisocyanates described hereinbefore, with, in an amount of from 30 to 70% of the stoichiometric amount, one or more compounds containing from 2 to 8 atoms of labile hydrogen per molecule, for example tripropyleneglycol, polyoxypropylene triols with an equivalent weight of 1000, or products of the polyaddition of propylene oxide on sorbitol having an equivalent weight of 240.

The mean equivalent weight of a compound comprising labiie hydrogen atoms corresponds to the ratio of its mean molecular weight to the mean number of labile hydrogen atoms in its molecule.

The isocyanate number as referred to hereinbefore is equal to the ratio of the number of isocyanate groups of the organic polyisocyanates to the number of labile hydrogen atoms of the compounds containing from 3 to 8 of them per molecule.

The halogenated compounds capable of being included in the materials of the invention may be for example chlorinated paraffins, chlorinated diphenyl or dibrnmoprnpanol. The phosphorus-bearing compounds may comprise for example triammonium phosphate, triphenyl phosphate or triphenyl phosphite. Such phosphorus-bearing compounds may also include phosphorus-bearing polyols, which are produced for example by the polyaddition of propylene oxide and, if appropriate, ethylene oxide on an ester of phosphoric acid, a polyphosphoric acid or a nitrogen derivative of phosphoric acid such as phosphoramide; the phosphorus-bearing polyols react with the organic polyisocyanates and are therefore capable of totally or partially replacing the compounds containing from 3 to 8 labile hydrogen atoms per molecule.The phosphohalogenated compounds may for example be trichloroethyl phosphate, trichloropropyl phosphate or tribromopropyl phosphate. The halogenated phosphorusbearing or phosphohalogenated compounds provide the materials according to the invention with increased resistance to penetration by the flame of a blowpipe because they repeatedly cause extinction of the blowpipe flame.

It is advantageous, particularly when the materials of the invention contain halogenated or phosphohalogenated compounds, for trivalent antimony oxide also to be included. The effect of this additive is to increase the resistance of the materials to heat.

Among the solid powdery fillers that are suitable for use in the materials of the invention, chalk powder, kaolin, silica and barium sulphate are particularly suitable. The liquid fillers may comprise esters such as dioctyl phthalate or heavy petroleum oils such as the 'aromatic extracts' sold for example by Societe Francaise des Petroles BP under the trade mark IRANOLIN. The pigments may comprise for example carbon black or yellow or red iron oxides.

The materials of the invention are prepared by casting, in a mould or in the internal cavities of the members to be protected, a liquid produced by mixing the constituents thereof before reaction between the component or components of the substance which can be polymerized, such as the organic polyisocyanates and the hydroxyl compounds, has resulted in the formation of a solid material.

When the polymerizable substance is a polyurethane, the material can favourably be prepared by first mixing all the constituents of the material, except for the organic polyisocyanates. The sulphur is advantageously used in the form of powdered sulphur such as flowers of sulphur, intimately mixed with the hydroxyl compounds. It is also possible for the sulphur to be used in liquid form and for it to be mixed with the hydroxyl compounds, or for sulphur in piece form to be melted at about 1 200C in the hydroxyl compounds and to be mixed with them.

The other constituents, except for the organic polyisocyanates, are also mixed with the hydroxyl compounds at a temperature of from 10 to 1300C; it is preferable for the mixing operation to be performed at a temperature of at least 700 C, under sub-atmospheric pressure, in order to cause the elimination of water that may be contained in the constituents. The remaining traces of water can be removed by the addition of a dehydrating agent such as dehydrating molecular sieve or a hydrolysable compound such as titanium tetrachloride or aluminium trichloride; the amount of dehydrating agent to be used may be calculated in known manner from measurements of the amount of water to be removed.

The resulting composition is cooled if necessary and then mixed with the polyisocyanates at a temperature of from 10 to 800 C; the resulting mixture is then cast in the mould or in the internal cavities of the strong walls, where it hardens by reaction between the hydroxyl compounds and the organic polyisocyanates; In order to reduce the duration of the reaction, it is possible for one or more catalysts that promote the reaction between the polyisocyanates and the hydroxyl compounds, such as organic compounds of tin, in particular stannous octoate or dibutyl-tin dilaurate, or amino catalysts, to be added to the mixture.

In an alternative form, the material of the invention may be used in the form of a concrete produced by using the mixture of the constituents, as described above, for encasing solid bodies of dimensions of from 0.5 to 20 mm, in a proportion which can reach 85% by weight with respect to the whole. Such solid bodies may comprise sand, gravel, small balls of vermiculite, mica or glass, or crushed plastics material waste or rubber waste. The concretes may be prepared before casting.

Alternatively, they may be produced by casting the mixture of the constituents other than the solid bodies in moulds or cavities of fire-arresting walls that have previously been filled with the solid bodies.

The materials of the invention can be particularly advantageous for the production of strong walls which are required to resist burglary. Indeed, they provide good resistance to penetration by a blowpipe flame, in particular when they contain halogenated, phosphorus-bearing and/or phosphohalogenated compounds, which cause the blowpipe to be repeatedly extinguished and which emit gas and/or fumes, which considerably hinder the operator. Particularly when they contain polyurethanes, these materials also have good mechanical properties, in particular surface hardness of at least 70 Shore A and a modulus of elasticity under tension of at least 100 daN/cm2, and good adhesion properties, which make it difficult to pierce them, cut them or pull them out.

Comparative Example C1 4500 g of a product of polyaddition of propylene oxide on glycerol with an equivalent weight of 280 and 5300 g of chalk in the form of fine powder are introduced into a 10 litre stainless steel reaction vessel provided with a mechanical agitator of the screw type and a double-jacket heating and cooling device. The constituents are mixed and the mixture is raised under vacuum to a temperature of 900C for a period of 1 hour 30 minutes, the residual pressure being 100 millibars. 200 g of powdered molecular sieve of quality 4 Angstroms and 1 g of dibutyl-tin dilaurate are then added.

The mixture is cooled to a temperature of 250C and 2800 g of crude MDI containing 31 weight percent of isocyanate groups is added. the isocyanate number is: 0.31 x2 800x280 =1.28 42x4 500 The mixture is then moulded in an open mould having a section of 15 cmx 5 cm and a height of 2.5 cm.

After being hardened for 10 days at a temperature of 250C, the sample is subjected to the tests set out below.

Comparative Example C2 The same constituents are used as in Comparative Example Cl, except that 1000 g of chalk is replaced by flowers of sulphur and, in some cases, by chlorinated or phosphochlorinated compounds, the nature and the quantities of which are set forth in Table I.

Examples 1 to 5 The same constituents as in Comparative Example C1 are used, except that the chalk is partially replaced by flowers or sulphur and, in some cases, by chlorinated or phosphochlorinated compounds, the nature and the quantities of which are set forth in able After hardening for 10 days at a temperature of 250 C, the samples are subjected to the test described hereinbelow.

Tests The samples are placed on a surface measuring 15 cmx2.5 cm, the surface which measures 15 cmxl 5 cm being disposed vertically. The centre of the vertical face is attacked by means of an oxyacetylene blowpipe, the flame of which is placed perpendicularly to the sample and at a distance of 5 mm from it. Measurements are taken in respect of the speed of penetration of the flame, the loss in weight of the sample per minute and the frequency at which the blowpipe is extinguished (number of extinctions of the blowpipe divided by the total duration of the test).

The results, which are set out in Table I, show that the sulphur considerably reduced the speed of penetration of the flame; in addition, the sample of Example 2, which contains about 30% of sulphur by weight, resulted in fouling or clogging of the blowpipe and termination of the test. The presence of chlorinated compounds, in particular trichloropropylphosphate, caused the blowpipe to be repeatedly extinguished, so that it had to be re-lit.

Table I Number Chlorin- of exated Speed of tinctions paraffin Trichloro- penetration of the with 50% propyl- of the Loss in blowpipe Duration Chalk Sulphur of Cl phosphate flame weight during of the test Example (g) (g) (g) (g) (mm/min) (g/min) the test (min) Remarks about the opening C1 5300 0 0 0 16 8 0 1 min 30 s Large conical hole C2 4300 0 1000 0 6 6 1 4 min 15 s Large conical hole 1 3800 1500 0 0 4 6.5 0 6 Medium hole, charry 2 2300 3000 0 0 2.2 2 0 11 min 30 s Small hole, charry 3 800 4500 0 0 0.8 1.2 2 25 The burnt depth is only 20 mm after 25 minutes 4 1300 3000 1000 0 1.6 2 4 16 Small charry hole 5 1300 3000 0 1000 1.3 2.2 8 15 The burnt depth is only 20 mm after 15 minutes

Claims (12)

Claims

1. Material having good resistance to mechanical stresses and to heat comprising, per 100 parts by weight of the material, from 30 to 70 parts by weight of a polymerizable substance; from 10 to 60 parts by weight of divided sulphur; from 0 to 1 5 parts by weight of one or more halogenated compounds, phosphorus-bearing compounds and/or phosphohalogenated compounds; from 0 to 5 parts by weight of trivalent antimony oxide; and from 0 to 50 parts by weight of one or more solid powdered fillers and/or liquid fillers and/or pigments.

2. Material as claimed in claim 1, containing 20 to 30 parts by weight of sulphur, 5 to 10 parts by weight of one or more halogenated compounds, phosphorus-bearing compounds and/or phosphohalogenated compounds; and 5 to 25 parts by weight of one or more solid powdered fillers and/or liquid fillers and/or pigments.

3. Material as claimed in claim 1 or 2, in which the polymerizable substance is a cast resin or thermosetting polymer.

4. A material as claimed in claim 1 or 2, in which the polymerizable substance is a polyurethane produced by the reaction of one or more organic polyisocyanates with one or more compounds containing from 3 to 8 atoms of labile hydrogen per molecule, the mean equivalent weight of which is from 100 to 400, such compounds being reacted with the polyisocyanates in amounts such that the isocyanate number is from 1 to 1.5.

5. Material as claimed in claim 4 in which the mean equivalent weight of the compound(s) containing labile hydrogen atoms is from 200 to 300.

6. A material as claimed in claim 2, 4 or 5, in which the compounds containing labile hydrogen atoms are polyether-polyols resulting from the addition of propylene oxide and possibly ethylene oxide on polyols, glucosides, alkanolamines or polyamines having from 3 to 8 hydrogen atoms capable of reacting with the alkylene oxides.

7. A process for the production of the material set forth in any one of claims 4 to 6, comprising mixing, at a temperature in the range 10 to 1 300C, all the constituents of the material except for the organic polyisocyanates and then, if necessary after removing water and cooling the resulting composition, mixing the latter at a temperature in the range 10 to 800C with the organic polyisocyanates, if appropriate in the presence of one or more catalysts that promote the reaction between the polyisocyanates and the hydroxyl compounds.

8. A process as claimed in claim 7 in which the sulphur is in the form of flowers of sulphur.

9. A process as claimed in claim 7, substantially as hereinbefore described in any one of Examples 1 to 5.

10. A material as claimed in claim 4 obtained by a process as claimed in claim 7, 8 or 9.

11. Strong walls of the type in armoured doors, walls of strong rooms or safes, containing a material as claimed in any one of claims 1 to 6 and 10, optionally in the form of a concrete that contains 0 to 85% by weight of solid bodies of from 0.5 to 20 mm in size.

12. Walls as claimed in claim 11 in which the mixture of the constituents of the material has been cast in the internal cativies of the walls.