IE43430B1 - Cellular building material - Google Patents

Abstract

1524266 Phenolic resin foam compositions RHONE-POULENC INDUSTRIES 23 Sept 1976 [23 Sept 1975 (2)] 39544/76 Heading C3C A load-bearing, insulating and/or fire-guard building material comprises 10-80% by vol. of expanded inorganic particles of 2-30 mm. diameter and 20-90% by vol. of a phenolic resin foam together with 30-80 parts by wt., 100 parts of foam, of a hydrated or non- hydrated calcium sulphate. The material is made by casting or injecting in a mould containing the inorganic expanded particles a mixture of a 100 parts by wt. phenolic resin having a water content of 10-40% by wt. and a formaldehyde : phenol molar ratio of 1 : 1 to 3 : 1, 5-30 parts by wt. of an acid, 30-80 parts by wt. of the calcium sulphate of a grain size less than 1 mm. and not more than 8 parts by wt. of a blowing agent which is a chlorinated or chlorofluorinated hydrocarbon, an alkali, alkaline earth metal or ammonium sulphide, carbonate or bicarbonate, or a nitrogen compound that evolves nitrogen on heating. The blowing agent may be absent when natural plaster is used as the calcium sulphate since that contains carbonates which liberate CO2 with acids. In the example expanded clay or glass spheres are placed in a heated mould and a mixture of a resin, natural plaster or phosphogypsum, a phenolsulphonic acid and optionally NaHCO3 was injected into the mould to form foams.

Description

The invention is concerned with the manufacture of cellular building materials such as panels, slabs, girders and blocks, and with the materials so produced and building components made from them.

Panels, slabs and blocks in the form of cellular materials made from plastics or resins such as polystyrene or polyurethane are used widely in the building industry.

The above-mentioned cellular materials may be associated with generally inorganic, expanded or non-expanded aggregates so as to give composite materials which have better mechanical properties than ordinary cellular materials.

But even composite cellular products based on the plastics mentioned have a very serious drawback, that is to say, their poor resistance to temperature and fire. These materials are in fact highly combustible, and in addition they give off extremely noxious fumes while burning.

Phenolic resins are known to be far more incombustible than polyurethanes. However, they have inadequate mechanical properties and if they are combined in foam form with expanded aggregates these properties are only very slightly improved because of the baring of the agglomerates.

The present invention is based on the discovery that a light concrete based on phenolic resins, which does not have the defects described above, can be made and in accordance with the present invention there is provided a 3 4 3 0 - 3 load-bearing and/or insulating and/or fire-guard material comprising (by volume) from 10 to 80% of expanded inorganic particles of a diameter ranging from 2 to 30 mm, and 20 to 90% of phenolic resin foam, together with 30 to 80 parts by weight, per 100 parts by weight of the phenolic foam, of a hydrated or non-hydrated form of calcium sulphate.

In a special embodiment of the invention the particles are of expanded clay and in aggregate have a , 2 compressive strength of from 10 to 60 kg/cm .

In another embodiment the particles are beads of expanded glass and in aggregate have a compressive strength 2 of from 4 to 12 kg/cm .

In one form of the invention the material additionally includes powdered and/or fibrous fillers.

Particularly in the case of fibrous fillers, compressive strength is far greater than that of the material without fibres; it is a function of the quantity of fibres.

The material is preferably in the form of slabs, panels or blocks.

The said materials and components made from them are manufactured according to the invention by casting or injecting a composition in a mould containing a suitable quantity of the said expanded inorganic particles and optionally reinforcements, bracings, or stud-bolts, the composition comprising 100 parts by weight of a phenolic resin with a water content of 40 to 10% by weight and with a formaIdehyde:phenol molar ratio in the range 1:1 to 3:1, 5 to 30 parts by weight of an acid, 30 to 80 parts by weight of a hydrated or non-hydrated form of calcium sulphate of a grain size less than 1 mm and preferably less than 100(.1., and not more than 8 parts by 3 4 3 0 - 4 weight of a pore-forming agent that is a chlorinated or chlorofluorinated hydrocarbon, an alkali metal, alkaline-earth metal or ammonium sulphide, carbonate or bicarbonate, or a nitrogen compound that gives off nitrogen when decomposed by heating.

In one embodiment natural plaster is used as the hydrated form of calcium sulphate, and in this case the quantity of pore-forming agent used is preferably nil, because the natural plaster itself contains carbonates which liberate carbon dioxide on treatment with acid.

In another embodiment phosphogypsum (chemical plaster) is used as the hydrated form. In this case 1 to 3 parts by weight of an alkali metal bicarbonate, e.g. sodium bicarbonate, or ammonium bicarbonate is preferably used as the pore-forming agent. In an embodiment for prefabrication in a workshop, the mould and/or the aggregates are heated to temperatures in the range 40 to 1OO°C. In the embodiment in which materials or structures are made with faces, the faces form all or part of the walls of the mould.

In a practical method of carrying out the method of the present invention, one of the raw materials is a resol, which is a product prepared by phenol-formaldehyde condensation in a formaldehyde-phenol molar ratio in the range 1:1 to 3:1 and preferably 1.2:1 to 1.3:1 with a catalyst based on an alkali metal or an alkaline-earth metal, neutralisation with an inorganic or organic acid and dehydration to a water content in the range 40 to 10% by weight. It is also possible to use Novolak-resol mixtures, the Novolak being a condensation product of formaldehyde and phenol with a molar ratio less than 1:1, or a resol-Novolak4 3 4 3 0 - 5 aldehyde mixture, the total molar ratio still being in the range 1:1 to 3:1. The phenolic resin nay be modified by polyvinyl alcohol or its esters, polycaprolactons, epoxy resins, nitrile rubbers or, more simply, by catechu oil or a residue from wood distillation.

The resins marked by the Applicants under the trademarks Ervaphene M5, Ervaphene MIO and Ervaphene M30 were used for the tests described below.

For the manufacture of the resin, it is possible to use substituted phenols such as cresols, xylenols or diphenols, e.g. resorcinol, hydroquinone and bisphenol A, instead of phenol itself, and to use hexamethylene tetramine, acetaldehyde, butyraldehyde, furfuraldehyde or acetone or mixtures thereof, instead of aqueous or polymerized formaldehyde.

The acid hardener-catalyst may be a conventional strong acid such as hydrochloric, sulphuric or phosphoric acid or an aromatic sulphonic acid. It is preferable to use an aromatic sulphonic acid, such as phenol-sulphonic acid, or a condensation product thereof with formaldehyde, the quantity being 5 to 30% by weight relative to the resin.

In a preferred embodiment of the invention, the mineral particles are beads or pieces of expanded material such as glass, coal shales or clay with a diameter from 3 to 30 mm. It is possible, for example, to use the aggregates described in Table 1 below, which are marketed under the trademarks Argi 16 and Expanver. 3 4 3 Ο NAME Nature Apparent specific gravity Compressive strength in kg/cm2 Thermal conductivityin Kcal/m/h°C Wa ter -per meab i 1 ity TABLE I ARGI 16 Expanded clay 0.25 - 0.45 - 200 λ 0.2 - 0.7 not known EXPANVER Expanded glass 0.13 - 0.14 0.04 - 0.05 none Hydrated or non-hydrated form of calcium sulphate refers to well known products which are dehydrated to varying degrees and derived from gypsum, more particularly natural plaster or chemical plaster recovered in the phosphoric acid and fertilizer industry.

The fillers included in the formulation may be powdered fillers such as talc, mica and silica or fibrous fillers such as glass and asbestos fibres.

The following Example illustrates the process of the present invention.

EXAMPLE.

A mould is heated to between 30 and 120°C and aggregates heated to between 40 and 90°C are placed in it.

Thus, the mould and aggregates are heated to 50°C in the case of glass spheres and to 80°C in the case of clay aggregates.

The resin + plaster + catalyst composition and the pore-forming agent are injected, using a Secmer 3-compo20 nent mixer, which is a machine for preparing a very fine emulsion from three components and injecting the emulsion under pressure. 3 4 3 0 The table sets out the results obtained with the given compositions in four typical tests, namely: No 1 expanded clay + resin No. 2 expanded clay + resin + natural plaster No. 3 expanded glass spheres + resin No. 4 expanded glass spheres + resin + natural plaster No. 5 expanded glass spheres + resin + phosphogypsum.

For reasons of simplicity and clear reading only the tests with Ervaphene M5 resin have been recorded, the catalyst used being phenolsulphonic acid in quantities of 12 kg/m1 of material. The quantities indicated are expressed in kg and are the quantities introduced 3 when making 1 m of material. 3 4 3 ί) - 8 X Μ rd Ε Φ ffl φ Ο -Ρ ίθ tn tn β Φ •rd Ρ Ρ tn ro tn ffl rd 0 . 01 tn Φ £2 Ρ •rd φ ρ χ: Γ0 Qj ffl 01 TABLE II 0) ω -Ρ οι tnm <υ c ε Li Φ ϋ Οι 14\ ε -ρ tn ο ω ί XI σ» CO ιη οο ο >1 •Ρ •Ρ 'ύ •Ρ £ X r—i nJ £ Μ C Ο Φ Ρ Φ tn β Ή β Qj p O tn tn tn tn tn Φ xj Φ Φ •P Ai Ai Ai Ai a tn Ql tn -P •P 4J £ β 0) ro X 44 •P O O O O m •P 0 p tn (0 43 00 CM rp k£> 44 £ Φ -P C 3* in CQ CM CM •P Φ (*) £ ε Ρ φ β Ρ xj cn Μ -Ρ Φ Φ Φ η Ρ Μ £ £ Φ 3 Π5 -Ρ Ό Μ Η Id C Φ ffl ffl ίΰ Οι ip P i-4 P 0 01 •P nJ Φ tn nJ Φ tn XJ ε tn Φ P •P A P •P A Qi 3 X •P u 3 01 o 3 01 01 Ul ta o -P ro o •P ra o 0 & O tn o rd i-4 rd rp XJ >i T φ CM ffl 04 ffl Qj ffl tP p tn •P tn flJ (ti Μ β Φ Φ Qj < φ «Ρ I -Ρ Ρ XJ ί) c ί tn Ρ Φ -Ρ ·Ρ Ο tn rd Φ ffl φ β > Φ Ο β tn Φ Α tn = m co 1-4 «-d · Cm rP «xj* Φ U β tn φ λ: tn = α co oo rP rP · kl p M* ffl g P 0 P 44 •Ρ χ: cn •rd cn a e -rd ω φ m φ φ ί Ο Μ Qj tn tn tn tn tn tn Φ ‘P X λ; X X X β P tn •P c o o o o o ip II o oo 00 00 co corQ «Ρ β tn Φ 3 β Λ 01 43 P P •P Φ C Φ U c X •P ra Qj ϋ Ρ ra kO tn U3 tP to tP 01 01 m P •P rd tn Φ -P rp a: Φ A Φ tn Φ X Φ P b Φ P XJ 01 P 01 u a; UJ P XJ •P Φ P 3 tn £ H r> Η O 01 Q) O 01 Φ w Φ o 4-» 43 43 tn -P (4 υ G O rd x; co rd X! O rd XJ cn •P β rd tn ro Φ ffl K rP Qj rP ip Qj m rP Qi rp Φ ϋ Ρ < 13 s X (5 01 G 01 «Ρ G 0] β ϋ 4-» , ,—. 0 rd Λ ϋ ffl ip CM m in — 3 4 3 0 - 9 The compressive strength of tho material according to the invention will be seen to vary with the strength of the aggregate. As to the thermal and insulating properties, these similarly vary according to the nature of the aggregate. Xn cases where the aggregates are contiguous, the mechanical and thermal properties obtained come close to those of the aggregates. Consequently these may be chosen according to the use and required property. Thus spheres of expanded clay with high compressive strength and an average coefficient of insulation will give a material with high compressive strength and an average coefficient of insulation; on the other hand, glass spheres with a high coefficient of insulation and average compressive strength will give a material with average compressive strength and an average coefficient of insulation. By choosing the materials with discernment a whole range of products can be made, and these can be further improved by incorporating fillers,reinforcements and bracing during manufacture.

Another feature of the present invention is that it produces materials which show excellent ageing, that is to say, mechanical and thermal properties which are constant in time and, in particular, no baring of the aggregates.

Finally, the combination of a non-inflammable expanded organic binder, which does not give rise to the emission of fumes or gives off only non-toxic fumes, with inorganic expanded materials produces remarkable fire-resisting properties (fire-break materials). The fire-breaking action lasts 2 or 3 times as long as that of ordinary materials.

Claims (4)

1. A load-bearing and/or insulating and/or fireguard material comprising (by volume) from IO to 80% of expanded inorganic particles of a diameter ranging from 5 2 to 30 mm, and 20 to 90% of phenolic resin foam, together with 30 to 80 parts by weight, per 100 parts by weight of the phenolic foam, of a hydrated or non-hydrated form of calcium sulphate.

2. A material as claimed in Claim 1 in which the 10 particles are of expanded clay and in aggregate have a compressive strength of from 10 to 60 kg/cm .

3. A material as claimed in Claim 1 in which the particles are beads of expanded glass and in aggregate 2 have a compressive strength of from 4 to 12 kg/cm . 15 4. A material as claimed in any preceding claim additionally containing powdered and/or fibrous fillers. 5. A material as claimed in any preceding claim in the form of a slab, panel or block. 6. A method of making building materials as claimed 20 in Claim 1 and components made from such materials, comprising casting or injecting a composition in a mould containing a suitable quantity of the said expanded inorganic particles and optionally reinforcements, bracings or stud-bolts, tho composition comprising 100 parts 25 by weight of a phenolic resin with a water content of 40 to 10% by weight and with a formaldehyde:phenol molar ratio in the range 1:1 to 3:1, 5 to 30 parts by weight of an acid, 30 to 80 parts by weight of a hydrated or nonhydrated form of calcium sulphate of a grain size less 30 than 1 mm and not more than 8 parts by weight of a pore4 3 4 3 0 forming agent that is a chlorinated or chlorofluorinated hydrocarbon, an alkali metal, alkaline-earth metal or ammonium sulphide, carbonate or bicarbonate, or a nitrogen compound that gives off nitrogen when decomposed by heating. 7. A method as claimed in Claim 6 in which the calcium sulphate has a grain size less than 100μ. 8. A modification of a method as claimed in Claim 6 or 7 in which natural plaster is used as the hydrated form of calcium sulphate and no pore-forming agent is used. 9 A method as claimed in Claim 6 or 7 in which phosphogypsum is used as the hydrated form of calcium sulphate and 1 to 3 parts by weight of a bicarbonate is used as the pore-forming agent, 10. A method as claimed in any one of Claims 6 to 9 in which the mould and/or the particles are heated to temperatures in the range 40 to 100°C. 11. A method of making building components, in which a core of a material obtained by a method as claimed in any one of Claims 6 to 10 is associated with a number of facings which form part or all of the walls of the mould. 12. Load-bearing building materials or components that have an insulating and a fire-guard function and are made according to any one of Claims 6 to 11, in which the inorganic particles are of expanded clay and the compres2 sive strength lies in the range 10 to 60 kg/cm . 13. Insulating and fire-guard building materials or components made according to any one of Claims 6 to 11,

4. 3 4 3 0 in which the inorganic particles are beads of expanded glass and the compressive strength lies in the range of 4 to 12 kg/cm 3 .